advances in-polymer-chemistry-and-methods-reported-in-recent-us-patents

ADVANCES IN POLYMERCHEMISTRY AND METHODSREPORTED IN RECENTUS PATENTS

ADVANCES IN POLYMERCHEMISTRY AND METHODS

REPORTED IN RECENTUS PATENTS

THOMAS F. DEROSA

Copyright 2008 by John Wiley & Sons, Inc. All rights reserved

Published by John Wiley & Sons, Inc., Hoboken, New Jersey

Published simultaneously in Canada

No part of this publication may be reproduced, stored in a retrieval system, or transmitted in any form or

by any means, electronic, mechanical, photocopying, recording, scanning, or otherwise, except as

permitted under Section 107 or 108 of the 1976 United States Copyright Act, without either the prior

written permission of the Publisher, or authorization through payment of the appropriate per-copy fee to

the Copyright Clearance Center, Inc., 222 Rosewood Drive, Danvers, MA 01923, (978) 750-8400, fax

(978) 750-4470, or on the web at www.copyright.com. Requests to the Publisher for permission should

be addressed to the Permissions Department, John Wiley & Sons, Inc., 111 River Street, Hoboken, NJ

07030, (201) 748-6011, fax (201) 748-6008, or online at http://www.wiley.com/go/permission.

Limit of Liability/Disclaimer of Warranty: While the publisher and author have used their best efforts in

preparing this book, they make no representations or warranties with respect to the accuracy or

completeness of the contents of this book and specifically disclaim any implied warranties of

merchantability or fitness for a particular purpose. No warranty may be created or extended by sales

representatives or written sales materials. The advice and strategies contained herein may not be

suitable for your situation. You should consult with a professional where appropriate. Neither the

publisher nor author shall be liable for any loss of profit or any other commercial damages, including but

not limited to special, incidental, consequential, or other damages.

For general information on our other products and services or for technical support, please contact our

Customer Care Department within the United States at (800) 762-2974, outside the United States at

(317) 572-3993 or fax (317) 572-4002.

Wiley also publishes its books in a variety of electronic formats. Some content that appears in print

may not be available in electronic formats. For more information about Wiley products, visit our web

site at www.wiley.com.

Library of Congress Cataloging-in-Publication Data

DeRosa, Thomas F.

Advances in polymer chemistry and methods reported in recent US patents / Thomas F. DeRosa.

p. cm.

Includes index.

ISBN 978-0-470-31286-5 (cloth)

1. Polymers. 2. Polymerization. I. Title.

QD381.D47 2009

668.9–dc22

2008009439

Printed in the United States of America

10 9 8 7 6 5 4 3 2 1

Dedicated in Loving Memory to My Father,

John G. DeRosa

November 27, 1921 – January 6, 1980

CONTENTS

Preface ................................................................................................ xix

I. ADDITIVES

Controlled Radical Acrylic Copolymer Thickeners ............................... 1Polymer-Filler Coupling Additives ..................................................... 5

II. ADHESIVES

(Meth)acrylate Block Copolymer Pressure Sensitive Adhesives ............. 11Absorbable a-Cyanoacrylate Compositions ......................................... 15Use of Polybenzoxazoles (PBOS) for Adhesion ................................... 20

III. BIOACTIVE

A. BioabsorbablesSegmented Urea and Siloxane Copolymers and Their

Preparation Methods ............................................................... 25Functionalized Polymers for Medical Applications ......................... 28Degradable Polyacetal Polymers .................................................. 31Lactone Bearing Absorbable Polymers .......................................... 35

B. Contact LensesLow Polydispersity Poly-HEMA Compositions .............................. 40

C. Drug DeliveryAmphiphilic Block Copolymers and Nanoparticles

Comprising the Same .............................................................. 44Heterofunctional Copolymers of Glycerol and Polyethylene

Glycol, Their Conjugates and Compositions ............................... 48Polyalkylene Glycol Acid Additives ............................................. 51Thermosensitive Biodegradable Copolymer ................................... 55Polyamide Graft Copolymers ....................................................... 58Bioerodible Poly(Ortho Esters) from Dioxane-Based

Di(Ketene Acetals) and Block Copolymers Containing Them ....... 61Water-Soluble Polymer Alkanals .................................................. 65

vii

Biodegradable Aliphatic Polyester Graftedwith Poly(Ethylene Glycol) Having Reactive Groupsand Preparation Method Thereof ............................................... 69

Coumarin End-Capped Absorbable Polymers ................................. 72Block Copolymers for Multifunctional Self-assembled Systems........ 76Methods of Making Functional Biodegradable Polymers ................. 80Monofunctional Polyethylene Glycol Aldehydes ............................ 84

IV. COATINGS

A. AnionicGlycopolymers and Free Radical Polymerization Methods ............... 89

B. AqueousMethod of Making Novel Water-Soluble

and Self-doped Polyaniline Graft Copolymers ............................ 93Oxyfluorination ......................................................................... 97Aqueous Dispersions of Crystalline Polymers and Uses ................... 99

C. FluorineMultifunctional (Meth)Acrylate Compound,

Photocurable Resin Composition and Article ............................ 102

D. HydrophilicPolyoxyalkylene Phosphonates and Improved

Process for Their Synthesis .................................................... 105

E. HydrophobicPolymers and Polymer Coatings ................................................. 108Photochemical Crosslinkers for Polymer

Coatings and Substrate Tie-Layer............................................ 112Use of Poly(Dimethyl Ketone) to Manufacture Articles

in Direct Contact with a Humid or Aqueous Medium................. 116

F. Thermally StablePolyaryleneetherketone Phosphine Oxide Compositions

Incorporating Cycloaliphatic Units for Use as PolymericBinders in Thermal Control Coatings and Methodfor Synthesizing Same ........................................................... 118

G. Vapor Deposition of PolymersFunctionalization of Porous Materials by Vacuum

Deposition of Polymers ......................................................... 121

viii Contents

H. Succinic Anhydride DerivativesLight Absorbent Agent Polymer for Organic Anti-reflective

Coating and Preparation Method and OrganicAnti-reflective Coating Composition Comprising the Same ........ 124

V. COSMETICS

Water-Soluble or Water-Dispersible Graft Polymers,Their Preparation and Use........................................................... 129

VI. DENTAL

A. Cement(Meth)Acrylate-Substituted Iminooxidiazine

Dione Derivatives ................................................................. 133

B. Dental Composites(Meth)Acrylic Ester Compound and Use Thereof ......................... 138

VII. ELECTROACTIVE

A. Charge Transport MaterialsHole Transport Polymers and Devices Made with Such Polymers ... 143Acrylic Polymer and Charge Transport Material ........................... 147

B. Dielectric MaterialsThermosetting Aromatic Dielectric Material ................................ 150

C. Donor-Acceptor ComplexesPolyester Having p-Conjugated Group in Side Chain

and Charge Transporting Material Using the Same .................... 155

D. ElectroconductiveHalogenated Thiophene Monomer for the Preparation

of Regioregular Polythiophenes .............................................. 158Electrically Conductive Polymeric Biomaterials, the Process

for Their Preparation and Use in Biomedical andHealth Care Fields ................................................................ 161

Dibenzodiazocine Polymers ....................................................... 164Redox-Active Polymer and Electrode

Comprising the Same ............................................................ 168

Contents ix

Use of Sulphonic, Phosphonic and Phosphoric Acidsas Dopants for Polyaniline and for ConductivePolyaniline-Based Composite Materials ................................ 172

3,4-Alkylenedioxy-Thiophene Copolymers ............................... 177

E. ElectroluminescenceElectroactive Polymer, Device Made Therefrom and Method ...... 180Polymers and Oligomers, Their Synthesis, and Electronic

Devices Incorporating the Same........................................... 185Process for Preparing Poly(Arylene Ethers) with Pendant

Crosslinkable Groups ......................................................... 190

F. SemiconductorsMono-, Oligo-, and Polythieno[2,3-b]Thiophenes ...................... 196Poly(Arylene Ether) Dielectrics............................................... 201Polythiophenes and Devices ................................................... 205Mono-, Oligo- and Polymers Comprising Fluorene

and Aryl Groups ................................................................ 211

VIII. ENERGETIC POLYMERS

Glycidyl Dinitropropyl Formal, Poly(Glycidyl DinitropropylFormal), and Preparation Method Thereof .................................. 217

Synthesis of Energetic Thermoplastic ElastomersContaining Both Polyoxirane and Polyoxetane Blocks ................. 220

IX. FIBERS

Rigid-Rod Benzobisazole Polymers IncorporatingNaphthalene-1,5-Diyl Structure Units ........................................ 223

Polybenzazole Fiber and Use Thereof ........................................... 227

X. FLUORINE

A. Critical PolymerizationProcess for Producing Fluoropolymer ...................................... 231

B. High StrengthFluorinated Terpolymer.......................................................... 234

C. Low Molecular WeightDirectly Polymerized Low Molecular Weight Granular

Polytetrafluoroethylene....................................................... 237

x Contents

Fluoroelastomers Containing CopolymerizedUnits of Vinyl Esters ............................................................... 241

D. Low Surface EnergyAmorphous Polyether Glycols Based on bis-Substituted

Oxetane and Tetrahydrofuran Monomers............................... 244

E. Silicon FluidsCyclic Siloxane Compounds and Making Method ...................... 247

F. SurfactantsFluorinated Organosilicon Compounds

and Fluorochemical Surfactants ........................................... 251

XI. GELS

A. Gelling AgentFerrocene-Containing, Organic Gelling Compound,

and Gel and Cast Film Using the Same ................................. 255

B. HydrogelsRandom Block Copolymers .................................................... 259(Meth)Acrylic Esters of Polyalkoxylated Trimethylolpropane ...... 262Prepolymers for Improved Surface Modification of

Contact Lenses .................................................................. 265Preparation of High Molecular Weight Polysuccinimides ............ 269Degradable Crosslinkers and Degradable Crosslinked

Hydrogels Comprising Them............................................... 272

C. Sol-gelThermosensitive Poly(Organophosphazenes), Preparation

Method Thereof and Injectable ThermosensitivePolyphosphazene Hydrogels Using the Same ......................... 278

XII. IMAGING AGENT

Polymerization Method for the Synthesis of PolypeptideImaging Agents ...................................................................... 283

XIII. INK

Process for Preparing Chain Extended ThermoplasticGuanidinium Polymers ............................................................ 289

Contents xi

XIV. LIQUID CRYSTALS

A. Liquid Crystal AlignerDiamines, Polyimide Precursors, and Polyimides Produced

by Using the Diamines and Liquid Crystal Aligning Agents .... 293Photosensitive Polyimides for Optical Alignment

of Liquid Crystals .............................................................. 298

B. Liquid Crystal MaterialsHomopolymers That Exhibit a High Level of Photo-inducable

Birefringence .................................................................... 303Liquid Crystalline Compound, Liquid Crystalline

Composition, and Retardation Film ...................................... 307Perfluoroallyloxy Compound and Liquid Crystal

Composition Containing the Same ....................................... 315Liquid Crystal Polymers......................................................... 318

XV. NANOPARTICLES

A. Carbon NanotubesMethod of Coating a Substrate with a Polymer Having

a Combination of Crown Ether and Carbon NanotubesHaving Guanidine Groups ................................................... 325

Process for Derivatizing Carbon Nanotubeswith Diazonium Species ..................................................... 329

Carbon Nanotube Adducts and Methods of Making the Same...... 333Modification of Nanotubes by Oxidation

with Peroxygen Compounds ................................................ 336Arylcarbonylated Vapor-Grown Carbon Nanofibers.................... 339

B. Inorganic NanotubesPolymeric and Carbon Compositions with Metal Nanoparticles ... 343Metal Oxide Nanotube and Process for Production Thereof......... 347

C. Nanotube DispersantMethods for the Synthesis of Modular

Poly(Phenyleneethynlenes) and Fine-Tuning theElectronic Properties Thereof for the Functionalizationof Nanomaterials ............................................................... 351

XVI. NEW SYNTHETIC METHODS

A. CompoundsSolid-Phase Preparation of [18F] Fluorohaloalkanes ................... 357

xii Contents

Vinyl Sulphone Modified Polymer .......................................... 362Ketone Peroxide Derivatives, Their Preparation and Use............ 367

B. PolymersSimplified Method of Producing Biodegradable

Aliphatic Polyesters .......................................................... 371Hydroaminomethylation of Olefins ......................................... 373Perdeuterated Polyiimides, Their Process of Preparation,

and Their Use as Materials Which Are Transparent withinthe Region from 2500 to 3500 cm�1 .................................... 376

Polybutadiene (Meth)Acrylate Composition and Method ........... 379Soluble Aniline-Thiophene Copolymers .................................. 381Process for the Preparation of Di- and Polyamines

of the Diphenylmethane Series ........................................... 384Method for Preparing Polymer Maleimides .............................. 386Method for Preparing Polymers Containing

Cyclopentanone Structures ................................................. 389Polypropylene Having a High Maleic Anhydride Content .......... 392Polyamide Graft Copolymers ................................................. 395Guerbet Polymers................................................................. 398Polymerization Method ......................................................... 401Process for Producing Polymerizable Polybranched Polyester..... 406N-Vinylformamide Derivatives, Polymers Formed Therefrom

and Synthesis Thereof ....................................................... 409Polymers............................................................................. 413Star-Shaped Polymer, Multiple Star Polymer, and Their

Preparation Methods ......................................................... 417

XVII. OPTICAL MATERIALS

Second-Order Nonlinear Optical MaterialsPolymers Having Pendant Nonlinear Optical Chromophores

and Electrooptic Devices Therefrom.................................... 419

XVIII. PHOTOACTIVE POLYMERS

A. PhotoluminscencePolymeric Compound and Organic Luminescence Device .......... 427Electroactive Fluorene Copolymers and Devices Made

with Such Polymers .......................................................... 432Light-Emitting Polymers ....................................................... 437Modified Suzuki-Method for Polymerization

of Aromatic Monomers ..................................................... 444

Contents xiii

Block Copolymer and Polymeric Luminescent Element ............ 448Soluble Poly(Aryl-Oxadiazole) Conjugated Polymers ............... 453

B. PhotorefractionFullerene-Containing Polymer, Producing Method Thereof,and Photorefractive Composition ........................................ 458

XIX. POLYMERIZATION METHODS

A. AnionicMethod for Anionic Polymerization of Oxiranes ...................... 463Amido-Organoborate Initiator Systems ................................... 465Process for Manufacturing Vinyl-rich PolybutadieneRubber ............................................................................ 467

Catalyst for Synthesizing High Transpolymers ......................... 469Method for the Preparation of Poly(a)-Methylstyrene ............... 472Use of Sulfur Containing Initiators for Anionic Polymerizationof Monomers ................................................................... 474

Production Method of Polyisocyanate by End-Cappingwith Acyl Chloride ........................................................... 478

B. Catalytic AgentsMethods for Making Functionalized Polymers ......................... 481

C. CationicPolymerization of i-Butene in Hydrocarbon MediaUsing bis(Borane) Co-Initiators .......................................... 486

Copolymers of Tetrahydrofuran, Ethylene Oxide,and an Additional Cyclic Ether ........................................... 489

D. Chain Transfer AgentsDithiocarbamic Esters .......................................................... 492

E. Emulsifing AgentsAmphiphilic Copolymers Useful Especially as Emulsifiers ........ 497Anionic Copolymers Prepared in an InverseEmulsion Matrix and Their Use in PreparingCellulosic Fiber Compositions ............................................ 501

F. Free Radical PolymerizationPerfluorodiacylperoxides as Polymerization Initiators ............... 504

G. MacroinitatorsPolymeric Photoinitiators...................................................... 507

xiv Contents

Radical Polymerization Method Performedin the Presence of Disulfide Compounds .............................. 511

Copolymers of Maleic Anhydride by Stable FreeRadical Polymerization...................................................... 514

H. Macromolecular Depolymerization CatalystsCatalysts and Methods for Polymerizing MacrocyclicOligomers........................................................................ 517

Catalytic Systems................................................................ 520

I. Metallocene CatalystsMetallocene Catalysts Containing a Cyclopentadienyl LigandSubstituted by a Siloxy or Germiloxy Group Containingan Olefinic Residue........................................................... 523

J. Ring-Opening Metathesis CatalystPhotochromic Polymers and Methods of Synthesizing Same...... 528Synthesis of A,B-Alternating Copolymers by Olefin MetathesisReactions of Cyclic Olefins or Olefinic Polymers with anAcyclic Diene .................................................................. 533

K. Ziegler–NattaHigh 1,4-cis Polybutadiene-Polyurethane Copolymerand Preparation Method Thereof ......................................... 539

Process for Producing Polymer ............................................. 542Polymerization Catalyst Composition .................................... 546Synthetic Polyisoprenes and a Process for Their Preparation ..... 550Polymerization Catalyst ....................................................... 552Use of Stannylenes and Germylenes as PolymerizationCatalysts for Heterocycles.................................................. 557

Process for Producing Polar Olefin Copolymer and PolarOlefin Copolymer Obtained Thereby ................................... 560

Carborane Trianion-Based Catalyst........................................ 565Catalyst for Polymerization of Norbornene ............................. 569

XX. REGULATORS

A. Chain Transfer AgentsMethod for the Production of Homo-, Co-,and Block Copolymers ...................................................... 575

Method for Radical Polymerization in the Presenceof a Chain Transfer Agent .................................................. 577

Use of C4-C6-Polymercaptopolyols as Regulatorsin Solution or Precipitation Polymerization .......................... 581

Contents xv

S-(a,a0-Disubstituted-a00-Acetic Acid) SubstitutedDithiocarbonate Derivatives for Controlled RadicalPolymerizations, Process, and Polymers Made Therefrom ...... 584

B. Chain Transfer ProcessesChain Transfer Agents for RAFT Polymerizationin Aqueous Media............................................................. 588

Hindered Spiro-Ketal Nitroxides ............................................ 592Controlled Polymerization .................................................... 595N-Alkoxy-4,4-Dioxy-Polyalkyl-Piperidines as RadicalPolymerization Inhibitors ................................................... 600

C. Photolytic Regulating AgentsMethod for Producing Polymers with Controlled MolecularWeight and End-Group Functionality UsingPhotopolymerization in Microemulsions .............................. 604

Ring-Opened Azlactone Photoiniferters for RadicalPolymerization ................................................................. 606

XXI. PHOTORESISTS

A. Fluorine ContainingMonomer Having Fluorine-Containing Acetal or KetalStructure, Polymer Thereof, and Chemical-Amplification-TypeResist Composition as Well as Process for Formationof Pattern with Use of the Same ........................................ 611

Polymers, Resist Compositions, and Patterning Process ............ 616Fluorine-Containing Polymerizable Cyclic Olefin Compound .... 623Photoresist Composition ....................................................... 627

B. NorborneneNorbornene-Type Monomers and Polymers ContainingPendent Lactone or Sultone Groups .................................... 632

Photoresists Containing Sulfonamide Component..................... 636

C. AdamantaneTertiary (Meth)Acrylates Having Lactone Structure, Polymers,Resist Compositions, and Patterning Process ........................ 642

Chemical Amplification Type Positive Resist Composition ........ 647

D. Diamantane AcrylatePositive Photosensitive Composition and Pattern-FormingMethod Using the Same .................................................... 651

xvi Contents

XXII. SEPARATIONS

A. GasesDithiolene Functionalized Polymer Membranefor Olefin/Paraffin Separation ............................................. 657

B. SolutionsTethered Polymer Ligands .................................................... 662Isolatable, Water-Soluble, and Hydrolytically StableActive Sulfones of Poly(Ethylene Glycol)and Related Polymers for Modification ofSurfaces and Molecules ..................................................... 665

Optically Active Maleimide Derivatives, Optically ActivePolymaleimide Derivatives, Process for Their Production,Separating Media Comprising the Optically ActivePolymaleimide Derivatives, and Method of SeparatingOptically Active Compounds Using Them............................ 669

Polymeric Membranes and Uses Thereof ................................ 674Separating Agent Including a Polysaccharide DerivativeHaving a Polycyclic Structure............................................. 678

Functionalized Polymers for Binding to Solutesin Aqueous Solutions ........................................................ 683

XXIII. THERMOSETS

A. Poly(Ethyl a-Acetoxyacrylate)Acrylic Copolymer ............................................................. 687

B. PolyethersulfoneHigh-Heat Polyethersulfone Compositions .............................. 689

C. PolynorboreneNovel (Co)polymer, Process for Producing the Same,and Process for Producing Carboxylated (Co)polymer ........... 692

D. PolyformalsPolyformals and Copolyformals with ReducedWater Absorption, Production, and Use Thereof .................... 695

E. Styrene and Zinc Diacrylate IonomersBranched Ionomers .............................................................. 699

F. PolycyclodieneCopolymer of Conjugated Cyclodiene .................................... 702

Contents xvii

G. a-Aromatic KetonesPoly(Aralkyl Ketone)s and Methods of Preparing the Same ....... 705

H. Polyimide SulfonesPolyimide Sulfones, Method and Articles Made Therefrom ....... 708

I. Benzoxazine ResinsMethod for Producing Benzoxazine Resin............................... 712

J. AcrylonitrileBlock Copolymer ................................................................. 714

K. PolycarbonatesAliphatic Diol Polycarbonates and Their Preparation ................ 717

L. Poly(Silarylene-Siloxane-Acetylene)High-Temperature Elastomers from Linear

Poly(Silarylene-Siloxane-Acetylene) ................................... 721

ContributorsAcademic Contributors ....................................................................... 725Government Contributors .................................................................... 725Industrial Contributors........................................................................ 726

Index ................................................................................................ 729

xviii Contents

PREFACE

Much has changed in polymer chemistry since thefirst resin/polymer patent issued. USPatent 125 (February 10, 1817) describes a method of waterproofing boots and shoesreported by inventor Patrick G. Nagel. The method entailed:

Taking two pounds of balsam-copiba, five pounds of the essence of the myrtle-tree, one pound of gum-copal, two pounds of rosin, and three pounds ofrendered suet.

The objective of this investigation has been to provide readers with current polymerchemistry research trends from academic, governmental, and industrial sourcesreported in US patents for the years 2006 to 2007. Twenty-three broad subject areaswere reviewed as provided below:

Additives Fibers Optical materialsAdhesives Fluorine Photoactive polymersBioactive Gels Polymerization methodsCoatings Imaging agents RegulatorsCosmetics Ink PhotoresistsDental Liquid crystals SeparationsElectroactive Nanoparticles ThermosetsEnergetic polymers New synthetic methods

Another objective of this review have been to provide the reader with explicitlaboratory methods for preparing agents/intermediates of interest, testing methodsused to assay material efficacy, and analytical data for structural conformation.

The text format has been designed to be used as a reference and synthetic guide forpolymer and organic chemists as well as graduate students. The text, however, is notrestricted to polymer chemistry. In many instances—and with only marginal mod-ifications—intermediates and products are readily convertible into other agents inrelated or dissimilar research concentrations. To underscore this point, structuraldepictions of reagents, intermediates, and products are provided to allow the researcherto more easily visualize other/future material applications.

Finally I thoroughly enjoyed compiling this review and trust the reader will find ituseful.

THOMAS F. DEROSA

December, 2007

xix

I. ADDITIVES

Title: Controlled Radical Acrylic CopolymerThickeners

Author: S. C. Schmidt et al., US Patent Application 2007-0082827 (April 12, 2007)Assignee: Arkema, Inc. (Philadelphia, PA)

SIGNIFICANCE

Di- and triblock polymers have been prepared by nitric oxide mediated polymer-ization using t-butyl 1-diethylphosphono-2,2-dimethylpropyl nitroxide. Materialsprepared from this process are useful as paint thickeners and viscosity indeximprovers in paint.

REACTION

c

OCH3OOCH3O O OC12H25

OCH3O

a b

Note 1

i

EXPERIMENTAL

Preparation of Poly(Methacrylate-b-(Dodecyl Methacrylate-co-Methacrylate))

A steel resin kettle was charged with t-butyl 1-diethylphosphono-2,2-dimethylpropylnitroxide (30.0mmol) and methyl acrylate (6.97mol) and then heated to 110�C for 3hours, at which point the reaction had reached 50% conversion. The reaction mixturewas cooled to ambient temperature and the Mw determined to be 12,600 daltons. In a

Advances in Polymer Chemistry and Methods Reported in Recent US Patents, by Thomas F. DeRosaCopyright � 2008 by John Wiley & Sons, Inc.

1

glass reactor dodecylmethacrylate (159.4mmol)washeated to100�Cand treatedwiththe previously prepared polymer mixture (25.3 g) and methyl acrylate (25.3mmol).This mixture was then treated with polymethacrylate (12.65 g) and methyl acrylate(4.83 g) and heated to 100�C to 105�C for several hours. The resultant viscousliquid was diluted with an equal volume of THF and precipitated into cold stirringmethanol; the product was isolated having a Mw of 56,500 daltons and Mn of 39,600daltons.

DERIVATIVES

NOTES

1. The nitric oxide mediated polymerization agent t-butyl 1-diethylphosphono-2,2-dimethylpropyl nitroxide, (I), was prepared according to the method ofGillet [1] as illustrated below:

t-C4H9 H

O

NH

t-C4H9P

t-C4H9

OC2H5

OOC2H5

Nt-C4H9

P

t-C4H9

OC2H5

OOC2H5

O

i ii

(I)

i: t-Butylamine, diethyl phosphateii: 3-Chloroperbenzoic acid

2. Randomcopolymers effective as paint viscosity index improverswere preparedby Shoaf as provided in Table 2.

TABLE 1. Selected di- and triblock polymers prepared by controlled free radicalpolymerization using t-butyl 1-diethylphosphono-2,2-dimethylpropyl nitroxide.

Entry Polymer*1 Mn PDI Notes

1C PDDMA-b-PS 28,000 1.6 PS¼ 16%1D PDDMA-b-PS-b-PDDMA 31,600 1.7 PS¼ 35%1E (PDDMA-co-PS)-b-PS-b-(PS-co-PDDMA) 31,600 1.7 PS¼ 48%1F PDDMA-b-PMA-b-PDDMA 23,000 1.5 PMA¼ 48%1I PDDMA-b-PMA-b-PDDMA 76,000 2.0 PMA¼ 60%

Note: All materials were used as viscosity index improvers in paint.*1PDDMA¼ Polydodecyl methacrylate

PMA¼ Polymethacrylate

2 Controlled Radical Acrylic Copolymer Thickeners

3. Blankenship [3] prepared polyethylene glycol carbamate, (II), as paint thick-eners containing poly(ethylene oxide-b-propylene oxide-b-ethylene oxide) andeither 1,6-hexamethylene diisocyanate or 4,40-methylene bis-(isocyanatocy-clohexane). Polycarbamates were also prepared by Bauer [4] using a blockpolymer initiated by stearyl alcohol and consisting of poly(ethylene oxide-b-propylene oxide-b-butylene oxide-b-dodecene oxide-b-tetradecene oxide)coupled with the diisocyanate, Desmodur N�.

aO

O

HN

O

6 265

(II)

4. Polycarbamates, (III), prepared by Martin [5] consisting of toluene diisocya-nate, methoxypolyethylene glycol, polypropylene glycol, and dihydroxy-methyl propanoic acid were also effective as paint thickeners and viscosityindex modifiers.

c

HN

NH

O

OO

O

O

HN

OOO

H3COa

b

(III)

TABLE 2. Random copolymers used as viscosity index improvers andthickeners in paints.

Entry Polymer*1 Monomer Ratio*2 (wt%)

1 PS-co-PEHA-co-PAAEM-co-PMAA 51.8/22.7/8.0/2.55 PS-co-PEHA-co-PAAEM-co-PMAA-co-PAA 45.9/21.1/8.0/1.25/3.757 PS-co-PEHA-co-PMAA 63.7/18.9/2.5

*1AA¼Acrylic acidAAEM¼Acetoacetoxy ethyl methacrylateEHA¼ 2-Hydroxylethyl acrylateMMA¼Methylmethacrylate*2The remainder of the composition consisted of alkyd.

Notes 3

References

1. J.-P. Gillet et al., US Patent 6,624,322 (September 23, 2003)2. G.L. Shoaf et al., US Patent Application 2006-0270769 (November 30, 2006)3. R.M. Blankenship et al., US Patent Application 2006-0106153 (May 18, 2006)4. S. Bauer et al., US Patent 7,189,772 (March 13, 2007)5. E. Martin et al., US Patent 7,144,945 (December 5, 2006)

4 Controlled Radical Acrylic Copolymer Thickeners

Title: Polymer-Filler Coupling Additives

Author: A. Fukushima et al., US Patent 7,186,845 (March 6, 2007)Assignee: Bridgestone Corporation (Tokyo, JP)

SIGNIFICANCE

A method for preparing and covalently bonding either 4-(2-oxazolyl)-phenyl- ormethyl-N-phenylnitrone to natural rubber in automotive tires is described. The effecthas been a 40% overall reduction in tire hysteresis and superior performance overexisting polyamine formulations.

REACTION

O

Cl O

H

O

HO

N

N

HO

N O

i ii iii

Model reaction product

O

NH O

HHO

iv

NO

O

N

Notes 1,2

i: 2-Aminoethanol, CCl3Hii: Sulfuric acid, sodium hydroxide, CCl3Hiii: N-Phenyl-hydroxyamine, ethanoliv: Cyclododecene

5

EXPERIMENTAL

1. Preparation of 4-Formyl-N-(2-Hydroxyethyl)-Benzamide

Asolutionof4-formyl-benzoylchloride (1 eq) in 300mlofCCl3Hwas addeddropwiseat �10�C to a solution of 2-aminoethanol (2 eq), dissolved in 200 ml of CCl3H, andthen stirred at 25�C for 2 hours. Themixturewas filtered, dried, and concentrated, and17.4 g of product were isolated as a yellow liquid.

2. Preparation of 4-(2-Oxazolyl)-Benzaldehyde

The Step 1 product (17.4 g) was treated dropwise with 50ml of 18MH2SO4 and thenheated to 100�C for 60 minutes. The mixture was added dropwise with stirring to500ml 20% sodium hydroxide and 500ml of CCl3H while the solution temperaturewas kept below 15�C. The organic phasewas separated and dried, and 6.3 g of productwere isolated.

3. Preparation of 4-(2-Oxazolyl)-Phenyl-N-Phenylnitrone

Amixtureof theStep2product (1 eq) andN-phenyl-hydroxyamine (1 eq)was refluxedin 100ml of ethanol for 30 minutes and then concentrated to 50ml. The concentratewas treated with 50ml of water and cooled in a refrigerator to 5�C overnight. Whitecrystals were obtained; these were isolated by filtration, dried, and 6.7 g of productwere isolated.

4. Model Reaction: Reactivity of 4-(2-Oxazolyl)-Phenyl-N-Phenylnitrone withCyclododecene

In selected amounts the Step 3 product was mixed with 1 ml cyclododeceneand then heated to 171�C. The amount of recoverable Step 3 compound at varioustimeperiodsduring the reactionwith cyclododecenewas an indicationof the reactivityof this productwith unsaturated carbon–carbon bonds. Scoping results are provided inTable 1.

DERIVATIVES

4-(2-Oxazolyl)-phenyl-N-methylnitrone, (I), was also prepared:

N

HO

N O

(I)

6 Polymer-Filler Coupling Additives

TESTING

1. Reactivities

Reactivities of the Step 3 product and 4-(2-oxazolyl)-phenyl-N-methylnitrone, (I),with cyclododecene at 170�C are provided in Table 1.

N

HO

N

R

O

2. Tan d

The effect of the experimental agents on natural rubber hysteresis was determinedby measuring tan d at 5% strain using an ARES-A Rheometer at 50�C and 15Hz.Testing results are provided in Table 2.

TABLE 1. Percent incorporation of the Step 3 product and derivativeinto cyclododecene at 170�C.

Entry RHeating Time @170�C (min)

NitroneAmount(mg)

Amount ofIncorporatedExperimentalNitrone (%)

2 Phenyl 5 5.52 974 Phenyl 15 5.65 1005 Phenyl 30 5.60 1007 Methyl 5 4.09 399 Methyl 15 3.83 7810 Methyl 30 4.05 98

Note: No characterization data for either experimental agents or cyclododecene addition products wereprovided by author.

Testing 7

NOTES

1. In a subsequent investigation by the author [1] styrene butadiene rubberfunctionalized with the Step 3 product was prepared and was effective inlowering tire hysteresis.

2. Bis-[2-2-thiazolyl-phenyl]disulfide, (I), derivatives were also prepared by theauthor [2] in a subsequent investigation and were effective in reducing tirehysteresis.

S

N

S

S

S

N

(I)

TABLE 2. Effect of experimental additives on tan d of natural rubberat various treatment levels.

N

HO

N

R

O

R Nitrone Dosage (mmol) Tan d

Unadditized — 0.21Reference*1 0.16 0.20Phenyl 0.2 0.18Phenyl 0.4 0.16Phenyl 0.8 0.14Phenyl 1.6 0.13Methyl 0.2 0.2Methyl 0.4 0.19Methyl 0.8 0.16Methyl 1.6 0.20

Note: Lower tan d values are preferred.*1Sumifine� 1162¼ (N,N0-di(2-nitro-2-methyl-propyl)-hexamethylenediamine

8 Polymer-Filler Coupling Additives

3. Polymer nanostrings consisting of block terpolymers of butadiene, styrene, anddivinyl-benzene having a Mn of 46,744 daltons were prepared Wang [3] andused as additives in natural and synthetic automotive tires. The nano stringswere then postmodified to enhance tire surface and bulk performance.

4. Parker [4] end-group functionalized poly(1,3-butadiene) polymers with iso-propyl hydroxyl-amines to improve the affinity and interaction with carbonblack and silica fillers to extend tire lifetime.

References

1. A. Fukushima et al., US Patent Application 2006-0084730 (August 20, 2006)2. S. C. Schmidt et al., US Patent Application (2007-0161756 (July 12, 2007)3. X. Wang et al., US Patent 7,179,864 (February 20, 2007)4. D.K. Parker,US Patent Application 2007-0004869 (January 4, 2007)

Notes 9

II. ADHESIVES

Title: (Meth)acrylate Block Copolymer PressureSensitive Adhesives

Author: A. I. Everaerts et al., US Patent 7,255,920 (August 14, 2007)Assignee: 3M Innovative Properties Company (St. Paul, MN)

SIGNIFICANCE

Block terpolymers consisting of butyl acrylate with either methylmethacrylate ormethyl acrylate have been preparedwhere the end segments are at least 10,000 daltonsand the center segment is at least 60,000 daltons. These materials were coated onto apolycarbonate surface and used to prepare an optical film and an optically clearpressure–sensitive adhesive layer that resists bubble formation when adhered to anoutgassing substrate.

REACTION

O

On-C4H9 OO

n-C4H9

OO

n-C4H9

OCH3

O

OCH3

O60K10K

60K10K

i ii

i: Copper (I) bromide, 1,4-dibromoadipate, n-butyl acrylate, anisole, hexadecane,tris[2-(dimethyl-amino)ethyl]amine

ii: Copper (I) chloride, n-butyl acetate, 1,1,4,7,10,10-hexamethyl-triethylenetetra-mine), methylethylketone, methylmethacrylate


11

EXPERIMENTAL

1. Preparation of a 60K Poly(Butyl Acrylate) Midblock Macroinitiator

A reactor was charged with a mixture consisting of CuBr (0.00478 g), 1,4-dibromoa-dipate (0.06 g), n-butyl acrylate (10.0 g), anisole (0.5 g), 0.5ml of hexadecane, and 9.0ml of tris[2-(dimethylamino)ethyl]amine. The mixture was heated to 60�C for 20hours, and the product was isolated having a molecular weight of 60,000 daltons.

2. Preparation Poly[(Methylmethacrylate)-b-Poly(Butyl Acrylate)-b-Poly(Methyl Methacrylate)]

The Step 1 product was dissolved in roughly 10 ml of n-butyl acetate and then treatedwith CuCl (0.0396 g) complexed with 108.8 ml of 1,1,4,7,10,10-hexamethyl-triethy-lenetetramine), 2 ml of methylethylketone, and 4 ml of methylmethacrylate. Themixturewas then heated to 60�C for 24 hours, cooled, dissolved in THF to 20% solids,and filtered through alumina to remove residual catalyst. The product poly(methyl-methacrylate)-b-poly(butyl acrylate)-b-poly(methylmethacrylate) was isolated hav-ing molecular weight segments of 10,000/60,000/10,000 daltons, respectively.

DERIVATIVES

TESTING

Accelerated aging testing and dynamicmechanical analysis were used to evaluate thestability of coated laminates. Testing results are provided in Table 2.

TABLE 1. Selected block terpolymers and corresponding segmented molecularweights.

Entry Polymer*1Segment MolecularWeights (daltons)

1 PolyMMA-b-polyBA-b-polyMMA 10K–60K–10K3 PolyMMA-b-polyBA-b-polyMMA 14K–120K–14K6 PolyMMA-b-polyBA-b-polyMMA 14K–60K–147 pMMA-b-p(BA/MA)-b-pMMA 10K–60K–1010 (pBA-b-pMMA)3 (30K–10K)3

Note: Entry 10 is a tri-arm block copolymer.*1MMA¼MethylmethacrylateBA¼ n-Butyl acrylateMA¼Methyl acrylate

12 (Meth)acrylate Block Copolymer Pressure Sensitive Adhesives

NOTES

1. In an earlier investigation by Yang [1] triblock urethane acrylate oligomersterminated with acrylic acid were prepared and used in curable pressuresensitive adhesive compositions.

2. Additional block terpolymers containing propyl acrylate and star block terpo-lymers containing styrene were previously prepared by the author [2] and usedin hot-melt pressure-sensitive and heat-activatable adhesives.

3. Random terpolymers consisting of ethyl, butyl, and behenyl acrylate wereprepared by the author [3] and used as heat-activatable adhesives. Randonterpolymers consisting of iso-octyl/acrylic acid/styrene macromonomer, 92/4/4mol%, respectively, were prepared by Joseph [4] and used as a reinforcedpressure sensitive adhesive.

4. Linear and star diblock polymers consisting of methyl and n-butyl acrylateswere prepared by Paul [5] and used as high performance, low viscosity hot-meltadhesives. A single star block terpolymer containing 2-ethylhexyl acrylate wasalso prepared.

5. Husemann [6] prepared UV-transparent adhesives consisting of acrylic acid,acrylamide, and 2-ethylhexyl acrylate that were effective as pressure-sensitiveadhesives.

TABLE 2. Thermal aging stability and storagemodulus analysis of laminates coatedwith selected experimental agents using PMMA or PC as the coating substrate.

Entry Substrate90�C AgingTest Results

80�C with90% HumidityTest Results

Log (G0) at25�C (Pascals)

Log (G0)at 150�C(Pascals)

1 PC*1 Pass Marginal 5.34 4.841 PMMA Pass Pass — —3 PC Bubbles Bubbles 4.63 4.223 PMMA Bubbles Bubbles — —6 PC Pass Pass — —6 PMMA Pass Pass7 PC Pass Bubbles — —7 PMMA Marginal Pass — —10 PC Bubbles Pass 5.60 4.8310 PMMA Pass Pass — —

*1PC¼ Polycarbonate

Notes 13

References

1. J. Yang et al., US Patent 6,887,917 (May 3, 2005)2. A.I. Everaerts et al., US Patent 7,084,209 (August 1, 2006) and US Patent 6,806,320 (October 19,

2004)3. A.I. Everaerts et al., US Patent 7,008,680 (March 7, 2006)4. E.G. Joseph et al., US Patent 6,994,904 (February 7, 2006)5. C.W. Paul et al., US Patent Application 2004-0122161 (June 24, 2004)6. M. Husemann et al., US Patent 7,144,928 (December 5, 2006)

14 (Meth)acrylate Block Copolymer Pressure Sensitive Adhesives

Title: Absorbable a-Cyanoacrylate Compositions

Author: H. Liu, US Patent 7,238,828 (July 3, 2007)Assignee: Ethicon, Inc. (Somerville, NJ)

SIGNIFICANCE

Polymerizable3-(2-cyano-acryloyloxy)-butyric acid ethyl ester hasbeenprepared in atwo-step process using3-hydroxybutyrate and cyanoacetic acid followedby treatmentwith formaldehyde. This and related alkyl ester a-cyanoacrylate monomers are usefulas tissue adhesives/sealants in surgical and related medical applications.

REACTION

OH

O

ONC

O O

O O

i ii

O O

O O

CN

CN

OO

OO

Note 1

a

Oligomeric intermediate

i: Cyanoacetic acid, 4-dimethylaminopyridine, CH2Cl2, DMF, dicyclo-hexylcarbodiimide

ii: Paraformaldehyde, piperidine, benzene, phosphorous pentoxide

15

EXPERIMENTAL

1. Preparation of 3-(2-Cyano-Acetoxy)-Butyric Acid Ethyl Ester

A reactor was charged with ethyl-3-hydroxybutyrate (194.0 g), cyanoacetic acid(149.83 g), 4-dimethylaminopyridine (10.76 g), and 1500ml of CH2Cl2 and thentreated with 75ml of DMF. The solution was chilled in an ice-water bath and treatedwith dicyclohexylcarbodiimide (363.45 g) dissolved in 600ml of CH2Cl2. A whiteprecipitate formed within five minutes after the start of the addition, and the mixturewas stirred overnight. The precipitate was then removed by filtration and the filtrateconcentrated. The product was isolated in 73% yield after being distilled twice undervacuum, bp¼ 100–109�C/0.20–0.27mmHg.

2. Preparation of 3-(2-Cyano-Acryloyloxy)-Butyric Acid Ethyl Ester

A mixture consisting of the Step 1 product (39.84 g), paraformaldehyde (6.6 g),0.06ml of piperidine, and 150ml of benzene was stirred in a 250ml round bottomedflask containing a Dean–Stark trap and refluxed overnight. The solution was thenconcentrated, and a viscous residue that turned into a solid gel after cooling to ambienttemperature was isolated. The solid oligomer was de-polymerized by treating withhydroquinone (0.20 g) andphosphorous pentoxide and byheating to 160�C.The crudemonomerwasdistilled under vacuumand theproduct isolated in20%yield, bp¼ 114–115�C/0.17mmHg

A very small amount of this monomer product was placed between two moistfingertips and bonded the fingertips strongly within one minute.

TESTING

1. General Procedure for Lap Shear Testing Using Pig Skin

Fresh pig skinwas harvested from the backof a pigwithin 5 hours postsacrifice and thefat attached to the inside skin surface trimmed away. The skin was cut into 2

00 � 100

coupons and covered by saline moist paper towels before use. The external surface ofthe skin was used as the bonding surface to prepare the lap shear joint samples.

The coupons were dried prior to forming a lap shear joint. About 100 ml of theexperimental adhesive was deposited to one coupon and smoothed to cover a1=2

00 � 100area. Another coupon was placed over the area of the initial coupon and

a l lb weight placed on top. It was cured for 20 to 30min and the strength of the joint

1H NMR (CDCl3) d: 7.03(s, 1H), 6.60(s, 1H), 5.43(m, 1H), 4.15(q, 2H), 2.65(m, 2H), 1.40(d, 3H),1.23(t, 3H)

GC-MS: 98.3%

1H NMR (CDCl3) d 5.39(m, 1H), 4.16(q, 2H), 3.42(s, 2H), 2.62(m, 2H), 1.37(d, 3H), 1.27(t, 3H)GC-MS: 99.4%

16 Absorbable a-Cyanoacrylate Compositions

evaluated using an Instron (Model 5544) with a pulling rate of 5mm/min. A summaryof testing results is provided in Table 1.

2. In vitro Degradation Testing of Polymeric Films

A 1� 1 inch Prolene mesh was rinsed with 0.5 wt% of NaHCO3 and dried. Themesh was then placed on a freshly prepared Agar plate in a petri dish and roughly100mg of a selected experimental adhesive applied across the mesh. The selectedadhesive was cured overnight then sealed with parafilm; the film thickness wasabout 0.6 mm.

The filmwas then placed into a hydrolysis chamber with 100ml of water while thetemperature of the solution was maintained at 75�C. The pH of the solution wasmaintained at 7.27 with addition of 0.05M of a NaOH solution throughout thedegradationof thepolymer film.Thedegradation timewasdefined as the time requiredfor the medium to consume 90% of the total consumed NaOH solution. Thedegradation and glass transition temperatures of each polymer are summarized inTable 2.

TABLE 1. Instron lap shear testing results for selected a-cyanoacrylate monomericderivatives.

Entry Source Structure Load Strength (lb)

1B Invention OCN

O

O

O

4.09

2B Invention OCN

O

O

O

4.49

Et-e-CPL-CA Comparison OO

CN

O

O

3.68

Et-a-CPL-CA Comparison OO

CN

O

O1.29

Testing 17

NOTES

1. The polymerization was conducted accorded to the method of Leung[1].

2. Bioabsorbable adhesive compounds and compositions containing a polyalk-ylene oxide backbone having branched or multi-arm structure derived fromreacting with two or more isocyanate substituents were prepared by Roby [2]and used as surgical adhesives and sealants.

3. Photochemical tissue bonding comprising a skin graft and Rose Bengal to forma skin tissue-RB complex with fibrin or a fibrinogen adhesivewere prepared byRedmond [3]. The material was crosslinked by the application of electromag-netic energy having awavelength of at least 488 nmandwas used as an adhesivefor repairing musculoskeletal tissue damaged by a laceration or rupture inhumans.

TABLE 2. In vitro degradation and glass transition temperatures of selecteda-cyanoacrylate polymeric derivatives.

Entry Source Precursor Monomer

PolymerDegradationTime (h) Tg (

�C)

1B Invention OCN

O

O

O

54.6 32

2B Invention OCN

O

O

O

39.4 �11

Bu-Lac-CA Comparison OCN

O

O

O

49.4 52

Note: Polymers formed from compositions having Tg’s lower than body temperature (37�C) are particularlypreferred for medical applications.

18 Absorbable a-Cyanoacrylate Compositions

4. An absorbable a-cyanoacrylate adhesive composition, (I), was prepared byJonn [4] and used as a soft tissue adhesive.

CN

OO

OO

C4H9

(I)

References

1. J.C. Leung et al., US Patent 5,928,611 (July 12, 1994)2. M.S. Roby,US Patent 7,241,846 (July 10, 2007) and US Patent 7,129,300 (October 31, 2006)3. R.W. Redmond et al., US Patent 7,073,510 (July 11, 2006)4. J.Y. Jonn et al., US Patent 6,620,846 (September 16, 2003)

Notes 19

Title: Use of Polybenzoxazoles (PBOS) for Adhesion

Author: A. Walter et al., US Patent 7,052,936 (May 30, 2006)Assignee: Infineon Technologies AG (Munich, DE)

SIGNIFICANCE

A single-step method for preparing polybenzoxazole adhesives is described. Theseagents are particularly useful in the semiconductor industry for chip and wafer stackapplications.

REACTION

O O

HO

H2N

OH

NH2

O O

ON N

O

O

i

O O

HOH2N N

O

O O

ON N

O

O

O O

OH

NH NO

Not isolated

O

Notes 1,2

a

a

i: Phosphorus (V) oxide, methane sulfonic acid, 4,40-hydroxycarbonyl dipheny-lether, methacrylic acid

20

EXPERIMENTAL

Preparation of Polybenzoxazole End-capped with Methacrylic Acid

A reaction vessel was charged with 9,9-diphenyl-(4-amino-3-hydroxyl)dipheny-lether)fluorene (0.3mol) and 800 ml of methane sulfonic acid and then treatedwith the dropwise addition of 4,40-hydroxycarbonyl diphenylether (0.24) dissolvedin 400ml of methane sulfonic acid. The solution was heated for 5 hours at 80�C.After cooling to 40�C, the mixture was treated with the dropwise addition ofmethacrylic acid (0.12mol) dissolved in 100ml of methane sulfonic acid andheated an additional 6 hours at 100�C. The reaction product was isolated byfiltering through a glass frit and the filtrate added dropwise to a mixture of 2 literof water, 2 kg of ice, and 200ml of this 12M NH4OH; additional NH4OH wasadded during the filtration to ensure that the pH did not fall below 8. During theneutralization procedure the rate was such that the temperature did not exceed30�C. The precipitated polymer was isolated by filtration and washed with 3 literof cold water. Thereafter the solid was stirred in 3 liter 3% NH4OH at ambienttemperature for 1 hour and then suspended repeatedly in water. After filtration anddrying, 219 g of product were isolated.

DERIVATIVES

TABLE 1. Polybenzoxazole derivatives prepared using aminophenols anddicarboxylic acids with selected endcapping agents.

EntryAminophenol

Reagent Diacid ReagentEnd-capping

Agents

3

F3C CF3

H2N

HO

NH2

OHO2S

HO2C CO2H

—

4 H2N NH2

HO OHNHO2C CO2H

HO2C

5

O2S

H2N

HO

NH2

OHHO2C CO2H —

(continued)

Derivatives 21

TESTING

A 4-inch silicon wafer was sputtered with a titanium nitride layer 50 nm thick andthen a selected polybenzoxazole adhesive applied by spin-coating. Following ashort softbake at 120�C for 1 minute and at 200�C for 2 minutes on a hotplate, asecond 50 nm titanium nitride was sputtered onto the surface. A force of 2 N wasthen applied to the polybenzoxazole film at 340�C. The samplewas further heated to400�C in an oven under a nitrogen atmosphere for 60 minutes. After cooling toambient temperature the adhesion test was carried out by means of a shear testerusing a Dage Series 400. Testing results are provided in Tables 2 through 4.

EntryAminophenol

Reagent Diacid ReagentEnd-capping

Agents

6

F3C CF3

H2N

HO

NH2

OHHO2C CO2H O

O

O

8

O O

HO

H2N

OH

NH2 NHO2C CO2H

O

—

10

F3C CF3

H2N

HO

NH2

OHO2S

HO2C CO2H O

OH

TABLE 2. Average shear force of polybenzoxazole bonded to a titanium nitridesurface.

PolybenzoxazoleAdhesive ShearForce (N/mm2) Coating Type

3 17.94 Spray4 20.67 Spin coat5 18.69 Spray

TABLE 1. (Continued)

22 Use of Polybenzoxazoles (PBOS) for Adhesion

NOTES

1. In an earlier investigation by the author [1] phenyl-linked polyoxazole deri-vatives, (I), were prepared and converted into cyanates by reacting withisocyanate derivates. Cyanate derivatives were used as dielectrics because oftheir good adhesive and filling properties.

O O

ON N

O

O O

HOH2N N

O

O

O

O N

N

O

(I)

a

b

2. Polyhydroxyamides, (II), prepared by Halik [2] were converted intopolybenzoxazole-based adhesives by curing at 300�C to 350�C. Polyhydroxy-amides, (III), were also prepared and converted into the corresponding

TABLE 3. Average shear force of polybenzoxazole bonded to a tantalum nitridesurface.


6 17.03 Spray8 18.47 Spray10 17.26 Spin coat

TABLE 4. Average shear force of polybenzoxazole bonded to a copper surface.


Step 1 product 21.28 Brushing3 20.06 Powder melting

Notes 23

polybenzoxazoles by curing 60 minutes at 425�C.

a

a

CO O

NH

CH

OH

HN

OH

O

(II)

OH

HN

OH

NH

O

O

NH

O

(III)

3. Hall [4] prepared crossliked polymers that were effective as adhesives by UVcuring of the neutralization product of diallylamine with selected carboxylicacids, (IV). Additional UV curable diallyl amine adhesives, (V), were preparedby Milne [5].

NH2 O2C

CO2H

(IV)

O O

N N

(V)

References

1. A. Walter et al., US Patent 6,824,642 (November 30, 2004)2. M. Halik et al., US Patent 7,064,176 (June 20, 2006)3. R. Sezi et al., US Patent 7,108,807 (September 19, 2006)4. A.W. Hall, US Patent 7,112, 639 (September 26, 2006)5. P.E. Milne et al., US Patent 7,026,419 (April 11, 2006)

24 Use of Polybenzoxazoles (PBOS) for Adhesion

III. BIOACTIVE

A. Bioabsorbables

Title: Segmented Urea and Siloxane Copolymersand Their Preparation Methods

Author: I. Yilgor et al., US Patent 7,262,260 (August 28, 2007)Assignee: Virginia Tech Intellectual Properties, Inc. (Blacksburg, VA)

SIGNIFICANCE

Copolymersand terpolymerscontaining siloxane-urea segmentshavebeenpreparedbycondensing a,o-N-methylaminopropyl terminated polydimethyl-siloxane with bis(4-isocyanatocyclohexyl) methane then postreacting with a,o-N-methylaminopropylterminated polypropylene oxide. Polymeric biocompatible materials including mem-branes and adhesives obtained in this process had controlled modulus, high ultimatetensile strength, and favorable refractive index properties.

REACTION

ba

aOSi

O NH

NH

OSi

O NH

NH

NH

O

NH

NH

OHN

NH

HNPPO

O

O

PPO

i

i: a,o�N-Methylaminopropyl terminated polydimethylsiloxane, isopropylamine, bis(4-isocyanatocyclohexyl) methane, a,o�N-methylaminopropyl terminated poly-propylene oxide


25

EXPERIMENTAL

Preparation of Poly(Dimethylsiloxane-Urea-Propylene Oxide)

Amixture consisting of a,o-N-methylaminopropyl terminated polydimethylsiloxane(80mol%) having a Mn of 2500 daltons dissolved in isopropylamine and bis(4-isocyanatocyclohexyl)-methane (20mol%) were mixed at ambient temperature thenposttreated with a,o-N-methylaminopropyl terminated polypropylene oxide. Thereaction extent was determined by FTIR spectroscopy by monitoring the disappear-ance of the isocyanate peak at 2270 cm�1. Reaction mixtures were always homoge-neous and usually clear throughout the reactions. No precipitation was observed.

DERIVATIVES AND TESTING

TABLE 1. Comparison of tensile properties of bis(4-isocyanatocyclohexyl)methane-basedpolydimethylsiloxane-urea and polyether/polydimethylsiloxane-urea segmentedcopolymers.

Entry Polyether

PolyetherMn

(daltons)

PolymerUrea

Content(wt%)

[Z](dL/g)

Modulus(MPa)

TensileStrength(MPa)

Elongation(%)

1 PDMS*1 2500 20 0.48 20.6 7.90 2053 PDMS 2500 19 0.54 21.3 8.30 1804 PEO 2000 20 0.81 4.30 25.4 13206 PEO 2000 19 0.72 4.50 26.5 1450

*1Polydimethylsiloxane

NOTES

1. High purity and highmolecular weight siloxane-urea/urethane copolymers, (I),were prepared byKuepfer [1] at ambient temperature using dibutyl tin diacetateas catalyst under anhydrous conditions. Additional siloxane-urea/urethanecopolymer derivatives were prepared by Schafer [2].

SiO

Si NH

OHN

O

NH

O

ONH

O

HN O

Oa

(I)

26 Segmented Urea and Siloxane Copolymers and Their Preparation Methods

2. Mixed urea block copolymers consisting of amine-terminated polydimethyl-siloxane were prepared by Sherman [3] and used as pressure sensitive adhe-sives. Other urea-based pressure sensitive adhesives containing polydimethyl-siloxanes are described by Zhou [4].

3. Brandt [5] prepared a nontacky spray on bandage—“patch in a bottle”—consisting of the reaction product of isophorone diisocyanate, polydimethyl-siloxane diamine having a Mn of 5400 daltons, and polypropylene oxidediamine having a Mn of 2000 daltons.

References

1. J. Kuepfer et al., US Patent 7,153,924 (December 26, 2006)2. O. Schafer et al., US Patent 7,026,424 (April 11, 2006)3. A.A. Sherman et al., US Patent 7,012,110 (March 14, 2006)4. Z. Zhou et al., US Patent 7,090,922 (August 15, 2006)5. A. Brandt et al., US Patent 6,958,154 (October 25, 2005)

Notes 27

Title: Functionalized Polymers for MedicalApplications

Author: A. Nathan, US Patent 7,253,248 (August 7, 2007)Assignee: Ethicon, Inc. (Somerville, NJ)

SIGNIFICANCE

Biodegradable and biocompatible a,b-unsaturated polyesters have been prepared bycondensing maleic anhydride with monoleoyl glycerol alone or in combination withmonoleoyl glycerol polyethylene glycol.Mercaptoethylaminewas then free radicallyincorporated into the a,b-unsaturated site using azobisisobutyronitrile. These poly-meric agents were used to preparemedical devices including sutures, staples, surgicaltacks, clips, and plates.

REACTION

O

OHOH

C17H30

O O

OO

C17H30

O

O O

OO

OO

O

OO

C17H30

O

O O

OO

OO

S S

H2N NH2

i ii

aa

i: Monoleoyl glycerol, maleic anhydrideii: DMF, 2,20-azobisisobutyronitrile, mercaptoethylamine

EXPERIMENTAL

1. Preparation of Poly(Monooleoyl Glyceride-co-Maleic Anhydride)

Areactorwas chargedwithmonoleoyl glycerol (142.6 g) and thenheated to 140�Candtreated with maleic anhydride (39.2 g). The reaction mixture was further heated to

28

190�C for 3 hours and cooled to ambient temperature. The product was isolated as apale yellow viscous liquid having a Mn of 1383 daltons and a Mw of 6435 daltons.

2. Addition of Mercaptoethylamine to Poly(MonooleoylGlyceride-co-Maleic Anhydride)

A mixture consisting of the Step 1 product (5.0 g), 0.85ml of mercaptoethylamine,11mlofDMF, and2,20-azobisisobutyronitrile (54mg)washeated to 60�Cfor24hoursand then cooled to ambient temperature. The polymer was diluted with 10ml ofEtOAc, washed once with 0.01M of NaOH, twice with brine, dried with MgSO4, andfiltered. The solution was concentrated, and the product was isolated as a yellow,transparent viscous liquid.

DERIVATIVES

NOTES

1. Poly(monostearoyl glycerol-co-succinate) containing upto 5% polyethyleneglycol, (I), was prepared by Arnold [1] and Nathan [2] and used as abioabsorbable and biocompatible polymeric wax. Poly(monostearoyl-glyceride-co-succinate) containing 5% N-methyl diethanoamine, (II), wasprepared by the author [3] in an earlier investigation.

OO

O

O

C17H35

O

O

OO 5 mol%

(I)

95 mol%

TABLE 1. Co-components used in reacting with maleic anhydride forming thecorresponding a,b-unsaturated polyester and corresponding physical properties.

Entry Co-component – 1 Co-Component – 2 Mn (daltons) Mw (daltons)

2 Monooleoyl glycerol 5mol% PEG-400 1122 56473 Monooleoyl glycerol 25mol% PEG-400 1230 4481

1HNMR (CD3Cl, ppm): d 0.86 triplet (3H), 1.26 multiplet (22H), 1.61 multiplet (2H), 2.00 multiplet (4H),2.30 multiplet (2H), 2.80 multiplet (2H), 3.60 multiplet (2H), 4.20 multiplet (3H), 5.38 multiplet(2H); no a,b-unsaturated ester remaining in the polymer

FTIR (ZnS, cm�1): 3346, 2920, 2860, 1745, 1660, 1456, 1168

Notes 29

95 mol%OO

O

O

C17H35

O

O

ONH

O

(II)

5 mol%

2. The biodegradable and biocompatible polymer poly(monostearoyl glyceride-co-succinate-co-caprolactone), (III), was prepared by Nathan [4] and used inmedical devices.

O NH

O

O

O

O

C17H35

O

O

(III)

a

3. Block copolymers, (IV), consisting of succinic acid coupled with propyleneglycol and then capped with hexamethylene diisocyanate and reacted withpolylactic acid were prepared by Imamura [5] and used as biodegradablecontainers.

OOO

OO

OHN

O

HN O

O

O

O

O

ac

(IV)

b

References

1. S. Arnold et al., US Patent 7,034,037 (April 25, 2006)2. A. Nathan et al., US Patent 7,030,127 (April 18, 2006)3. A. Nathan et al., US Patent 6,866,860 (March 15, 2005)4. A. Nathan et al., US Patent 6,967,234 (November 22, 2005)5. S. Imamura et al., US Patent 7,223,815 (May 29, 2007)

30 Functionalized Polymers for Medical Applications

Title: Degradable Polyacetal Polymers

Author: S. J. Brocchini et al., US Patent 7,220,414 (May 22, 2007)Assignee: A. P. Pharma, Inc. (Redwood City, CA)

SIGNIFICANCE

Polyacetal polymers containing polyethylene glycol have been prepared whichare stable at physiological pH but which readily degrade at lower pH’s. BoltonHunter reagent conjugates prepared from these materials showed a favorable bio-distribution profile of the 125I product.

REACTION

a

a

a

HO OH

NH2

HO OH

HN

O

OO

HN

O

O

OOOO

OO

3 360

O

NH2

OOOO

OO

3 360

O

HN

OOOO

OO

3 360O

I

HO

I

i ii

iiiiv

125

125

i: Sodium hydroxide, N-(9-fluorenylmethoxycarbonyl)chloride, CH2Cl2ii: Polyethylene glycol, p-toluene sulfonic acid, divinyl tri(ethylene glycol),THF,

triethylamine

31

iii: Piperidine, CH2Cl2iv: N-Succinimidyl 3-(4-hydroxy 5-[125I]iodophenyl) propionate), benzene, DMF,

sodium hydroxide

EXPERIMENTAL

1. Preparation of N-(9-Fluorenylmethoxycarbonyl) Intermediate

A reactor containing 2-amino-1,3-propanediol (10.0mmol) and 25ml of 1M NaOHwas cooled to 0.2�C and treated with N-(9-fluorenylmethoxycarbonyl)chloride(13.1mmol) dissolved in 10ml of CH2Cl2 over a 1 hour period. The solution wasstirred for 1 hour at 0�C and 4 hours at ambient temperature. The organic solvent wasevaporated and the aqueous residue poured into 70ml of EtOAc. The organic phasewas isolated, washed with 5% aqueous HCl, dilute NaHCO3, brine, and dried. Themixture was concentrated, the residue re-crystallized in chloroform, and the productwas isolated.

2. Preparation of Polyether N-(9-Fluorenylmethoxycarbonyl) Intermediate

Polyethylene glycol having a Mn of 3400 daltons (1.47mmol) and p-toluene sulfonicacid (0.012 g) were added to a 100-ml flask and heated to 80�C to 90�C for 3 hours at0.5 to 1.0 torr. Themixturewas cooled and treatedwith the Step 1 product (1.47mmol)and 10.0ml of THF; it was further treated with divinyl tri(ethylene glycol)(2.94mmol) in 10ml of THF. This reaction mixture was stirred for 2 hoursat ambient temperature and then treated with 0.3ml triethylamine. The reactionmixturewasprecipitated in 100mlof hexane, and theproductwas isolatedhavingaMn

of 25,000 daltons.

3. Preparation of Polyether Acetal Amine Intermediate

A solution of the Step 2 product (2.050 g) in 20% piperidine containing 10ml ofCH2Cl2 was stirred at ambient temperature and monitored by thin layer chromatog-raphy. The amino functionalized polyacetal was then isolated by partitioning thepiperidine into hexane and next CH2Cl2. The residue was dissolved in THF, and thepolymer was precipitated by pouring into 100ml of hexane. The product was isolatedhaving a Mn of 23,000 daltons.

4. Preparation of 125I Polyether Acetal

The Step 3 product (50mg) was dissolved in 10mg/ml of 0.1M borate with a pH 8.5buffer by theadditionofa small amountofNaOHand then treatedwithN-succinimidyl3-(4-hydroxy5-[125I]iodophenyl) propionate), 500 mCi, dissolved in benzene contain-ing DMF, and stirred for 15 minutes at ambient temperature. The mixture was diluted

32 Degradable Polyacetal Polymers

with phosphate buffer solution to 10ml, transferred to dialysis tubing, and dialyzedagainst water until no radioactivity was found in the dialysate, and the product wasisolated.

DERIVATIVES

Three additional divinyl ether derivatives were prepared as illustrated below.

O NH

HN

O

NH

O

O

O NH

O

NH

O

O

O NH

O

NH

O

O

NH2

NOTES

1. Bleach resistant polyacetals consisting of 98% trioxane and 2% dioxolane wasprepared by Notorgiacomo [1] and used in molding compositions.

2. Branched polyformals and copolyformals, (I), were prepared Heuer [2] andused in the production of molded articles.

O O O Oa b c(I)

3. Polyvinyl butyral resins, (II), were prepared by Miyake [3] and used in heat-developable photosensitive material film.

O

O

(II)

a

b

Notes 33

4. Polyacetal resin compositions having excellent wear resistance were pre-pared by Kim [4]. These resins consisted of polyoxymethylene polymer,ethylene vinylacetate, melamine, triethyleneglycol-bis-3-(3-t-butyl-4-hydroxy-5-methylphenyl)-propionate, and hydroxyl pentaerythritol fatty acid ester.

References

1. V.J. Notorgiacomo et al., US Patent 7,223,809 (May 29, 2007)2. H.-W. Heuer et al., US Patent 7,208,564 (April 24, 2007) and US Patent 7,199,208 (April 3, 2007)3. Y. Miyake, US Patent 7,176,257 (February 13, 2007)4. T.-K. Kim et al., US Patent 7,098,262 (August 29, 2006)

34 Degradable Polyacetal Polymers

Title: Lactone Bearing Absorbable Polymers

Author: F. X Ingnatious, US Patent 7,205,378 (April 17, 2007)Assignee: Societe de Conseils de Recherches et d’Applications Scientifiques

(Paris, FR)

SIGNIFICANCE

A procedure for the slow and sustained release of the growth hormone inhibitorLanreotide� is described. The method entails incorporating Lanreotide� to theisocitric acid lactone component on the backbone of a polyester block copolymerusing sodium hydroxide as the saponification agent.

REACTION

aO

HO2C CO2H

O

O

O

O

O

O

OHO OH

O

O

O

O

O

OHO O

O

O

O

OH

R

R

O

O

O

O

O

OHO O

O

O

O

OH

R

R

Lanreotide(R)

a b

a b

i ii

iii

R = H or CH3

NH3

O

Na

Note 1

i: Propanediol, benzeneii: dl-Lactide, glycolide, stannous octanoate, tolueneiii: Sodium hydroxide, acetone, Lanreotide�

35

EXPERIMENTAL

1. Preparation of Poly(isocitric Acid Lactone-co-Propanediol)

A reactor containing a Dean–Stark trap was charged with isocitric acid lactone(14.3mmol), propanediol (15.7mmol), and benzene was then refluxed at 90�Covernight. The mixture was concentrated and a viscous liquid isolated that solidifiedon cooling.

2. Preparation of Poly[(Isocitric Acid Lactone-co-Propanediol)-block-(Glycolide-co-Lactide)]

The reaction vessel containing the Step 1 product was transferred to a dry box andtreated with dl-lactide (25.2 g), glycolide (7.25 g), and 0.2ml of stannous octanoatesolution in toluene. The polymerization reaction was performed at 160�C for 8 hoursand then quenched in liquid nitrogen. The polymer was isolated, dissolved in acetone,and precipitated in cold water, with the product isolated having a Mn of 3790 daltonsand Mw of 7040 daltons.

3. Preparation of Poly[(Isocitric Acid Lactone-co-Propanediol)-block-(Glycolide-co-Lactide)] Ionically Complexed with LanreotideR

The Step 2 product (1 g) was dissolved in acetone and treated with 0.45ml of 1MNaOH, then stirred for 20 minutes, and further treated with Lanreotide� (0.29 g)dissolved in 2ml of 1:1 acetone/water. The polymer solution was left stirring for2 hours and then precipitated in cold water. The product was filtered and dried; theproduct isolated had a 17.6% nitrogen content.

DERIVATIVES

No additional derivatives were prepared.

TESTING

In vivo Testing

The Step 3 product was ground and sieved with a mortar and pestle and passedthrough a 125 m sieve. Rats were administered 6.75mg of the experimental agentby injection in a medium consisting of 2% carboxymethylcellulose, 1% Tween20�, and saline. Blood samples were collected at various time intervals, and theplasma levels of Lanreotide� was determined by radioimmuno assay. Test resultsfor are provided in Table 1.

36 Lactone Bearing Absorbable Polymers

NOTES

1. Lanreotide� has the formula H-b-D-Nal-Cys-Tyr-D-Trp-Lys-Val-Cys-Thr-NH2, where, the two Cys are bonded by a disulfide bond. Lanreotide� is asomatostatin analogue that inhibits the release of growth hormones.

2. In a subsequent investigation by the author [1] biodegradable microparticlessuch as poly(l-lactic-co-glycolic-co-d,l-malic acid), (I), were prepared andused as a drug delivery agent for the acetate salt of Lanreotide�.

baOO

O

O

R O

R O O

O

Lanreotide NH3

R = H or CH3

(I)

OAc

3. Shalaby [2] prepared ionic molecular conjugates of the hydrolyzeddrug delivery agent chitosan and Somatuline�, (II), in the treatment ofacromegaly.

TABLE 1. In vivo test results for Lanreotide� in plasma levels using radioimmunoassay.

Sample

Lanreotide�

Levels after6 Hours(ng/ml)

Lanreotide�

Levels after8 Days (ng/ml)

Lanreotide�

Levels after22 Days (ng/ml)

Step 3 product 21 – 4.5 30.2 – 7.5 0.05 – 0.02Entry 4*1 24.4 – 5.2 20.8 – 7.2 0.141– 0.09*1Entry 4 was obtained by replacing NaOH with an equivalent amount of NaHCO3 in Step 3.

Notes 37

aO

OO

O

HO

NH3

OH

OH

NH3

CO2OH

HO

O

HO

CO2

NH3

OH

CO2

CO2

CO2

CO2Somatuline

NH3

NH3

NH3SomatulineSomatuline

(II)4. Li [3] prepared ionic complexes of aminated polyrotaxanes with bulky bio-

cleavable end caps as a method for delivering nucleic acids.

5. Polyfunctional monomers, (III), prepared by Li [4] were used to synthesizecationic polymers having degradable crosslinks for therapy involving thedelivery of nucleic acids into cells.

O

O O

OO

O O

O

O

O

O

O(III)

6. Leong [5] and Dang [6] used cyclic phosphate monomers, (IV), and eitherlactide or caprolactone monomers to prepared phosphate based biodegradablepolymers, (V), illustrated below, that were then converted into microspheresand used as drug deliver agents for anti-neoplastic medicaments.

OP

O

H3CO O

OO

PO

O

O

O

O

OCH3

(IV) (V)

ia b

i: d,l-Lactide, benzene, methanol

38 Lactone Bearing Absorbable Polymers

References

1. F.X Ingnatious et al., US Patent Application 2006-0121120 (June 8, 2006)2. S.W. Shalaby et al., US Patent 7,005,420 (February 28, 2006)3. J. Li et al., US Patent Application 2006-0211643 (September 21, 2006)4. S. Li et al., US Patent 7,163,677 (January 16, 2007)5. K.W. Leong et al., US Patent 6,805,876 (October 19, 2004)6. W. Dang et al., US Patent 6,800,672 (October 5, 2004)

Notes 39

B. Contact Lenses

Title: Low Polydispersity Poly-HEMA Compositions

Author: T. Kindt-Larsen et al., US Patent 7,256,246 (August 14, 2007)Assignee: Johnson & Johnson Vision Care, Inc (Jacksonville, FL)

SIGNIFICANCE

Cross-linked pre-polymers having fractionalized molecular weights between 35,000and 70,000 daltons with polydispersity indexes of less than 3.4 have been prepared bythe free radical addition of 2-hydroxethyl methacrylate, HEMA,with 2%methacrylicacidorglycerolmethacrylate.Oncecrosslinked, thesematerials are particularlyusefulas contact lenses because of their limited shrinkage and expansion.

REACTION

O

O

OH

O O OO

OH O O

O OHi ii

Fractionalization

a b c d

Note 2Note 1

i: Ethanol, dodecyl mercaptan, methacrylic acid, 2,20-azobis (2-methylbutyronitrile)ii: Ethanol, hexane

EXPERIMENTAL

1. Preparation of Poly(2-Hydroxethyl Methacrylate-co-Methacrylic Acid)(poly-HEMA)

A 5-liter stainless steel reactor was charged with ethanol (1911.6 g), 2-hydroxethylmethacrylate (1056.6 g), dodecyl mercaptan (3.00 g), and methacrylic acid (21.00 g)

40

at 25�C. The temperature was raised to 68�C and then the mixture treated with2,20-azobis(2-methylbutyronitrile) (7.50 g). After heating for 18 hours at 68�Cthe mixture was heated to 80�C an additional 22 hours then cooled. The productwas isolated with a solid content of 37.2% with a Mn of 68,000 daltons and a PDIof 3.75.

2. Fractionalization of Poly(2-HydroxethylMethacrylate-co-Methacrylic Acid)

Step 1 Fractionalization ProcessThe Step 1 product was initially diluted with ethanol to give a 10% solution of poly-HEMA in ethanol. The solution initially became turbid at 24�C and clear andhomogeneous at 40�C. The solution was cooled to 21�C; the solution then separatedinto two clear phases after three days. The bottom fraction had a molecular weight of144,000 daltonswith a polydispersity of 3.34 andwas discarded. The top soluble layerhad amolecularweight of 64,000 daltonswith a polydispersity of 2.28 andwas furtherfractionated at 8�C. After 24 hours the solution was again separated into two phases.The bottom phase constituted 15 vol% of the total solution and contained 35.7 wt% ofpoly-HEMAhavingamolecularweight of 83,800daltonswith apolydispersity of 2.18that was further fractionated.

Step 2 Fractionalization ProcessAfter addition of 2% hexane to the lower layer, the solution had a cloud point at31�C. The mixture was heated to 40�C to make it homogeneous, and then it stoodat 28�C for five days before it separated into two clear phases. The top phasecontained 77.1% of the polymer and was siphoned off, and the bottom phase wasdiscarded.

Step 3 Fractionalization ProcessThe amount of hexane in the top phase was adjusted to 7%, which resulted in a cloudpoint of 54�C. The solution was re-heated to 57�C to make it homogeneous, and afterfour days at 29�C the solution separated into two clear phases. The top phasecontaining the low molecular weight fraction of the polymer was siphoned off,and the bottom phase was given a third fractionation.

Step 4 Fractionalization ProcessIn this procedure the hexane concentration was adjusted to 8%, and the solution stoodfor four days at 30�C. The top phase containing the low molecular weight fraction ofthe polymer was siphoned off, and the lower retained as the Step 1 fractionalizedproduct.

Experimental 41

FRACTIONALIZATION PROFILE

DERIVATIVES

Poly(2-hydroxethyl methacrylate-co-glycerol methacrylate) was also prepared hav-ing a molecular weight of 41,000 daltons with a PDI of 2.80.

NOTES

1. The preparation of molded contact lenses using the polymers of the currentinvention are described by the author [1] in an earlier investigation.

2. Ford [2] determined that isopropanol, dipropylene glycol dimethyl ether,dipropylene glycol methyl ether acetate, dipropylene glycol methyl ether, andtripropylene glycol methyl ether were also effective in fractionating analoguesof the current invention.

3. Wettable polymer silicon hydrogels were prepared by Laredo, (I), [3] andZanini, (II), [4], respectively, and used in contact lenses.

O

O

NH

O

O

OSi

OO N

H

O

NHO

OCH2CF2(OCF2)aCF326

(I)

Si O OSi

OSi(CH3)3

(H3C)3SiO

OHO

OH

(H3C)3SiO

OSi(CH3)3

(II)

TABLE 1. Fractionalization effectiveness for poly(2-hydroxethyl methacrylate-co-methacrylic acid) using selected extraction solvents.

Entry

FractionalizationTemperature

(�C)Fractionalization

Solvent

MolecularWeight(daltons) PDI

5 82 2-Propanol 35,000 3.46 78 2-Propanol 40,000 3.47 74 Ethanol 50,000 2.68 72 Ethanol 60,000 3.69 68 Ethanol 70,000 3.3

42 Low Polydispersity Poly-HEMA Compositions

4. Biocompatible contact lenses having high oxygen and water permeability wereprepared by Nicolson [5] by reacting the polysiloxane macromonomer, (III),with ethylene glycol, and 2% 2-hydroxyethyl methacrylate.

OSi

OOHN

O

OCN

OHN

O

NCO

(III)

a b

References

1. T. Kindt-Larsen et al., US Patent 6,846,892 (January 25, 2005)2. J.D. Ford et al., US Patent 7,112,652 (September 26, 2006)3. W.R. Laredo et al., US Patent 7,249,848 (July 31, 2007)4. D. Zanini et al., US Patent 7,214,809 (May 8, 2007)5. P.C. Nicolson et al., US Patent 7,045,248 (October 4, 2005)

Notes 43

C. Drug Delivery

Title: Amphiphilic Block Copolymersand Nanoparticles Comprising the Same

Author: M.-F. Hsieh et al., US Patent Application 2007-0104654(May 10, 2007)

Assignee: Industrial Technology Research Institute (Hsinchu, TW)

SIGNIFICANCE

A biocompatible and biodegradable amphiphilic block copolymer consisting ofhydrophobic and hydrophilic segments containing zwitterions has been prepared.This agent is useful as a drug delivery agent for water-insoluble drugs, includinggrowth factors and genes, and in cosmetic formulations.

REACTION

O

O

H3COO O

H H3COO O

P O

O

O

H3COO O

PO

O

ON(CH3)3a b

aa biii

iii

O O

O

ivNanoparticles

i: Poly(ethylene glycol), stannous 2-ethylhexanoateii: Triethylamine, 2-chloro-2-oxo-1,3,2-dioxaphospholane, CH2Cl2iii: Acetonitrile, trimethylamine, CH2Cl2

EXPERIMENTAL

1. Preparation of Poly(Ethylene Glycol-b-Valerolactone)

A glass reactor was charged with poly(ethylene glycol) (60g; 5000 daltons) andd-valerolactone (12g), which was gradually heated until dissolved. This mixture was

44

then treatedwith 0.38ml of stannous 2-ethylhexanoate and heated for 8 hours at 160�C.Thereafter themixturewasdissolved inCH2Cl2 andprecipitatedbyaddingdiethyl ether.The white precipitate was washed and dried, and the block copolymer was isolated.

2. Preparation of Poly(Ethylene Glycol-b-Valerolactone)-2-oxo-1,3,2-Dioxaphospholane

The Step 1 product (5 g) and triethylamine (0.43 g) were dissolved in 70ml of CH2Cl2at 0�C, then added dropwise to 2-chloro-2-oxo-1,3,2-dioxaphospholane (3.5 g) dis-solved in 30ml of CH2Cl2 and stirred at 0

�C for 6 hours. The resulting solution waswarmed to ambient temperature, filtered through 0.45 mm filter paper, and concen-trated, and the product was isolated.

3. Preparation of Poly(Ethylene Glycol-b-Valerolactone)-Trimethylammonium Phosphate

The Step 2 product was dissolved in 70ml of acetonitrile at ambient temperature andthen treated with 10ml of 33% trimethylamine in ethanol and heated for 24 hours at60�C. The solution was next concentrated and extracted three times with CH2Cl2/water. After re-concentrating and drying, the product was isolated as a white solid.

4. Preparation of Polymeric Nanoparticles

Tenmilligrams of the Step 3 product were dissolved in 1ml of dimethyl sulfoxide andthen removed by freeze-drying. Thereafter 1ml of 10% sucrose was added to thehydrate, and the freeze-dried solids were re-dissolved to form a suspension. Afterultra-sonicating for 10 minutes, polymer nanoparticles were formed.

DERIVATIVES

Two additional derivatives were prepared as illustrated below.

H3COO

O

O

a bNHR

H2C N SO3

O

O

HCCO2H

N

N

R________________

Derivatives 45

TESTING

Micelle Formation

A solution of 10mg of a selected polymer dissolved in 1ml THFwas gradually addedto 30ml deionized water and stirred. The solution was placed in a dialysis membranefor 24 hours to form a micelle solution. Then the 3 to 5ml micelle of the solution wasplaced in an acrylic cuvette to measure micelle sizes and their distribution by photoncorrelation spectroscopy. Testing results are provided in Table 1.

NOTES

1. Amphiphilic block copolymers consisting of polyethylene glycol and poly-lactide, (I), were prepared by Seo [1] and used as drug delivery agents forPaclitaxel�.

H3COO

OO

O

O

O

44 24

(I)

2. Block cationomers, (II), consisting of polyisobutylene and poly(2-dimethyl-amino)ethyl methacrylate) were prepared by Kennedy [2] and used as timedrelease agents for pharmaceuticals.

OBr

OO

N(CH3)3 I(II)

aPolyisobutylene

TABLE 1. Effect of terminus and block segment compositionin poly(ethylene-glycol-b-valerolactone) on CMC formation.

Polymer TerminusPEO Block(daltons)

Lactone Block(daltons)

CMC(10�2 wt%)

Trimethylammonium phosphate 5000 1900 3.265000 1100 17.92

Dimethylammonium sulfate 2000 1000 1.462000 2000 4.475000 2500 3.955000 3700 7.76

46 Amphiphilic Block Copolymers and Nanoparticles Comprising the Same

3. Wang [3] prepared the amphiphilic biocompatible cyclodextrin graft polymer,poly(ethylene glycol-g-cyclodextrin), (III), containing modified cyclodextrinwhich was used as a bioactive drug delivery agent.

OO

NHO

SS

HNCyclodextrin

a b

(III)

4. Dai [4] modified oxidized carbon nanotubes, (IV), and thesewere subsequentlyused as transporters for the delivery of biologically active agents into cells.

aNH

O

ONH

O

S

NH

HNO

H

H

Oxidized nanotube(IV)

References

1. M.-H. Seo et al., US Patent 7,217,770 (May 15, 2007)2. J.P. Kennedy et al., US Patent 7,196,142 (March 27, 2007)3. L. Wang et al., US Patent 7,141,540 (November 28, 2006)4. H. Dai et al., US Patent Application 2006-0275371 (December 7, 2006)

Notes 47

Title: Heterofunctional Copolymers of Glyceroland Polyethylene Glycol, Their Conjugatesand Compositions

Author: F. Ignatious, US Patent 7,196,145 (March 27, 2007)Assignee: SmithKline Beecham Corporation (Philadephia, PA)

SIGNIFICANCE

Block- and copolymers consisting of ethylene oxide and glycidol were preparedanionically containing an d-hydroxy butyric acid terminus. The acidic terminus wasthen converted into a-succinimidyl and conjugated with the protein, Grob-t, and thelipid, di-stearoyl phosphatidyl-ethanolamine.

REACTION

OO O

O

O OH

OH

O

HO

O

OO O

O

O OH

OH

O

ON

O

O

OO O

O

O OH

OH

HN

OO

O O

O

O OH

OH

t-Grob-HN

ODi-stearoyl phosphatidyl O

i ii

iii iv

b

aa b

a

b

a b

Note 1

i: 4-Hydroxy butyric acid-sodium salt, potassium, glycidol, THFii: N,N0-Dicyclohexyl carbodiimide, N-hydroxysuccinimide, CH2Cl2iii: Grob-t, Dulbeccu’s phosphate, hydrochloric acidiv: Di-stearoyl phosphatidyl-ethanolamine, triethylamine, CCl3H

48

EXPERIMENTAL

1. Preparation of a-Carboxyl-d-Hydroxyl Poly(Ethylene Oxide-block-Polyglycidol)

A reactor was charged with 4-hydroxy butyric acid-sodium salt (0.045mol) andpotassium (0.046mol) in 400ml of THF, refluxed 12 hours, and transferred to ahigh-pressure reactor. The reactor temperature was lowered to �10�C and treatedwith 95ml of ethylene oxide using a stainless steel capillary and the solutionstirred at 50�C for 24 hours. Glycidol previously dissolved in THF was slowlyadded through a stainless steel capillary, and the solution was stirred at 50 �C for12 hours. The reactor was cooled, and the contents were poured into 5ml 35%hydrochloric acid whereupon KCl precipitated. The solution was filtered. Thenthe filtrate, was precipitated in cold 2-propanol containing 20% hexanes and alight yellow precipitate was isolated. The dried residue was dissolved in 500mldistilled water and extracted with CH2Cl2 to remove the unreacted initiator. Afterremoval of the solvent, the product was washed twice with water and isolated.

2. Preparation of d-Hydroxy-a-SuccinimidylPoly(Ethylene Oxide-block-Polyglycidol)

A reactor was charged with the Step 1 product (0.011mol), N,N0-dicyclohexylcarbo-diimide (0.0176mol), andN-hydroxysuccinimide (0.0176mol) dissolved in 150ml ofCH2Cl2 and then stirred overnight at ambient temperature. A cloudy heterogeneouswhite formed, which was removed by filtration and the filtrate concentrated. Theresidue was precipitated in cold diethyl ether and the product isolated after re-crystallization with ethanol.

3. Conjugation of d-Hydroxy-a-SuccinimidylPoly(Ethylene Oxide-block-Glycidol) to Grob-t

The Step 2 product was added to a 2.5mg/ml solution of Grob-t in Dulbeccu’sphosphate buffered at pH 7.0 at a molar ratio of the Step 2 product/protein 2:1, 4:1, or10:1, respectively. The reaction was stirred for 3 hours at 40�C and quenched with0.5M glycine, and then the pHwas lowered to 4.5 with 3M of hydrochloric acid. Theconjugate was isolated after purification by diafiltration.

4. Conjugation of d-Hydroxy-a-SuccinimidylPoly(Ethylene Oxide-block-Polyglycidol) to a Lipid

The Step 2 product (0.8mmol) dissolved in CCl3H was treated with di-stearoylphosphatidyl-ethanolamine (0.70mmol) containing triethylamine (1.4mmol) andheated to 40�C to 45�C for 2 hours. The conjugate was isolated after purificationby diafiltration.

Experimental 49

DERIVATIVES

Poly(ethylene oxide-co-glycidol) was also prepared.

NOTES

1. In a subsequent investigation by the author [1], the aldehyde-terminated Step 1analogue was prepared and used as a conjugate with selected biomolecules.

OO O

O

O OH

OH

H

Oba

OH

(I)2. Miyanaga [2] preparedmoderate molecular weight polyglycidol ethers, (II), by

polymerizing the corresponding glycidol ether with samarium triisopropoxide,samarium tris(tetramethyl heptanedionate), and yttrium tris(tetramethyl hep-tanedionate) with methyl aluminoxane.

O

O

R

a R aOH 760CH3 700Steryl 820CH2C8F17 250

(II)3. Polyglycidol containing cyanoethyl, (III), trimethylsilylacetyl, and cyanoben-

zoyl termini were prepared by Sata [3] and used as a component in ion-conductive polymer electrolyte compositions.

OONC

OCN

(III)

CN

a

References

1. F. Ignatious et al., US Patent Application 2005-0048650 (March 3, 2005)2. S. Miyanaga et al., US Patent 6,906,167 (June 14, 2005) and US Patent 6,800,723 (October 5, 2004)3. T. Sato, US Patent 6,472,106 (October 29, 2002) and US Patent 6,469,107 (October 22, 2002)

50 Heterofunctional Copolymers of Glycerol and Polyethylene Glycol

Title: Polyalkylene Glycol Acid Additives

Author: P. S. Bailon et al., US Patent 7,193,031 (March 20, 2007)Assignee: Hoffmann-La Roche, Inc. (Nutley, NJ)

SIGNIFICANCE

A new class of activated biological conjugates has been prepared. Methoxy polyeth-ylene glycol having a molecular weight of 2000 daltons was converted into thecorresponding valeric acid succinimidyl ester then conjugated with AZT, T-20polypeptide, and human erythropoietin. These conjugates materials produced biolog-ically active agents useful in pharmaceutical applications.

REACTION

H3COO

OOH H3CO

OO

O OC2H5

O

H3COO

OO OH

OH3CO

OO

O O

ON

O

O

H3COO

OO

O

O

NO

HN

O

i ii

iiiiv

20

20 20

2020

Note 1

i: Toluene, ethyl-5-bromovalerateii: Sodium hydroxideiii: N-hydroxy-succinimide, dicyclohexylcarbodiimideiv: 30-Azido-30-deoxy-thymidine, 1-hydroxybenzotriazole, (4-dimethylamino)pyr-

idine, dicyclohexylcarbodiimide

51

EXPERIMENTAL

1. Preparation of Methoxy-Polyethylene Glycol Valeric Ethyl Ester

Areactorwas chargedwith polyethyleneglycol (0.5mol;Mn10,000), and treatedwith50ml of toluene, and azeotropically dried by refluxing for 2 hours. The resultingmixture was dissolved in 30ml of THF and treated dropwise with sodium hydride(5mmol) dissolved in 20ml of THF and refluxed overnight. This mixture was thentreated with ethyl-5-bromovalerate (5mmol) and refluxed overnight and concentrat-ed. The residue was precipitated by the addition of 2-propanol/diethyl ether, 1:1, andthen filtered to yield 4.5 g of isolated product.

2. Preparation of Methoxy-Polyethylene Glycol Valeric Acid

The Step 1 product (4 g) was dissolved in 100ml of 1MNaOH and stirred at ambienttemperature overnight. The pH of the mixture was adjusted to 2.5 using 6Mhydrochloric acid; the mixture extracted using 50ml, 40ml, and 30ml of CH2Cl2,dried with Na2SO4, and concentrated. The concentrate was precipitated in diethylether, and 3 g of product were isolated.

3. Preparation of Methoxy-Polyethylene Glycol Valeric AcidSuccinimidyl Ester

The Step 2 product (0.2mmol) was dissolved in 10ml of CH2Cl2 and treated withN-hydroxy-succinimide (0.41mmol) and dicyclohexylcarbodiimide (0.42mmol).The mixture was stirred overnight at ambient temperature and then filtered and con-centrated. The residuewas precipitated in 2-propanol/diethyl ether, 1:1, and filtered toyield 1.6 g of isolated product.

4. Preparation of PEG-AZT Conjugate

TheStep3product (0.02mmol)wasdissolved in2mlofDMFand treatedwith30-azido-30-deoxy-thymidine (0.04mmol), 1-hydroxybenzotriazole (0.04mmol), 4-dimethyla-minopyridine (0.042mmol), and dicyclohexylcarbodiimide (0.046mmol) and stirredovernightatambient temperature.Themixturewasfiltered,concentrated,precipitatedin2-propanol/diethyl ether, 1:1, and 0.17 g product was isolated.

1H-NMR (d6-DMSO) d 1.18 ppm (m, 3H, H1); 1.51 ppm (m, 2H, H9); 2.23 ppm (m, 1H, H4); 2.37 ppm (t,2H, H8); 3.21 ppm (s, H12); 3.5 ppm (s, H11). 4.2 ppm (m, 1H, H5); 6.12 ppm (m, H3, H6);7.45 ppm (s, 1H, H2); 11.35 ppm (br, 1H, H10)

1H-NMR (d6-DMSO) d 1.50 ppm (q, 2H, –CH2CH2–COOH); 2.21 ppm (t, 2H, –CH2CH2–COOH);3.21 ppm (s, –OCH3); 3.5 ppm (s, –O–CH2CH2–O–).

1H-NMR (d6-DMSO) d 1.58 1.67 ppm (m, 4H, –CH2CH2CH2–COO–); 2.69 ppm (t, 2H, –CH2CH2CH2–COO–); 2.81 ppm (s, 4H, NHS); 3.21 ppm (s, –OCH3); 3.5 ppm (s, –O–CH2CH2–O–).

52 Polyalkylene Glycol Acid Additives

DERIVATIVES

Two linear derivatives were prepared using the Step 4 product:

H3COO

OO G

O20

G = T-20 polypeptide, human erythropoietin

One branched derivative was also prepared.

H3COO

O

HN O

NHO

OH3CO

ON

O

O

20

20

NOTES

1. In subsequent investigations by the author [1] and Ley [2] the Step 4 productwas used as a conjugate for the granulocyte colony stimulating factor andKunitz domain polypeptides, respectively.

2. In other investigations by the author [3–5] an aldehyde terminated Step 4analogue (I) was prepared and used as conjugates for T-20 polypeptide, humanerythropoietin, and T1249 polypeptide, respectively.

H3COO

OO CHO

20

(I)

3. A blended composition for facilitating delivery of a biologically active conju-gatedmaterial was prepared byKabanov [6] and consisted of a block copolymerof ethylene oxide and acrylic acid salt of cetylpyridinium bromide, (II).

O

OO

N176 186

14(II)

4. Oh [7] prepared biodegradable lactide derivatives, (III), for conjugation withbiologically active agents for use as drug delivery agents.

Notes 53

aHOO

OO

O

O

O

O

O O

NO2(III)

5. Roberts [8] prepared polyethylene glycol 2-pyridylthioester derivatives, (IV)for conjugating with a-amine polypeptides.

H3COO

O S

O

Na(IV)

References

1. P.S. Bailon, US Patent Application 2005-0196378 (September 8, 2005)2. A.C. Ley, US Patent Application 2007-0041959 (February 22, 2007)3. P.S. Bailon et al., US Patent 7,049,415 (May 23, 2006)4. P.S. Bailon et al., US Patent 6,583,272 (June 24, 2003)5. P.S. Bailon et al., US Patent Application 2004-0171542 (September 2, 2004)6. A.V. Kabanov et al., US Patent 7,169,411 (January 30, 2007)7. J.E. Oh et al., US Patent 7,163,698 (January 16, 2007)8. J.H. Roberts et al., US Patent 7,078,496 (July 18, 2006)

54 Polyalkylene Glycol Acid Additives

Title: Thermosensitive Biodegradable Copolymer

Author: K.-Y. Chang et al., US Patent 7,179,867 (February 20, 2007)Assignee: Industrial Technology Research Institute (Hsinchu, TW)

SIGNIFICANCE

Amethod for increasing the biodegradability of low cytotoxic poly(ethylene glycol-b-(lactide-co-glycolide)) derivatives is described. The block copolymers are thermo-sensitive and can be easily implanted into the human body through injection for timedrelease of biologically active agents.

REACTION

H3COO

OOH

O

O

O

OO

O

H3COO

OO

O

O

Oa b c a b c 11

i ii

i: Lactide, methoxypolyethylene glycol, tin octanateii: Lauric acid, dicyclohexylcarbodiimide, CH2Cl2, CHCl3

EXPERIMENTAL

1. Preparation of Poly(Ethylene Glycol-b-(Lactide-co-Glycolide))

A reaction vessel was heated under nitrogen until the temperature reached 110�C andthen treated with lactide (50.0 g), glycolide (11.36 g), and methoxypolyethyleneglycol (24.02 g). After the monomers had melted, the contents were treated with0.05% tin octanate while the temperature slowly increased to 160�C for 9 hours; thevessel was then cooled to ambient temperature. The solid was dissolved in 80ml ofCH2Cl2, then poured into n-hexane/ether, 9:1, respectively, and stirred for 3 hours. Thesolution was next separated into two phases. The upper liquid was discarded, thebottom liquid was washed three times with n-hexane/diethyl ether, dried, and theproduct was isolated.

55

2. Preparation of Poly(Ethylene Glycol-b-(Lactide-co-Glycolide))Lauric Ester

Separate solutions of lauric acid (1.53 g) and dicyclohexylcarbodiimide (1.58 g) wereprepared by dissolving each into 30ml and 20ml of CH2Cl2, respectively. The twosolutions were mixed and stirred for 30 minutes and then added to the Step 1 product(10 g) dissolved in 50ml ofCHCl3. Thismixturewas treatedwith triethylamine (1.5 g)and stirred for 24 hours. The mixture was filtered and washed with n-hexane/diethylether, and the product was isolated after drying.

DERIVATIVES

The cholic acid analogue of the Step 1 product was also prepared.

H3COO

OO

O

O

a b c

OHHO

OH

O

TESTING

Gel Formation

Data collection were correlated with viscosity, time, thermocouple temperature, andrheometer torque. The rotation speed of the rheometer was adjusted so that torquevalue fell between 80% to 100%. The gel formation time was defined as the timeneeded for a sample to increase its viscosity up to 10000 cP from its starting viscosity.Viscosity testing results are provided in Table 1.

1H-NMR (CCl3D)d1.58 (d, J¼ 6.5Hz,H-4), 3.39 (s, –OCH3), 4.29 (m,H-1,2), 4.80 (m,H-5), 5.14 (m,H-3)1H-NMR (CCl3D)d0.86 (t, J¼ 6.8Hz,H-8), 1.23 (m,H-7), 1.58 (d, J¼ 6.5Hz,H-4), 2.38 (m,H-6), 3.39 (s,

–OCH3), 4.29 (m, H-1,2), 4.80 (m, H-5), 5.14 (m, H-3)

TABLE 1. Gel formation for the Step 2 product at varying times and temperatures.

Time(s)

Temperature(�C)

15 wt% SolutionViscosity (cp)



8 5 Fluid Fluid Fluid9 10 7,500 Fluid Fluid10 13 17,000 Fluid Fluid11 15 — Fluid Fluid12 18 — 7,500 5,00013 20 — >25,000 >25,000

56 Thermosensitive Biodegradable Copolymer

NOTES

1. Amphiphilic block copolymers consisting of polylactic acid or poly(lactic acid-b-glycolic acid) terminated with tocopherol or cholesterol were prepared bySeo [1] and used as drug delivery agents for Paclitaxel�.

2. Negatively charged amphiphilic block copolymers, (I), prepared by Seo [2]were effective as cationic drug carriers and provided the advantages ofincreased blood concentration and improved drug stability. Stable polymericmicelle-type drug compositions were prepared by Seo [3].

H3COO

OO

O

O

a b cX X = PO3

- Na+

= SO3- Na+

(I)

3. Thermosensitive block terpolymers consisting of poly(ethylene oxide-b-gly-colide-b-dl-lactide) were prepared by Piao [4] and used as drug delivery agentsfor insulin.

4. Block terpolymers prepared by Cheng [5] consisting of poly(N-isopropylacrylamide-b-polyethyleneoxide-b-N-isopropyl acrylamide), (II), were effec-tive as thermally reversible gels and used as subcutaneous implants, joint ortissue spacers, and biological filler for wrinkles or cosmetic implants. Metha-crylamide analogues were prepared by Gutowska [6].

aaO

OHN

O NH

113

(II)

References

1. M.H. Seo et al., US Patent Application 2005-0201972 (September 15, 2005)2. M.H. Seo et al., US Patent 6,890,560 (May 10, 2005)3. M.H. Seo et al., US Patent 7,217,770 (May 15, 2007)4. A-Z. Piao et al., US Patent 7,135,190 (November 14, 2006)5. Y.-L. Cheng et al., US Patent 7,160,931 (January 9, 2007)6. A. Gutowska, US Patent 6,979,464 (December 27, 2005)

Notes 57

Title: Polyamide Graft Copolymers

Author: A. B. Brennan et al., US Patent 7,169,853 (January 30, 2007)Assignee: University of Florida Research Foundation, Inc. (Gainesville, FL)

SIGNIFICANCE

Polyamide copolymers containing a macromolecular graft substituent were preparedby condensing 4-amino-benzoic acid or amixture of 1,4-phenylene diamine and adipicacid with 33%, 66%, and 90% S-(poly(n-butylacrylate)cysteine macromonomer. Asecond macromolecular monomer, S-(poly(methyl methacrylate)-cysteine, was alsoprepared and free radically copolymerized with perfluoromethyl methacrylate.

REACTION

O

On-C4H9

H2N OH

S

O

Poly(butyl acrylate)

NH

NH

S

OO


i iia

i: 2,20-Azobisisobutyronitrile, cysteine, THF, hydrochloric acidii: Triphenylphosphite, lithium chloride, pyridine, N-methyl-pyrrolidinone

EXPERIMENTAL

1. Preparation of S-(Poly(n-Butyl Acrylate)-Cysteine Macromonomer

The synthesis of poly(butyl acrylate) in the presence of cysteinewas carried out usingTHF, ethyl alcohol, and water where the molar ratio of butyl acrylate monomer/cysteine/azobisisobutyronitrile was 1000:30:1, respectively. The mixture was thenrefluxed for 6 hours at 65�Cwhile under constant stirring. After cooling the cysteine-modified product consisted of a white precipitate dispersed within poly(butyl acry-late). The precipitate was isolated from the polymer by dissolving the poly(butylacrylate) in THF and filtering.

58

2. Preparation of Poly(4-Amino-Benzoic Acid-co-(Cysteine-g-Poly(n-Butyl Acrylate))

The Step 1 product (1.37 g; Mn 26,000 daltons), 4-aminobenzoic acid (2.24mmol),triphenylphosphite (5mmol), and LiCl (0.09 g) were dissolved in 30ml N-methyl-pyrrolidinone/pyridine solution, 80:20, and heated to 100�C for 4 hours. The reactionmixturewas thenprecipitated in an excess ofwater/methanol, 1:1, filtered, andwashedwith methanol. The material was dried overnight under vacuum at 40�C, and theproduct was quantitatively isolated.

DERIVATIVES

TABLE 1. Selected comonomers reacted with cysteine macromolecular comonomerand corresponding macromolecular content.

CysteineMacromolecularComponent Comonomer(s)

MacromoleculeContent In

Copolymer (wt%)

Poly(butyl acrylate) 4-Amino-benzoic acid 33Poly(butyl acrylate) 4-Amino-benzoic acid 66Poly(butyl acrylate) 1,4-Phenylene diamine and adipic acid 66Poly(butyl acrylate) 1,4-Phenylene diamine/adipic acid 90Poly(methyl methacrylate) Perfluoromethyl methacrylate 65

Note: Polymers derived from 4-amino-benzoic acid were insoluble in all solvents except concentratedsulfuric acid. Elemental analysis for all experimental agents supplied by author.

NOTES

1. Polylysine-g-histidine derivatives, (I), prepared by Pack [1] were effective asbiocompatible endosomolytic delivery agents.

HN

NH2

O

HN

O

NH2

N

NH

a b

(I)

b = 10% –100%

Notes 59

2. Kaneko [2] prepared compatibilizing agents consisting of methacrylate, (II),and styryl, (III), macromolecules. These materials were polymerized usingtitanium-based Ziegler–Natta catalysts.

O

OR R = Polyethylene

Polypropylene Poly(ethylene-co-propylene)

O

R(II)

(III)

3. TEMPO-modified poly(ethylene-co-propylene-g-maleic anhydride), (IV), andpoly((ethylene-co-1-decene)-g-alkylacrylates), (V), were prepared byMatsugi[3] and used as polymer blend compatibilizing agents.

O

O

R

R = CH3 CH(CH3)CH2CH3

O O

O

O

N

O

O

N

(V)

(IV)

7

a b

a b

c

References

1. D.W. Pack et al., US Patent Application 2001-0006817 (July 5, 2001)2. H. Kaneko et al., US Patent 7,067,587 (June 27, 2006)3. T. Matsugi et al., US Patent 7,022,763 (April 4, 2006)

60 Polyamide Graft Copolymers

Title: Bioerodible Poly(Ortho Esters)from Dioxane-Based Di(Ketene Acetals)and Block Copolymers Containing Them

Author: J. Heller et al., US Patent 7,163,694 (January 16, 2007)Assignee: A.P. Pharma, Inc. (Redwood City, CA)

SIGNIFICANCE

Bioerodible poly(ortho ester) copolymers containing hydrophilic and hydrophobicblocks have been prepared from di(ketene acetals) and oligomeric diols. Thesematerials form micelles in aqueous solution making them useful as hydrophobicencapsulation agents or as bioerodible matrices for the sustained release ofmedicaments.

REACTION

HO

HO

O

C2H5C2H5

OH

OH

O

O

O

C2H5C2H5

O

O

O

O

O

C2H5C2H5

O

Oiii

iii

O

O

O

C2H5C2H5

O

O

O

C2H5

OO

C2H5

O

O

a33

i: Toluene, di(trimethylolpropane), acrolein diethyl acetal, pyridinium p-toluene-sulfonate, potassium t-butoxide

ii: Pentane, iron pentacarbonyl, triethylamineiii: Triethylene glycol, triethylene glycol monoglycolide, THF, salicylic acid,

triethylamine

61

EXPERIMENTAL

1. Preparation of Di[(5-Ethyl-2-Vinyl-[1,3]Dioxan-5-yl)Methyl]Ether

A reactor containing 300ml of toluene was charged with di(trimethylolpropane)(120mmol), 45.6ml of acrolein diethyl acetal, and pyridinium p-toluenesulfonate(6mmol), and then refluxed for 4 hours and cooled to ambient temperature. Themixture was further treated with potassium t-butoxide (6mmol), and then concen-trated under reduced pressure; the residue was distilled in a Kugelrohr apparatus togive 91% yield of the two crude isomers. The crude product was purified bychromatography using Silica Gel 60 and eluting with EtOAc/heptane, 20:80, and71% yield of di[(5-ethyl-2-vinyl-[1,3]dioxan-5-yl)methyl]ether isolated as a lightyellow oil. This material was re-purified by a second chromatographic separationusing Silica Gel 60 while eluting with EtOAc/heptane, 10:90, and the product wasisolated in 42% yield.

2. Preparation of Di[(5-Ethyl-2-Ethylidene-[1,3]Dioxan-5-yl)Methyl]Ether

The Step 1 product (43.9mmol) was added to a photochemical reactor containing220ml pentane and degassed by refluxing vigorously for 20minutes and then treatingwith iron pentacarbonyl (0.87 mmol). The mixture was further refluxed and irradiatedfor 1 hour until no evidence of vinyl signals were detected using 1H-NMR. It wascooled to ambient temperature, treatedwith 0.5ml triethylamine, and spargedwith dryair for 4 hours. This mixture was concentrated under reduced pressure, distilled in aKugelrohr apparatus, and a 63% yield of product was isolated as a colorless oil.

3. Preparation of Poly(Ortho Esters) Containing Triethylene Glycol

A reactor was charged with the Step 2 product (3.5mmol), triethylene glycol(4.95mmol), triethylene glycol monoglycolide (0.05mmol), and 5ml of THF. Themixturewas thenpolymerized using salicylic acid solution inTHFas catalyst.After 30minutes 0.1ml of triethylamine was added, and the product was isolated in 99% yieldafter the mixture was concentrated.

MS (observed): 363, 345 for C18H35O7 and C18H33O6

MS (calculated) 345 for C18H33O6

DERIVATIVES

O

O

O

C2H5C2H5

O

O

O

C2H5

OO

C2H5

Aa3

62 Bioerodible Poly(Ortho Esters) from Dioxane-Based Di(Ketene Acetals)

NOTES

1. In other investigations by the author [1] bioerodible block copoly(ortho esters),(I), consisting of the Step 2 produce and polyethylene oxide were prepared andused as controlled drug release agents.

O

O

O

C2H5C2H5

O

O

O

C2H5C2H5

O45

45(I)

a

2. Ng [2,3] prepared bioerodible copoly(ortho esters) consisting of the Step 2product with monomethyl polyethylene glycol ether termini and 1,4-cyclohex-anedimethanol and either an a-hydroxy carboxylic acid, (II), or N-methyl-di-ethanol amine (III), for use as bioerodible matrices for the sustained release ofbiologically active agents. Other dioxalane bioerodible analogues were pre-pared by Ng [4] in an earlier investigation.

O

O

OC2H5

C2H5

O

O

O

C2H5

O

O

O

C2H5

OH3CO

3

45

O a

(II)

TABLE 1. Selected poly(ortho ester) copolymers having bioerodible matrices usedfor the sustained release of medicaments.

Entry A Mn (daltons) Viscosity (poise)

3 O–(CH2)10–O 5,700 78,0004 (OCH2CH2)3 4,700 32,0006 O

O

11,400 —

7 (OCH2CH2)45 — —

Note: Only limited characterization data supplied by author.

Notes 63

O

O

OC2H5

C2H5

O

O

O

C2H5

NO

C2H5

OH3CO 45

Oa

(III)

3. Biocompatible ortho aromatic polyanhydrides, (IV), prepared by Uhrich [5]were used in drug delivery systems and as scaffolding implants for tissuereconstruction.

a = 6, 8

(IV)

b

a

O O

O

O

O

OO O

References

1. J. Heller et al., US Patent 7,045,589 (May 16, 2006) and US Patent Application 2006-0155101 (July 13,2006)

2. S.Y. Ng et al., US Patent Application 2003-0152630 (August 14, 2003)3. S.Y.Ng et al.,USPatentApplication 2003-0138474 (July 24, 2003) andUSPatent 6,946,145 (September

20, 2005)4. S.Y. Ng et al., US Patent 6,822,000 (November 23, 2004)5. K.E. Uhrich,US Patent 7,122,615 (October 17, 2006) and US Patent Application 2004-0096476 (March

20, 2004)

64 Bioerodible Poly(Ortho Esters) from Dioxane-Based Di(Ketene Acetals)

Title: Water-Soluble Polymer Alkanals

Author: A. Kozlowski US Patent 7,157,546 (January 2, 2007)Assignee: Nektar Therapeutics AL Corporation (Hunstville, AL)

SIGNIFICANCE

A high yielding method for preparing methoxypolyethylene glycol alkylaldehydesthrough an acetal intermediate is described. Drug delivery conjugates were thenprepared from these aldehydes by condensing with biologically active peptides orproteins such as IFNs-a, b, andj, factors VII, VIII, and IX, insulin, or erythropoietin.

REACTION

H3COO

OH

H3COO

OO

OC2H5

OC2H5

H3COO

OO

H

O

H3COO

OO

NH Erythropoietin750 750

750750i ii

iii

Note 1

i: Toluene, butylated hydroxytoluene, potassium t-butoxide, t-butanol, 4-chloro-butyraldehyde diethyl acetal, potassium bromide, CH2Cl2, diethyl ether

ii: Water, phosphoric acid, sodium chloride, sodium hydroxideiii: Erthropoietin, sodium acetate, sodium cyanoborohydride

EXPERIMENTAL

1. Preparation of Methoxypolyethylene Glycol-ButyraldehydeDiethyl Acetal

Amixture consisting ofmethoxypolyethylene glycol (30,000 daltons; 60%solution intoluene; 3.30 g), 30ml of toluene, and butylated hydroxytoluene (0.004 g) wereazeotropically dried by distilling off toluene under reduced pressure. Dried methoxy-polyethylene glycol was then dissolved in 15ml toluene and treated with 4ml of1.0M potassium t-butoxide in t-butanol, 4-chloro-butyraldehyde diethyl acetal(0.00277mol), and potassium bromide (0.05 g). The mixture was stirred overnight

65

at 105 �C. The mixture was filtered, concentrated, and the crude was product wasdissolved in 20ml of CH2Cl2. The product was isolated by precipitation in 300mldiethyl ether, and 1.92 g was isolated with a purity of 95%.

2. Preparation of Methoxypolyethylene Glycol-Butyraldehyde

Amixture of the Step 1 product (1.0 g), 20ml of deionized water, and 5% phosphoricacid was stirred for 3 hours at ambient temperature and then treated with sodiumchloride (1.0 g) and sufficient 0.1M sodium hydroxide to obtain a pH of 6.8. Theproduct was extracted three times with 20ml of CH2Cl2, dried with MgSO4,concentrated, and 82 g of product were isolated.

3. Preparation of Methoxypolyethylene Glycol-Butyl Amine-Erythropoietin

Erythropoietin (�2mg) was dissolved in 1ml of 0.1mM sodium acetate with a pH of5, and then treated with the Step 2 product (10 mmol) and cyanoborohydride andstirred for 24 hours at 4�C. Confirmation of N-terminal modification was determinedby peptide mapping. Increasing the ratio of methoxyPEG-butyraldehyde to eythro-poietin increased the degree of erythropoietin incorporation.

NOTES

1. In an earlier investigation by the author [1] 1-benzotriazolyl carbonate esters ofpoly(ethylene glycol), (I), were prepared and used as drug delivery templatesfor lysine and lysozyme.

H3COO

OO O

N

O N N

a = 200–4000

a

(I)

1H-NMR (d6-DMSO): d 1.75 ppm (p, –CH2–CH2–CHO–) 2.44 ppm (dt, –CH2–CHO), 3.24 ppm(s –OCH3), 3.51 ppm (s, PEG backbone), 9.66 ppm (t, –CHO)

1H-NMR (d6-DMSO): d 1.09 ppm (t, CH3–C–) 1.52 ppm (m, C–CH2–CH2–), 3.24 ppm (s, –OCH3),3.51ppm (s, PEG backbone), 4.46 (t, –CH, acetal)

66 Water-Soluble Polymer Alkanals

2. A drug delivery template consisting of methoxypolyethylene glycol containingsuccinimidyl esters, (II), was prepared by Harris [2] and used to form amidesfrom the amine portion of proteins.

OO

OH3CO

HN

O

O O

O

O

N

N

O O

O

O

(II)

a

3. Bhatt [3] prepared antineoplastic agents consisting of poly-L-glutamic acid--camptothecin conjugates, (III) and (IV), as a method for improving the limitedsolubility of 20(S)-camptothecin and analogues in aqueous medium.

N

N

O

OO

O

O

N

N

O

OHO

OO

O

Poly-L-glutamic acid

(III) (IV)

Poly-L-glutamic acid

4. Polydipeptides consisting of glutamic acid with alanine, asparagine, (V),glycine, or glutamine were prepared by Xu [4] and used as biodegradablepolymeric carriers to which was covalently attached the cytotoxic agent,Paclitaxel�.

Notes 67

HO OO

O

O

OH

O

O

O

O

O

HO

NHO

O

HN

NH

OCO2H

O

a

Paclitaxel(R)

Biodegradable dipeptide

(V)

References

1. A. Kozlowski, US Patent 7,101,932 (September 5, 2006)2. J.M. Harris et al., US Patent 7,030,278 (April 18, 2006)3. R. Bhatt et al., US Patent 7,153,864 (December 26, 2006)4. J. Xu,US Patent Application 2001-0041189 (November 15, 2001)

68 Water-Soluble Polymer Alkanals

Title: Biodegradable Aliphatic Polyester Grafted withPoly(Ethylene Glycol) Having Reactive Groups andPreparation Method Thereof

Author: J.-K. Park et al., US Patent 7,151,142 (December 19, 2006)Assignee: Korea Advanced Institute of Science and Technology (Daejeon, KR)

SIGNIFICANCE

Poly[lactide-g-butene)-g-poly(ethylene glycol)] has been prepared by initially copo-lymerizing L-lactide and1,2-epoxy-5-hexene formingpoly(lactide-g-butene) contain-ingpendent 1-butene, thenpost-reactingwithpoly(ethyleneglycol)methacrylate.Theproductwas both hydrophilic and biodegradable and used as a drug delivery agent andin biochips.

REACTION

OO

O

O

OO

OO

O

OO

OO

O

O

OOH

i ii

a

a

b

b

c

i: 1,2-Epoxy-5-hexene, toluene, triethylaluminum pentahydrateii: Poly(ethylene glycol) methacrylate, THF, 2,20-azobisisobutyronitrile

69

EXPERIMENTAL

1. Preparation of Poly(Lactide-g-Butene)

Three 500-ml reflux flasks were each charged with a mixture of L-lactide (5.88 g) and1,2-epoxy-5-hexene (4.12 g) dissolved in 50ml of toluene, and then treated withtriethylaluminum pentahydrate (98.6mg). Each vessel was then sealed and heated to90 �C for 12, 24, and 36 hours, respectively, and the contents were precipitated indiethyl ether. The polymers obtained were washed with diethyl ether three timesand dried in a vacuum oven for 1 day. The polymers were shown to have a double bondcontent of 7.0, 7.5, and 8.1mol%, respectively, with a Mn of roughly 10,000 daltons.

2. Preparation of Poly[Lactide-g-Butene)-g-Poly(Ethylene Glycol)]

Three 500-ml flaskswere each chargedwith amixture consisting of the Step 1 product(1 g) having an 8.1mol% double bond content, poly(ethylene glycol) methacrylate(3.6 g;Mn¼ 360 daltons), and 50ml ofTHF.The flaskswere placed into a bath heatedto 70�C.Eachmixturewas then treatedwith 2,20-azobisisobutyronitrile (2.7mg, 9mg,and 18mg, respectively) and heated 25 hours and precipitated in methanol. Thepolymers were then washed three times with methanol, dried, and the poly(ethyleneglycol) content determined to be 16.6, 18.4, and 7.0mol%, respectively. Polyethyleneglycol incorporation scoping reactions are provided in Table 1.

RESULTS

NOTES

1. Arnold [1] prepared the hydrophilic and bioabsorbable copolyester, poly(monostearoyl glycerol-co-succinate) (I), which was used in the sustainedrelease of Risperidone�.

TABLE 1. Scoping reactions to determine the effect of 2,20-azobisisobutyronitrileand reaction times on the incorporation of poly(ethylene methacrylate) into the Step 1product, poly(lactide-g-butene).

EntryButene

Content (mol%)ReactionTime (h)

AIBN(mg)

Graft Ratio ofPEG (mol%)

1 7.0 48 8 9.52 7.0 48 3.0 10.03 7.5 48 8.0 19.54 7.5 48 3.0 15.05 8.1 25 2.7 16.66 8.1 25 9.0 18.47 8.1 25 18.0 7.0

70 Biodegradable Aliphatic Polyester Grafted with Poly(Ethylene Glycol)

O

OO

O

O

16

a

(I)

2. Wilson [2] prepared biodegradable copolymers that were hydrolysable at pH> 10, consisted of ethylene and selected monomers, (II–V), and were used ascomponents in disposable syringes.

O

O

O

OSi

OSi O

O

O O

(II) (III) (IV) (V)

3. Polymer films prepared by Hayes [3] consisting of bis(2-hydroxyethyl)tere-phthalate, lactic acid, tris(2-hydroxyethyl)trimellitate, ethylene glycol, poly(ethylene glycol), and the colorant titanium dioxide were both biodegradableand compostable.

4. Biodegradable polymers, (VI), containing the hydrophobic biodegradablepolyester block and hydrophilic polyethylene glycol block segment wereprepared by Piao [4] and used as drug release agents. The gel matrix erosionrates reflected the hydrophobic/hydrophilic content, monomer ratios, andmolecular weights.

HO

OO

O

O

O

a bc abO

O

O

OH

(VI)

References

1. S. Arnold et al., US Patent 7,034,037 (April 25, 2006)2. R.B. Wilson Jr. et al., US Patent 7,037,992 (May 2, 2006)3. R.A. Hayes, US Patent 7,144,972 (December 5, 2006)4. A.-Z. Piao et al., US Patent 7,018,645 (March 28, 2006)

Notes 71

Title: Coumarin End-Capped Absorbable Polymers

Author: T. Matsuda et al., US Patent 7,144,976 (December 5, 2006)Assignee: Ethicon, Inc. (Somerville, NJ)

SIGNIFICANCE

Poly(lactone-co-trimethylene carbonates) containing photocurable coumarin esterend groups have been prepared which are crosslinkable upon irradiation with ultra-violet light by a [2þ 2] cycloaddition. Thesematerials are useful in the preparation ofin vivo implants.

REACTION

OHO O OO OC2H5O

O

OO OHO

O

OO OCl

OO

O

O

O

O

Oa b c

OO O

O

OO

O

O

O

Oa b cOO O

O

i ii iii

ivNote 1

OO

OO

O

O

O

O

O

O

a

b c

v

i: Ethyl bromoacetate, potassium carbonate, acetoneii: 1,4-Dioxane, sodium hydroxide, hydrochloric acidiii: Thionyl chloride

72

iv: Poly(e-caprolactone-co-trimethylene carbonate), pyridine, CH2Cl2v: CH2Cl2

EXPERIMENTAL

1. Preparation of 7-Coumarin Ethyl Acetate Ether

A mixture consisting of 7-hydroxycoumarin (0.125mol), K2CO3 (0.179mol), ethylbromoacetate (0.150mol), and 450ml of acetone were refluxed for 2 hours and thenfiltered. Themixturewas concentrated, the residue re-crystallized fromethanol, dried,and the product was isolated in 89% yield.

1HNMR (270MHz, DMSO-d6) d 1.18 (3H, triplet, J¼ 8.1Hz), 4.16 (2H, quartet, J¼ 8.1Hz), 4.91 (2H,singlet), 6.28 (1H, doublet, J¼ 9.9Hz), 6.96 (1H, doublet, J¼ 2.0Hz), 6.98 (1H, quartet, J¼ 2.0,and 8.9Hz), 7.61 (1H, doublet, J¼ 8.9Hz), 7.96 (1H, doublet, J¼ 9.9Hz)

2. Preparation of 7-Coumarin Acetic Acid Ether

The Step 1 product (27.9mmol), 280ml of 1,4-dioxane, and NaOH (0.405mol) werestirred overnight at ambient temperature then acidified with 12M HCl. The mixturewas extracted into a mixture of CCl3H and methanol and then concentrated bydistillation under reduced pressure. The residuewas re-crystallized from ethanol, andthe product was isolated in 90% yield.

1HNMR (270MHz, DMSO-d6) d 4.83 (2H, singlet), 6.28 (1H, doublet, J¼ 9.9Hz), 6.95 (1H, doublet,J¼ 2.0Hz), 6.97 (1H, doublet, J¼ 2.0, and 8.9Hz), 7.62 (1H, doublet, J¼ 8.9Hz), 7.97 (1H,doublet, J¼ 9.9Hz), 13.13 (1H, s)

3. Preparation of 7-Chlorocarbonylmethoxycoumarin

The Step 2 product (17.1mmol) and thionyl chloride (0.277mol) were refluxed 3hours. Excess thionyl chloridewas removed by distillation, and the crude product wasisolated in 98% yield and used without additional purification.

1HNMR (270MHz, DMSO-d6) d 4.83 (2H, singlet), 6.28 (1H, doublet, J¼ 9.9Hz), 6.94(1H, doublet, J¼2.0Hz), 6.96 (1H, quartet, J¼ 2.0, and 8.9Hz), 7.62 (1H, doublet, J¼ 8.9Hz), 7.97 (1H, doublet,J¼ 9.9Hz)

4. Preparation of Coumarin Ester End-CappedPoly(�-Caprolactone-co-Trimethylene Carbonate)

A mixture consisting of poly(e-caprolactone-co-trimethylene carbonate)(0.129mmol), the Step 3 product (1.79mmol), pyridine (0.62mmol), and 20.5mlof CH2Cl2 were stirred overnight at ambient temperature. The end-capped polymerwas precipitated in diethyl ether and then purified by fractionation using DMF anddiethyl ether/methanol, 8:2; the product was isolated in 86% yield.

FTIR (KBr, cm�1) 2953, 2866, 1743, 1614, 1250, 1164, and 10361HNMR coumarin groups (270MHz, CDCl3) d 4.69 (2H, doublet), 6.26 (1H, doublet, J¼ 9.3Hz), 6.79

(1H, doublet, J¼ 2.4Hz), 6.87 (1H, quartet, J¼ 2.4, and 8.3Hz), 7.39 (1H, doublet, J¼ 8.3Hz),7.62 (1H, doublet, J¼ 9.3Hz)

UV Polymer equivalent weight 3.65� 104 daltons

Experimental 73

5. Photogelation of Coumarin Ester End-CappedPoly(�-Caprolactone-co-Trimethylene Carbonate) Using Ultraviolet Light

The Step 4 product (40mg) was dissolved in 1.00ml CH2Cl2 and 150 ml and placedonto a 14.5mm diameter cover glass. CH2Cl2 was then removed under reducedpressure to prepare a thin film having a thickness of roughly 0.03mm. The film wasirradiated with ultraviolet light of varying intensities and times from a Hg–Xe lamp.The polymeric network or gel that formed was washed with CH2Cl2, dried underreduced pressure to constant weight, and isolated.

RESULTS

NOTES

1. The preparation of poly(e-lactone-co-trimethylene carbonate) is described bythe author using the procedure of Bezwada [1].

2. The preparation of other in vivo implants using photocurable coumarin end-groups and at least one lactone monomer selected from e-caprolactone,glycolide, or DL-lactide is described by the author [2].

3. Additional crosslinkable macromolecules are described by the author [3] in anearlier investigation.

4. Crosslinkable monomers N-[3-(7-methyl-9-oxothioxanthene-3-carboxamido)-propyl]methacrylamide, (I), and poly(e-caprolactone-co-trimethylene carbon-ate) (II), were prepared by Chudzik [4] and used in UV photo-crosslinkableimplants.

O

HN

O

S

O

(I)

TABLE 1. Effect on molecular weight of poly(�-caprolactone-co-trimethylenecarbonate) end capped with coumarin after a [2þ 2] photo cycloaddition using UVirradiation.

Mn Poly(e-Caprolactone-co-Trimethylene Carbonate)(daltons)

OH value(mol/g)

Mn of Post UV Cured End-CappedPoly(e-Caprolactone-co-TrimethyleneCarbonate) Coumarin Ester (daltons)

2900 8.34� 10�4 36004200 5.88� 10�4 51006100 3.52� 10�4 85005900 3.55� 10�4 8500

74 Coumarin End-Capped Absorbable Polymers

O

OO

O

O

Oa b c O

O O

O

O

O

O

O

O(II)

5. Rhee [5] prepared crosslinkable macromolecules containing collagens, (III),and glycosamino-glycans using a bi-succinimidyl intermediate, (IV); themacromolecules were then used in biomaterial compositions.

SS

O

O

NH–CollagenCollagen–NH

(III)

O SS O

N

O

O

N

O

O

O

O(IV)

6. Crosslinkable bioresorbable hydrogel block copolymer compositions, (V),were prepared by Loomis [6] for implantable prostheses and as scaffoldingfor tissue engineering applications.

OO

O

O

Ob a a = 50–300

b = 10–100

(V)

References

1. R.S. Bezwada et al., US Patent 5,468,253 (November 21, 1995)2. T. Matsuda et al., US Patent 7,144,976 (December 5, 2006)3. T. Matsuda et al., US Patent 7,105,629 (September 12, 2006)4. S.J. Chudzik et al., US Patent 7,094,418 (August 22, 2006) and US Patent 6,924,370 (August 2, 2005)5. W. Rhee, US Patent 7,129,209 (October 31, 2006)6. G.L. Loomis et al., US Patent 7,109,255 (September 19, 2006)

Notes 75

Title: Block Copolymers for MultifunctionalSelf-assembled Systems

Author: J. A. Hubbell et al., US Patent 7,132,475 (November 7, 2006)Assignee: Ecole Polytechnique Federale de Lausanne (Lausanne, CH)

SIGNIFICANCE

A block copolymer effective as a controlled release agents of biologically activematerials have been prepared. This agent consisted of ethylene oxide-propylenesulfide-ethylene oxide terpolymer that had been end-capped with a selected cysteine-containing peptide. Thesematerials resist degradation prior to reaching their intendedtargets because they behave as multilamellar vesicles.

REACTION

H3COO

OH H3COO

O

O 2S

H3COO

S

O

H3COO

SS

OO

O16

161616

i ii

iii

H3COO

SS

OO

O16

ivCystein-containing peptide

25 8

Note 1

iv

25 8

i: Triethylamine, p-toluene sulfonyl chloride, CH2Cl2ii: Potassium thioacetate, acetoneiii: Sodium methoxide, methanol, propylene sulfide, poly(ethylene glycol)

monoacrylateiv: Triethanolamine, HEPES buffered saline, hydrochloric acid

76

EXPERIMENTAL

1. Preparation of Methoxypoly(Ethylene Glycol) Tosylate

Methoxypoly(ethylene glycol) (7� 10�3mol) was dissolved in 30ml of CH2Cl2 andthen treated with triethylamine (0.016mol) and p-toluene sulfonyl chloride(0.0135mol). The mixture was stirred for 24 hours at ambient temperature. Themixture was then filtered to remove precipitated triethylammonium hydrochloride,concentrated, and the product was isolated after precipitation in cold diethyl ether.

2. Preparation of Methoxypoly(Ethylene Glycol) Thioacetate

The Step 1 product (2.22� 10�3mol) was dissolved in 30ml of acetone and treatedwith potassium thioacetate (6.67� 10�3mol), it was stirred overnight at ambienttemperature. The mixture was filtered, concentrated, and precipitated in cold diethylether. The residuewas dissolved inCH2Cl2, extractedwithwater, dried usingNa2SO4,and the product was isolated after re-precipitation in cold diethyl ether.

3. Preparation of Methoxy-Poly[Ethylene Glycol-b-PropyleneSulfide-b-(Ethylene Glycol) Monoacrylate)]

The Step 2 product was dissolved in THF and treated with one equivalent of 0.5Msodium methoxide in methanol at ambient temperature. The mixture was thentreated with between 25 and 50 equivalents of propylene sulfide and polymerizedfor 30 minutes. It was further treated with approximately 10 equivalents of poly(ethylene glycol) monoacrylate as the end-capping agent. The reaction mixture wasstirred overnight at ambient temperature and isolated by precipitation in methanol.

4. Preparation of Methoxy-Poly[Ethylene Glycol-b-PropyleneSulfide-b-(Ethylene Glycol) Monoacrylate)]-Cysteine-ContainingPeptide End Functionalized

The Step 3 product (230 mmol) was dissolved in HEPES buffered saline (10mmolHEPES; 8 g/l NaCl; pH¼ 7.4) and then treated with triethanolamine (5.3 ml/ml), andthe pH adjusted to pH 8 using 6M HCl. Cysteine-containing peptides dissolved in5ml of HEPES buffered saline were next added to 40ml of the Step 3 product withstirring and incubated for 6 hours. The solution was dialyzed against pure water for24 hours and freeze-dried. The polymer was dissolved in 5ml of CH2Cl2, and theproduct was isolated after precipitation in hexane.

DERIVATIVES

Only the single derivative was prepared.

Derivatives 77

NOTES

1. Block copolymers containing acrylate termini, (I), were prepared by Cellesi[1], and they were subjected to either a Michael-type addition or were photo-polymerized and used as drug delivery agents or biomaterials.

O

O

OO

O

Oa b a

(I)

2. Polymers, (II) and (III), containing hydrolytically susceptible segments ata physiological pH between 6.5 and 7.5 were previously prepared by the author[2] and used as viscoelastic liquids containing gel microparticles.

OO

O O

O

O

O

OPEG2

a

(II)

S O O

O

O O

O

S

(III)

a2

3. Poly(ethylene glycol)-poly(glutamic acid) block copolymers containing cis-diamine-dichloroplatinum, (IV), were prepared by Kataoka [3]. The micellediameters were roughly 22 nm, and these block copolymers were used asantineoplastic drug delivery agents.

ONH

HN

O

CO2 Pt(NH2)(NH3)Cl2

5 a

(IV)

a = 40, 79

78 Block Copolymers for Multifunctional Self-assembled Systems

4. Ho [4] prepared nanoscale helicalmicrostructures and channels frompoly(aryl-TEMPO-b-L-lactide) block copolymers, (V).

ON

X

OO

O

O

O

(V)X = CH, N

a

b

References

1. F. Cellesi et al., US Patent Application 2003-0044468 (March 6, 2003)2. J.A. Hubbell et al., US Patent 6,943,211 (September 13, 2005)3. K. Kataoka et al., US Patent 7,125,546 (October 24, 2006)4. R.-M. Ho et al., US Patent 7,135,523 (November 14, 2006)

Notes 79

Title: Methods of Making Functional BiodegradablePolymers

Author: Y. Huage et al., US Patent 7,037,983 (May 2, 2006)Assignee: Kimberly-Clark Worldwide, Inc. (Neenah, WI)

SIGNIFICANCE

Acrylic acid and derivatives have been free radically grafted onto the backbone ofbiodegradable polycaprolactone and poly(lactic-co-glycolic acid). These functiona-lized biocompatible materials are useful as drug delivery agents.

REACTION

OO

O

O

OO

O

O

O OH

O

O

a b a b c

d

i

i: Acrylic acid, 2,20-azobisisobutyronitrile

EXPERIMENTAL

1. Preparation of Poly[(Lactic-co-Glycolic Acid)-g-Acrylic Acid]

To prepare the graft copolymer, poly[(lactic-co-glycolic acid) (5.7 g) was dissolved inacrylic acid (5.7 g) and, upondissolution, treatedwith 98%2,20-azobisisobutyronitrile(0.014 g). The mixture was then heated to 70�C and continued heating until thereaction mixture solidified. The solid was then placed into a vacuum oven to removeunreacted acrylic acid, and the product was isolated.

80

DERIVATIVES

TESTING

The solution behavior of the Step 1 productwas evaluated using aCoulter tester. In thistest NaOHwas used to raise the solution’s pH to 9.6 whereupon a milky solution withan average particle size of 2 mwas formed. By one additional day, particle aggregationand precipitation became significant.When the solution pHwas raised to 13.7, a clearsolution formed with an average particle size of 347 nm.

NOTES

1. In another investigation by the author [1], poly(acrylic acid)-g-poly(lacticacid), (I), was prepared and used as a bioadhesive conjugated with bio-degradable components in drug delivery systems.

a b

cOO

O

OHO

(I)

TABLE 1. Biodegradable poly[(lactic-co-glycolic acid) substrates free radicallyfunctionalized with grafted acrylic acid or 2-hydroxylethyl acrylate.

Entry Drug Delivery Agent Structure

2 Polycaprolactone-g-acrylic acid O O

O

O

HOO

ab

c

3 Poly[(lactic-co-glycolic acid)-g-2-hydroxylethylacrylate O

O

O

O

O O

OO

a b c

d

OH

Notes 81

2. Wang used reactive-extrusion polymerization with 2,5-di-methyl-2,5-di-t-bu-tylperoxy hexane to prepared a graft copolymer, (II), by free radically graftingpolyethylene-glycol malonic acid onto the biodegradable substrate of poly(b-hydroxybutyrate-co-b-hydroxyvalerate).

a b

d

O O O

O O O

O O

O O

c

(II)

3. Langer [3] coupled 1,4-butanediol diacrylate with poly(N,N0-dimethylethyl-enediamine), (III), piperazine, and 4,40-trimethylenedipiperidine to preparepoly(b-amino esters) that were particularly suited for the delivery of poly-nucleotides. Nanoparticles containing polymer/polynucleotide complexeswere also prepared. Hubbell [4] and Zhao [5] prepared polymeric biomaterialsby the nucleophilic addition of cysteine, (IV), and polyethylenimine, (V),respectively, to a,b-unsaturated macromolecular diacrylates.

O NN

O

O

O

(III)

O

O

O S

O O

OH

H2N

a

(IV)

NNH

ON

O

O

NH2

OO7

7

(V)

a b

n

c

82 Methods of Making Functional Biodegradable Polymers

4. Acrylated terminated multi-block micelle-forming biodegradable macromo-lecular hydrogels, (VI), prepared by Pathak [6], were used in drug deliverydevices and as tissue coatings.

OO

OO

O

O

O

O

OO

O

O

aba b 182

a = 4, b = 1a = 3, b = 2a = 2, b = 3a = 1, b = 4

(VI)

References

1. Y. Huage et al., US Patent Application 2003-0232088 (December 18, 2003)2. J.H. Wang et al., US Patent 7,053,151 (May 30, 2006)3. R.S. Langer et al., US Patent 6,998,115 (February 14, 2006)4. J.A. Hubbell et al., US Patent 7,119,125 (October 10,2006)5. G. Zhao et al., US Patent Application 2006-0258751 (November 16, 2006)6. C.P. Pathak et al., US Patent 7,094,849 (August 22, 2007)

Notes 83

Title: Monofunctional Polyethylene Glycol Aldehydes

Author: P. Rosen et al., US Patent 7,041,855 (May 9, 2006)Assignee: Sun Bio, Inc. (Orinda, CA)

SIGNIFICANCE

Monofunctionalmethoxypolypropyleneglycol aldehydeswere prepared in a five-stepsynthetic route. Thesematerials are useful as protein conjugates, and they induce verymild immunogenic responses.

REACTION

H3COO

OOH H3CO

OO

OO

OC2H5

H3COO

OO

OH

O

H3COO

OO

O

ON

O

O

H3COO

OO

O

O HN OC2H5

OC2H5

H3COO

OO

O

O HN

O

H

i ii

iiiiv

v452452

452452

452452

Notes 1,2

i: Potassium t-butoxide, ethyl bromoacetate, t-butyl alcoholii: Sodium hydroxideiii: CH2Cl2, N-hydroxysuccinimide, dicyclohexylcarbodimideiv: CH2Cl2, 1-amino-3,3-diethoxypropanev: Phosphoric acid, sodium bicarbonate

EXPERIMENTAL

1. Preparation of Polyethylene Glycol Ethyl Acetate

Methoxypolyethylene glycol and potassium t-butoxide were dissolved in t-butylalcohol, stirred at 60�C, and then next treated with ethyl bromoacetate. The mixturewas next stirred an additional 15 hours at between 80�C and 85�C, filtered, and

84

concentrated. The residue was dissolved in distilled water, washed with diethyl ether,and extracted twicewithCH2Cl2.The extractwasdriedoverMgSO4andconcentrated.Precipitation was induced by the addition of diethyl ether to the residue, and themixture was filtered. The solid was dried under vacuum, and the product was isolatedas a white powder.

2. Preparation of Polyethylene Glycol Acetic Acid

The Step 1 product was dissolved in 1M sodium hydroxide and stirred for 15 hours atambient temperature. The reaction mixture pH was then adjusted to 2 using 1Mhydrochloric acid and extracted twice with CH2Cl2. The mixture was worked up asdescribed in Step 1, and the product was isolated as a white powder.

3. Preparation of Polyethylene Glycol Succinimidyl Acetate

A solution of the Step 2 product dissolved in CH2Cl2 was cooled up to 5�C and treated

with N-hydroxysuccinimide followed by a solution of dicyclohexylcarbodimidedissolved in CH2Cl2. The mixture was stirred for 15 hours at ambient temperatureand then filtered and concentrated, and the residue was re-crystallized from EtOAc.The product was washed twice with diethyl ether was dried, and the product wasisolated as a white powder.

4. Preparation of Polyethylene Glycol Diethyl Acetal

The Step 3 product was dissolved in CH2Cl2, treated with 1-amino-3,3-diethoxypro-pane dissolved in CH2Cl2, and stirred 2 hours at ambient temperature. Precipitationwas then induced by the addition of diethyl ether. The mixture was filtered, re-crystallized using EtOAc, and dried; the product was isolated as a white powder.

5. Preparation of Polyethylene Glycol Aldehyde

The Step 4 product was dissolved in an aqueous solution containing phosphoric acid atpH1andstirredfor2hoursatbetween40�Cand50�C.Aftercoolingthe reactionmixtureto ambient temperature, the pH was raised to 6 using 5% aqueous NaHCO3 solution.Brinewasthenadded,and theresultingmixtureextractedtwicewithCH2Cl2.Theextractwas dried over MgSO4, filtered, and concentrated. Precipitation was induced by theaddition of diethyl ether to the residue, and the product was isolated as a white powder.

ALTERNATIVE SYNTHETIC PATHWAYPROPOSED BY THE AUTHOR

OH

OH

HOO

OHO

OO

O

O

O2N

OOO

HN

O

OO

H3CO

O

HO

HN

O

OO

H3CO

i iiiii

iv

aa

Alternative Synthetic Pathway Proposed by the Author 85

i: 4-Toluene sulfonic acid, acetone, light petroleum etherii: 4-Nitrophenyl chloroformate, acetonitrile, 4-dimethylaminopyridineiii: Polyethylene glycol 2-ethylamine, 4-dimethylaminopyridine, CH2Cl2iv: Hydrochloric acid, hydroperiodate acid

NOTES

1. In an earlier investigation by the author [1] methoxypolyethylene glycolderivatives containing pendant aldehydes, (I), were prepared as illustratedbelow.

H3COO

OOH

aH3CO

OO

OHa

OH

O

H3COO

OOH

O

O

N

O

O

aH3CO

OO

OH

NH

Oa

O O C2H5C2H5

H3COO

OOH

NH

Oa

O H

(I)

i ii

iiiiv

i: Acrylic acid, t-butyl peroxybenzoateii: CH2Cl2, N-hydroxysuccinimide, dicyclohexylcarbodimideiii: CH2Cl2,1-amino-3,3-diethoxypropaneiv: Phosphoric acid, water

2. In a subsequent investigation by the author [2] bi-functional polyethyleneglycol derivatives, (II), were prepared.

AO

OB

a(II)

A BSO2CH=CH2 CONHCH2CH2CHO

Malimide–CH2CO Malimide–CH2COMalimide–CH2CO CONHCH2CH2CHO

CONHCH2CH2CHO CONHCH2CH2CHO

3. Additional methoxypolyethylene glycol derivatives, (III), were prepared byHarris [3] in earlier investigations.

HN

OO

H3CO aR

R

RCH2OCH2C6H5

CH2OH

CH2SCH2CH2OH

CH2SCH=CH2(III)

86 Monofunctional Polyethylene Glycol Aldehydes

4. Acid-terminated methoxypolyethylene glycol, (IV), was prepared by Whitlow[4] and used to conjugate single-chain polypeptides.

H3COO

OO

aO

OH

O

(IV)

5. Hydroxyl/carboxylic acid terminated polyethylene glycol derivatives, (V),were prepared by Varshney [5] and used as intermediates.

HO2CO

OOH

(V)3 a

6. Azide- and acetylene-terminated polyethylene glycol derivatives were pre-pared by Wilson [6] and used in biomedical applications.

References

1. P. Rosen et al., US Patent 6,956,135 (October 18, 2005)2. P. Rosen et al., US Patent 7,217,845 (May 15, 2007)3. J.M. Harris et al., US Patent 6,541,543 (April 1, 2003) and US Patent 6,362,254 (March 26, 2002)4. M. Whitlow et al., US Patent 7,150,872 (December 19, 2006)5. S.K. Varshney et al., US Patent 7,009,033 (March 7, 2006)6. T.E. Wilson, US Patent 7,230,068 (June 12, 2007)

Notes 87

IV. COATINGS

A. Anionic

Title: Glycopolymers and Free Radical PolymerizationMethods

Author: E. L. Chaikof et al., US Patent 7,244,830 (July 17, 2007)Assignee: Emory University (Atlanta, GA)

SIGNIFICANCE

Heparin-like copolymers containing up to 100 units of sulfonated glucose or lactosehavebeen prepared by polymerizingwith acrylamide using arenediazonium saltswithcyanate anions to form a thrombo-resistant heparinized surface.

REACTION

OHOHO

HO

NHAc

OH

OHOHO

HO

NHAc

O

OHOHO

HO

NHAc

O+ Separate

OHOHO

HO

NHAc

O

OO3SO

O3SO

O3SO

NHAc

O

Cl

OH2N

OCN

OO

O3SO

O3SO

O3SO

NH

Ac

a b

i

iiiii


89

i: 4-Penten-1-ol, 10-camphorsulfonicii: Sulfur trioxide trimethylamine complexiii: 4-Chloroaniline, sodium nitrite, boron trifluoride hydrogen fluoride, cyanate

ions

EXPERIMENTAL

1. Preparation of N-Acetyl-d-Glucosamine Glycomonomer

N-Acetyl-d-glucosamine was treated with 4-penten-1-ol in the presence of10-camphorsulfonic acid as catalyst. This provided an a- and b-anomeric mixtureof the corresponding C4-spacer arm containing the glycomonomer. The a- andb-anomers were separated by column chromatography with CHCl3 and methylalcohol and were isolated in 31% and 11% yields, respectively.

2. Preparation of N-Acetyl-D-Glucosamine Glycomonomer Persulfates

Chemoselective sulfation of the hydroxy groups of the Step 1 a-anomer was obtainedusing SO3–NMe3 complex and the product purified by anion-exchange and size-exclusion chromatography.

3. Preparation of Glycopolymers

Cyanoxyl radicals were generated in situ by an electron-transfer reaction betweencyanate anions and p-chlorobenzenediazonium cations; arenediazonium salts werepreviously prepared in water through the diazotization reaction of p-chloroaniline.Copolymerizations were performed using the Step 2 product and acrylamide at 50�Cwith ClC6H4N2

þ BF4�/NaOCN as the initiating system. Copolymers were isolated byprecipitation in a 10-fold excess of methanol and characterized.

DERIVATIVES

Lactose-based glycomonomers were also prepared as illustrated below.

OO3HSO

O3SO

O3SO

O3SO

OO

O3SO

O3SOO3SO

O

90 Glycopolymers and Free Radical Polymerization Methods

NOTES

1. In a subsequent investigation by the author [1] multivalent glycopolymers withchain-terminating binding groups, (I), were prepared and used in carbohydrate-mediated biomolecular recognition processes.

HN NH

S

O

HN

ONCO

HN O

O O

HO

OH

OHO

O

HO

OHOH

OH

CONH2

a bc

(I)

2. Antithrombonic polymers consisting of poly(vinylidene fluoride-co-hexafluoropropylene-co-vinyl pyrrolidone), (II), 80/15/5 molar ratio,respectively, were prepared by Pacetti [2] and used as shunts in treatingatherosclerosis and thrombosis.

CF2

F2C

CF

CF3 N O

a cb

(II)

3. Antithrombonic esters, including co-poly-(N,N0-sebacoyl-bis-(L-leucine)-1,6-hexylene diester), (III), and polyethylene glycol derivatives, (IV), were pre-pared by Pacetti [3] and Hossainy [4], respectively, and used as bio-absorbablestent coatings.

NH

O ONH

O O

O O8 6 n

(III)

Notes 91

O

O

O

PEG300 O

O

O

O

O

(IV)4

4a b

References

1. E.L. Chaikof et al., US Patent Application 2005-0180945 (August 18, 2005)2. S.D. Pacetti, US Patent 7,244,443 (June 17, 2007)3. S.D. Pacetti et al., US Patent 7,220,816 (May 22, 2007) and US Patent 7,202,325 (May 22, 2007)4. S.F.A.Hossainy et al., USPatent 7,186,789 (March 6, 2007) andUSPatent 7,169,404 (January 30, 2007)

92 Glycopolymers and Free Radical Polymerization Methods

B. Aqueous

Title: Method of Making Novel Water-Solubleand Self-doped Polyaniline Graft Copolymers

Author: W.-H. Jo et al., US Patent 7,229,574 (June 12, 2007)Assignee: Seoul National University Industry Foundation (Seoul, KR) Cheil

Industries, Inc. (Kyeonggi-do, KR)

SIGNIFICANCE

Polyaniline has been grafted onto the poly(styrenesulfonic acid-co-aminostyrene)backbone using aniline, ammonium persulfate, and hydrochloric acid. The graftcopolymer is water soluble and self-doping and can be used in electrical and marineanticorrosive applications.

93

REACTION

NHBOC

NHBOC

SO3Na NH3Cl SO3H NH SO3

NH

NH

NH

i ii iii

Not Isolated

...

a baba b

Note 1

i: Styrene-4-sulfonic acid sodium, DMSO, 2,20-azobisisobutyronitrileii: Aniline, ammonium persulfate, hydrochloric acid

EXPERIMENTAL

1. Preparation of Poly(Styrene-4 Sulfonic Acid Sodium-co-Styrene-4-Amino-Butyl Carbonate)

A reactor was charged with styrene-4-sulfonic acid sodium (5 g), styrene-4-amino-t-butyl carbonate (0.5 g), and 2,20-azobisisobutyronitrile (0.1 g) dissolved in 60ml ofDMSO and polymerized for 15 hours at 80�C. The mixture was then precipitated inacetone, filtered, washed several times with acetone, dried, and the product wasisolated.

2. Preparation of Self-doped Polyaniline Graft Copolymer

Aniline and the Step 1 product were mixed with water and then treated with thedropwise addition of 20ml 1M ammonium persulfate and hydrochloric acid at 80�Cwhere themolar ratio of ammoniumpersulfate/anilinewas 1.0. After standardworkupthe polymer was isolated. Aniline grafting lengths greater than 20 units could not besolubilized in water.

94 Method of Making Novel Water-Soluble and Self-doped Polyaniline Graft Copolymers

NOTES

1. Polyaniline was converted into N-t-BOC polyaniline, (I), by Lee [1] to reduceintermolecular hydrogen bonding when used in conductive polymer appli-cations.

N NH N Na b

BOC

c(I)

2. Hwang [2] grafted polyaniline onto carbon nanocapsules having a diameterbetween 3-100 nm using ammonium persulfate and hydrochloric acid.

3. Polyaniline-grafted carbon black was prepared by Srinivas [3] and thenplatinized with chloroplatinic acid, as illustrated below, and used as a fuelcell component. Sulfurized analogues, (II), were prepared by Srinivas [4] andwere also used as fuel cell components.

NH2

NH NHia

Carbon black

PtPt

H2PtCl6

iiNaBH4 / H2

i: Ammonium persulfate, hydrochloric acid

NH NHa

Carbon black

HO3S HO3S

(II)

Notes 95

References

1. S.-H. Lee et al., US Patent 7,067,229 (June 27, 2006)2. G.-L. Hwang et al., US Patent 7,217,748 (May 15, 2007)3. B. Srinivas, US Patent 7,195,834 (March 27, 2007)4. B. Srinivas et al., US Patent Application 20040169165 (September 2, 2004)

96 Method of Making Novel Water-Soluble and Self-doped Polyaniline Graft Copolymers

Title: Oxyfluorination

Author: I. deVilliers Louw et al., US Patent 7,225,561 (June 5, 2007)Assignee: South African Nuclear Energy Corporation, Ltd. (ZA)

SIGNIFICANCE

Polypropylene has been oxyfluorinated using a gas mixture consisting of fluorine,nitrogen, and water.When cured with mortar slurry, oxyfluorinated surfaces had 20%greater shear bond strength than fluorinated surfaces.

REACTION

Polypropylene

OF OFOF

i

FF

Note 1

i: Fluorine, nitrogen, water

EXPERIMENTAL

1. Preparation of Polypropylene-g-Hypofluorite

Monofilament polypropylene fibres were prepared by direct extrusion having arectangular cross section of 0.5� 1.3mm, a length of 40mm, a specific gravity of0.91, a tensile strength of 120MPa, and an elongation at break of 14%.The fiberswereplaced under 18% humidity at ambient temperature air and then treated with 20% F2and 80%N2 at a pressure of 45 kPa at 38

�C for 2.5 hours. Thereafter the reactionvesselwas evacuated, and the product was isolated.

97

TESTING

NOTES

1. Oxyfluorination of polypropylene was previously done by Hruska [1], andthe material was used as an oxidative surface treatment method inelectrophotography.

2. Mori [2] developed a method for solid bonding without using a bonding agentby surface hydrofluorinating metal or glass in the presence of water vapor.

3. Oxyfluoropolymers-adhesive composites have also been prepared byVargo [3]using a radio frequency glow discharge of polytetrafluorineethylene.

4. Surface oxyfluorination was also performed on poly(methyl methacrylate) byJolet [4] as a method for manufacturing the outer panel of craze-resistantwindows.

References

1. Z. Hruska, US Patent 6,503,989 (January 7, 2003)2. Y.Mori et al., USPatentApplication 2001-0009176 (July 26, 2001) andUSPatent 6,620,282 (September

16, 2003)3. T.G. Vargo et al., US Patent 6,790,526 (September 14, 2004)4. L. Joret et al., US Patent 7,211,290 (May 1, 2007)

TABLE 1. Shear bond testing of surface modified polypropylene afteroxyfluorination curing in mortar slurry.

EntryShear Bond Strengthat 7 Days (MPa)

Shear Bond Strengthat 28 Days (MPa)

1 0.48 0.46Control 0.40 0.39

Note: The Control sample was prepared under anhydrous conditions.

98 Oxyfluorination

Title: Aqueous Dispersions of CrystallinePolymers and Uses

Author: R. F. Stewart et al., US Patent 7,175,832 (February 13, 2007)Assignee: Landec Corporation (Menlo Park, CA)

SIGNIFICANCE

Aqueousdispersions of crosslinkedcrystallinepolymers containingboth hydrophobicand hydrophilic components have been prepared. The hydrophobic componentsconsist of C6-, C12-, C14-, and C16-acrylates while methyacrylic acid constituted thehydrophilic comonomer. These dispersions are useful as coatings, particularly onhuman hair.

REACTION

O

O

O O

O

OC16H33

O OC6H13

OC16H33

O

C16H330

O

C16H33O

O

O OC6H13

OC16H33

O

O

C16H33O

OC16H33

O

i

a b c d e

jgf ih

i: Water, ethyl alcohol, hexyl acrylate, methyacrylic acid, 1,14-tetradecanediol,sodium dodecyl sulfate, ammonium dodecyl benzene sulfonate, potassiumpersulfate

99

EXPERIMENTAL

Amixture consisting of water (190 g), ethyl alcohol (10 g), hexadecyl acrylate (70 g),hexyl acrylate (25 g), methyacrylic acid (5 g), 3.2% sodium dodecyl sulfate, andammonium dodecyl benzene sulfonate (5 g) was charged into a reactor and degassedfor 30 minutes. Potassium persulfate (0.4 g) was then added, and the polymerizationwas conducted for 4 hours at 70�C under nitrogen. After the polymer was isolated, asharp DSC endotherm was observed at 22.5�C.

REACTION SCOPING

TABLE 1. Effects on terpolymer Tm for materials crosslinked with 1,14tetradecyldiol using varying amounts of surfactant and co-solvents.

Reaction Components Example 1 Example 3 Example 5 Example 7

Water (g) 200 190 200 180C16 Acrylate (g) 70 70 70 70C6 Acrylate (g) 25 25 25 25Methyacrylic acid (g) 5 5 5 51,14 Tetradecyldiol (g) 2 1.5 — —Sodium dodecyl sulfate (g) 5 5 2.5 2.5Ammonium dodecyl benzenesulfonate (g)

5 5 2.5 2.5

Potassium persulfate (g) 0.4 0.4 0.4 0.4Ethyl acetate (g) — 20 — 20Ethanol (g) 10 — — —Tm (�C) 30.7 21.9 33.0 32.6Tm Peak appearance Broad Sharp Multiple peaks Sharp

TABLE 2. Effects on the polymer Tm after eliminating the amorphorous effectsof both of C6-acrylate and 1,14 tetradecyldiol.

Reaction Components Example 9 Example 10 Example 11 Example 12

Water (g) 200 190 400 400C16 Acrylate (g) 35 35 70 —C14 Acrylate (g) — — — 95C12 Acrylate (g) 60 60 120 95Methyacrylic acid (g) 5 5 10 10Sodium dodecyl sulfate (g) 2 2 8 8DOSS (g) 2 2 8 8Potassium persulfate (g) 2 0.4 1.6 1.5Ethyl acetate (g) — 10 — —Dodecyl mercaptan (g) — — 0.1Tm (�C) 2.0 and 33.7 2.7 13.9 16.1Tm Peak appearance Two peaks Broad peak Sharp peak Sharp peak

100 Aqueous Dispersions of Crystalline Polymers and Uses

NOTES

1. Bitler [1] prepared sharply melting crystalline polymers consisting ofC8–C30 urea-ethyl-methacrylate, (I), and C22-acrylate, which reflected highside chain crystallinity and which were used as temperature-dependent coatingagents.

O

OHN O

O

C8H17 - C30H61

(I)

2. Copolymers, (II), consisting of 75% to 80%–C16-acrylate and 2-hydroxyethylacrylate having high side chain crystallinity were prepared by Bitler [2] andused as oil thickeners.

O O

O

OC16H33

O O

OC16H33

O

OC16H33

O

a b c d

OH OH

OC16H33

OO

OC16H33

(II)

References

1. S.P. Bitler et al., US Patent 6,831,116 (December 14, 2004)2. S.P. Bitler, US Patent 7,101,928 (September 5, 2006) US. Patent 6,989,417 (January 26, 2006)

Notes 101

C. Fluorine

Title: Multifunctional (Meth)Acrylate Compound,Photocurable Resin Composition and Article

Author: Y. Yoshikawa et al., US Patent Application 2007-0116971 (May 24, 2007)Assignee: Shin-Etsu Chemical Co., Ltd. (Annaka-shi, JP)

SIGNIFICANCE

Trifunctional (meth)acrylate fluorine-containing cyclic and acyclic silane compoundshave been prepared that form photocurable resin compositions. Coatings from theseresins are anti-fouling and resist organic stains from oil mist and fingerprints withoutdetracting from surface mar resistance.

REACTION

SiO

O

OO

H

H

H

F2CCF2

F2CCF2

F2CCF2

F2CCF3

SiO

O

OO

O

O

O

F2CCF2

F2CCF2

F2CCF2

F2CCF3

OO

OO

O

O

i ii Resin

i: 2-Hydroxyethyl acrylate, toluene, N,N-diethylhydroxylamine

ii: g-Acryloxypropyltrimethoxysilane, trimethylolpropane triacrylate, 1,6-hexane-diol diacrylate, DarocureRTM, UV irradiation

102

EXPERIMENTAL

1. Preparation of tri(2-Hydroxyethyl Acrylate) 1,1,1,2,2,3,3,4,4,5,5,6,6,7,7,8,8-Perfluoro-11-Decyl Cyclotrimethylsilane

A reactor was chargedwith 1,1,1,2,2,3,3,4,4,5,5,6,6,7,7,8,8-perfluoro-11-decyl cyclo-trimethyl-silane (0.1mol), 2-hydroxyethyl acrylate (0.315mol), and toluene (111.9parts) and then treated with N,N-diethylhydroxylamine (0.0126mol). Thereafter thereaction was heated for 8 hours at 70�C, cooled to ambient temperature, washed withwater, andconcentrated.Theproductwas isolatedhavingaviscosityof93.0mm2/switha refractive index of 1.4018.

2. Preparation of Photocurable Resin

A mixture consisting of silica (40 parts) previously treated with g-acryloxypropyl-trimethoxysilane, trimethylolpropane triacrylate (40 parts), 1,6-hexanediol diacrylate(20 parts), the Step 1 product (0.5 parts), and DarocureRTM (5 parts) as the free radicalinitiator were spin-coated and irradiated with UV light to form a coating having athickness of roughly 5 mm.

DERIVATIVES

O

Si

F2CCF2

F2CCF2

F2CCF2

F2CCF3

OOSi O O

Si

Si

O

O

OO

O

O

OSiO

O

OO

O

O

O

NH

OO

OO

O

O

CFOCF2

CFO

F2CCF2

OCF3

F3C

F3C

NOTES

1. A crosslinkable silicone rubber coating composition, (I), was prepared byAzechi [1] and used in preparing automotive airbags.

Notes 103

O

SiOSi

O

SiOSi

H

H

OO OO

(I)

2. Crosslinkable tetravinylsiloxane derivatives, (II), prepared by Hare [2] wereused as low-viscosity materials in dental impressions.

Si

O

O O

OSi

Si

Si

Si

(II)

3. Morita [3] prepared silsesquioxane resins using crosslinkable vinyl monomers,(III), for use in semiconductor devices.

OSiOSiO

SiOSiOSiOSi

O

O

Si

O

Si

OSi

O

Si

O

Si

O

OO

O

O

(III)

Si

References

1. S. Azechi et al., US Patent 7,153,583 (December 26, 2006)2. R.V. Hare, US Patent 6,561,807 (May 13, 2003)3. K. Morita et al., US Patent Application 20070054135 (March 8, 2007)

104 Multifunctional (Meth)Acrylate Compound, Photocurable Resin Composition and Article

D. Hydrophilic

Title: Polyoxyalkylene Phosphonates and ImprovedProcess for Their Synthesis

Author: S. Wo et al., US Patent 7,208,554 (April 24, 2007)Assignee: Rhodia Inc. (Cranbury, NJ)

SIGNIFICANCE

Hydrophilic surface active agents containing C1–C4 phosphoric acid derivativesprovide limited benefits because of their short aliphatic chain. To address this concern,hydrophilic phosphonic acid derivative containing an oligomeric ethylene glycolcomponent has been prepared.

REACTION

HO

O

OO

O

OO

O

POCH3

OOCH3

HO

O POH

OOH

iii iii10

10

1010 Note 1

i: Acetic anhydrideii: Di-t-butyl peroxide, dimethyl hydrogen phosphiteiii: Water

EXPERIMENTAL

1. Preparation of Acetyl Polyethylene Glycol Allyl Ether

A two-neck flask equipped with a Snyder distilling column and distilling head wascharged with polyethylene glycol allyl ether (1.0mol; Mw¼ 498 daltons) and then

105

treated with acetic anhydride (1.05mol). The mixture was heated to 110�C for3 hours during which time the acetic acid by-product was collected. At the end ofthe reaction excess acetic anhydride was removed under vacuum, and the productwas isolated.

2. Preparation of Acetyl Polyethylene Glycol Dimethyl Phosphite

The Step 1 product (1mol) was mixed with di-t-butyl peroxide (0.1mol) and thenadded to a second flask containing dimethyl hydrogen phosphite (1.1mol) and heatedfor 5.5 hours at between 130�C and 135�C. At the conclusion of the reaction excessdimethyl hydrogen phosphite was removed under vacuum, and the product wasisolated.

3. Preparation of Polyethylene Glycol Phosphonopropyl Ether

The entire Step 2 product was treated with excess water and hydrolyzed for 20 hoursfrom 135�C to 150�C. During this time the volume ratio of the Step 1 product/waterwas kept at 1:1, andmethanol and acetic acid by-productswere continuously removedby distillation. Thereafter the product was isolated and was completely soluble inwater.

DERIVATIVES


NOTES

1. Baker [1] determined that both polyethylene glycol phosphonopropyl ether, (I),with repeat units of 4 and 10 were effective as cerium oxide nanoparticledispersants.

aHO

O POH

OOH a = 4, 10

(I)

2. Zeller [2] prepared anionic and nonionic surface-active agents, (II), consistingof fatty alcohols and ethylene oxide which were used as surfactants.

aO

OX

13-15(II)

X = OH, PO(OH) 2, SO3Ha = 3–11

106 Polyoxyalkylene Phosphonates and Improved Process for Their Synthesis

3. In an earlier investigation by the author [3] sulfonated polyesters were preparedconsisting of ethylene glycol and terephthalate acid capped with dimethyl-5-sulfoterephthalate.

References

1. J.M. Baker et al., US Patent Application 2006-0241008 (October 26, 2006)2. E. Zeller et al., US Patent 7,183,446 (February 27, 2007) and US Patent 6,963,014 (November 8, 2005)3. S. Wo, US Patent 6,576,716 (June 10, 2003)

Notes 107

E. Hydrophobic

Title: Polymers and Polymer Coatings

Author: C. Ober et al., US Patent Application 2007-0053867 (March 8, 2007)Assignee: Cornell Research Foundation, Inc. (Ithaca, NY)

SIGNIFICANCE

A limited number ofmarine paint additives exist that can provide antifouling coatingsthat are nontoxic and “fouling repellant.” Silicon-free polyacrylates containing apendant semifluorinated alkyl substituent have been prepared to address this need.

REACTION

OO

t-C4H9

Br

OO

t-C4H9

OO OO

t-C4H9

OO

Br

OOO

Br

O

CF2

F2C

23

23

82

23 82

x

y

x = 0–15y = 1–7

i ii iii

OHOOO

Br

23 82iv

i: Acetone, pentamethyldiethylene triamine, copper(I) bromide, copper(II) bro-mide, methyl 2-bromopropionate

ii: Copper(I) bromide, styrene, pentamethyldiethylene triamineiii: Hydrochloric acid, dioxaneiv: Pyridine, 1,3-dicyclohexylcarbodiimide, 4-dimethylaminopyridine, Zonyl�

FSO-100, THF

108

EXPERIMENTAL

1. Preparation of Poly(t-Butylacrylate) Macroinitiator

A mixture containing 3ml of acetone, t-butylacrylate (80mmol), and pentamethyl-diethylene-triamine (0.8mmol) were added to CuBr (0.8mmol) and CuBr2(0.04mmol). This mixture was then treated with methyl 2-bromopropionate(1.6mmol) and heated for 6 hours at 60�C. It was cooled to ambient temperatureand treated with 50ml of acetone and neutral alumina. The acetone solution wasconcentrated and the residue purified by dissolving in diethyl ether. The purifiedmaterial was precipitated in a methanol/water mixture, 1:1, at 0�C, dried, and theproduct was isolated having a Mn of 3000 daltons with a polydispersity index of 1.1.

2. Preparation of Poly[(t-Butylacrylate)-block-Styrene]

Amixture consisting of the Step 1 product (0.67mmol) and CuBr (0.95mmol) mixedwith styrene (95mmol)was stirred until thepolymer dissolved. Pentamethyldiethylenetriamine (0.95mmol) was added, and the mixture was heated for 2 hours at 100�C.After cooling to ambient temperature the viscous polymer was dissolved in 150ml ofTHF and then passed through a column of neutral alumina. The solution wasconcentrated, the residue precipitated in methanol, and the polymer isolated havingpolydispersity index of 1.1.

3. Preparation of poly(Acrylic Acid)-block-Polystyrene

Twomilliliters of concentratedhydrochloric acid solutionwas added to a10%solutionof the Step 2 product dissolved in dioxane and refluxed for 6 hours. After cooling toambient temperature the polymer was precipitated in water, and the product wasisolated after recovering by filtration.

1H NMR (DMSO-d6): d 2.2 and 1.6 (br s, –CH2, >CH–); 6.5 and 7.1 (br s, 5H, styrene); 12.0 (br s, COOH)FTIR (film; cm�1): 3600-2400 (O–H stretching, carboxylic acid); 3026 (C–H stretching, aromatic); 2926

(C–H stretching, backbone); 1716 (C¼O stretching, ester); 1492, 1452 (C¼C stretching, aromatic);758 and 700 (C–H bending, aromatic)

1H NMR (CDCl3): d 1.5 (s, 9H, –C(CH3)3); 1.85 and 2.35 (br s, –CH2, , >CH–); (s, 3H, –OCH3) 4.1 (m, 1H,>CH–Br)

FTIR (film; cm�1): 2977 (C–H stretching, t-butyl); 2929 (C–H stretching, backbone); 1727 (C¼Ostretching, ester); 1367 (C–H bending, t-butyl).

1H NMR (CDCl3):d1.5 (s, 9H, –C(CH3)3); 1.85and2.35 (br s, –CH2, >CH–); 6.5AND7.1 (br s, 5H, styrene)FTIR (film; cm�1): 3026 (C–H stretching, aromatic); 2976 (C–H stretching, t-butyl); 2926 (C–H stretching,

backbone);1728(C¼Ostretching,ester);1493,1452(C¼Cstretching,aromatic);1367(C–Hbending,t-butyl); 758 and 700 (C–H bending, aromatic)

Experimental 109

4. Preparation of poly(Ethoxylated Fluoroalkyl Acrylate)-block-Polystyrene

In the first vessel the Step 3 product (1 g) was dissolved in 5ml of pyridine.In a second vessel 1,3-dicyclohexylcarbodiimide (6.57mmol), 4-dimethylamino-pyridine (0.823mmol), and Zonyl FSO-100 (6 g) were dissolved in THF and thenadded dropwise to the first vessel. The reaction was stirred for 2.5 days at ambienttemperature and filtered to remove dicyclohexylurea. The solution was concentratedand then precipitated by pouring into methanol. It was re-dissolved in THF and re-precipitated into methanol; the product was isolated after filtration.

DERIVATIVES


TESTING

Quantitative testing data on biofouling assays was not provided.

NOTES

1. Semifluorinated block copolymers, (I), were previously prepared by the author[1] and then blended with styrene-ethylene/butylene-styrene thermoplasticelastomers to provide surface-active block copolymers.

x y

x = 500–1000y = 200–1000z = 100–1000n = 4, 6

nCF2

F

O

CF2

F

n

8

O

z

(I)

8

1H NMR (300MHz, CDCl3): d 6.5 and 7.1 (5H, styrene); 4.16 (br s, 2H, –COOCH.sub.2–); 3.77 (t, 2H,–COOCH.sub.2CH.sub.2–); 3.64 (br s, –OCH.sub.2CH.sub.2O–); 2.42 (m, 2H, –CH.sub.2CF.sub.2–); 1.86, 1.43 (backbone)

19F NMR (CDCl3, CF3COOH reference) d: �126.65, �124.16, �123.38, �122.41, �113.95, �81.27(3F, –CF3)

FTIR (film; cm�1): 3026 (C–H stretching, aromatic); 2922 (C–H stretching, backbone); 1731 (C¼Ostretching, ester); 1490, 1450 (C¼C stretching, aromatic); 1400–1000 (C–F stretching); 754and 698 (C–H bending, aromatic)

110 Polymers and Polymer Coatings

2. Biofouling-resistant surfactant compositions, (II), were prepared by Swedberg[2] that had a hydrophobic domain that promoted adsorption of the surfactantmolecule to the surface of selected surface active materials.

(PEO)129 (PPO)100 (PEO)129 OHN

O

SO3H(II)

3. Pendant quaternary amine salts prepared by Price [3] were effective asantifouling additives in marine paint.

a

NH

O NH Palmitic

(III)

References

1. C. Ober et al., US Patent 6,750,296 (June 15, 2004)2. S.A. Swedberg et al., US Patent 7,201,834 (April 10, 2007)3. C. Price, US Patent Application 2007-0082972 (April 12, 2007)

Notes 111

Title: Photochemical Crosslinkers for PolymerCoatings and Substrate Tie-Layer

Author: P. Guire et al., US Patent Application 2007-0003707 (January 4, 2007)Assignee: SurModics, Inc. (Eden Prairie, MN)

SIGNIFICANCE

Two trifunctional benzophenone derivatives have been synthesized that are UVphotoactive at 254 nm and photolytically incorporated into poly(e-caprolactone) andpoly(vinylpyrrolidone). These agents are designed to be used in photopolymerizationreactions.

REACTION

HOO O

ONN

OHN

OH

O

O O

O

O

OH

O

i

Photochemical curing agent

i: Glycerol triglycidyl ether, potassium carbonate, acetone

EXPERIMENTAL

Preparation of tri(N-2-Hydroxy-3-(4-Benzophenoxy)Propyl))-s-Triazine

A round bottom flaskwas chargedwith 4-hydroxybenzophenone (2.26 g), 0.532ml ofglycerol triglycidyl ether, potassium carbonate (3.3 g), and 50ml of acetone and thenrefluxed 24 hours and concentrated. The residue was dissolved in CCl3H and filtered.The filtratewaswashed three timeswith 4MNaOHaqueous solution, oncewithwater,

112

twicewith 1MHCl, and re-washed three timeswithwater. The solutionwasdried overMgSO4, filtered, and concentrated. The residue was washed three times with diethylether and then re-dried, and the product was isolated.

TESTING

Wettable Testing

A coating solution was prepared in isopropanol using the Step 1 product (0.5mg/ml)and poly-vinylpyrrolidone (50mg/ml). A 100 ml of the coating solutionwas applied topolyvinylchloride coverslips and then dried overnight. All pieces were illuminated at254 nm light from 0 to 10 minutes and rinsed with 30 minutes in water with gentleagitating.The static contact anglewithwaterwas takenon agoniometerwith three 3 mldrops of water andmeasured three times. Contact angle testing results are provided inTable 1.

Photoreactive Surface Preparation and Testing

A photoreactive polymer solution was prepared by mixing poly(e-caprolactone)(50mg/ml) filmwith theStep1product (0.5mg/ml) and thencasting themixtureontoa glass slide. The film was treated with poly(vinylpyrrolidone) (10 ml 50mg/ml,30,000daltons),dissolved in isopropanol solution, and themixturewasconcentrated.The film was illuminated for 20 minutes using 254 nm light and then incubated inwater on a shaker for 3 hours to remove unbound PVP. After staining with 0.5%w/vaqueous solution of Congo Red the components of a film consisting of poly(vinyl-pyrrolidone) and poly(e-caprolactone) was determined to be homogeneouslydistributed. By contrast, films prepared without the triazine crosslinker showed nostainings, suggesting that the unbound poly(vinylpyrrolidone) was removed by therinse.

TABLE 1. Contact angles of PVC coated with the Step 1product followed by UV activation at 254 nm.

Illumination Time at 254 nm (min) Contact Angle (deg)

0 38.1 – 10.00.5 24.8 – 7.81 31.7 – 6.32 31.1 – 4.45 23.1 – 8.810 29.1 – 3.0Uncoated 61.9 – 1.4

Testing 113

NOTES

1. Oxime derivatives were prepared by Kunimoto [1] containing both esteroximeand aryl ketone components, (I), were particularly effective in photopolymer-ization reactions.

NO

O

S

O

(I)

2. Blood compatible surfaces were prepared by the author [2] by UV curing ofbenzophenone-containing polyethylene ether, (II).

O

ONH

O

CO2H4

13

(II)

3. Swan [3] prepared a benzene 1,3-disulfonic acid derivative, (III), as a surfacecoating agent for polyvinylpyrrolidone for subsequent use as a surfacemodifieron polyvinylchloride urinary catheters.

O

O

O

O

SO3KKO3S

(III)

4. Swan [4] prepared terpolymers, (IV), containing photoreactive groupsthat covalently bond to nucleic acids for use in preparing nucleic acidsmicroarrays.

114 Photochemical Crosslinkers for Polymer Coatings and Substrate Tie-Layer

NHO

O

O

2

NH2O OO

HN

O O

O

3

cba

(IV)

References

1. K. Kunimoto et al., US Patent 7,189,489 (March 13, 2007)2. P. E. Guire et al., US Patent 7,144,573 (December 5, 2006) and US Patent 7,071,235 (July 4, 2006)3. D. G. Swan, US Patent 7,138,541 (November 21, 2006)4. D. G. Swan et al., US Patent 6,762,019 (July 13, 2004)

Notes 115

Title: Use of Poly(Dimethyl Ketone) to ManufactureArticles in Direct Contact with a Humid or AqueousMedium

Author: B. Brule et al., US Patent 7,011,873 (March 24, 2006)Assignee: Arkema (Puteaux, FR)

SIGNIFICANCE

The low water permeability of polydimethyl ketone has been found to be effective inpreparing hermetically sealed industrial food packaging that comes in direct contactwith a humid or aqueous medium.

REACTION

O

O O

C O O

O

iiia bNotes 1, 2

a > b

i: Pyrolysisii: Aluminium tribromide, carbon tetrachloride

EXPERIMENTAL

1. Preparation of Dimethylketene

Isobutyric anhydride was pyrolysized between 550�C and 675�C under an absolutepressure of between 30 and 40mmHg and while under a nitrogen stream of 1.5 ft3/h.Gaseous products from the pyrolysis chamber passed through awater-jacketed coppercondenser and then through two glass cylinder separators. The residue vapors werenext passed though a cold trap at �50�C and conducted to a cold condenser andreceiver to collect the dimethylketene, BP¼ 34�C.

116

2. Preparation of Poly(Dimethyl Ketone)

Dimethylketene (15.2 g) enclosed in a tubular reactor was placed in an acetone Dewarflask at �30�C and treated with 38ml of carbon tetrachloride and 2.5ml of 0.86Maluminium tribromide solution. Thereafter the mixture was stirred for 5 hours at�30�C and at ambient temperature for 19 hours. The reaction was quenched by theaddition of 20ml of methanol, and the polymer was isolated after precipitation in200ml of methanol containing 4ml of hydrochloric acid.

DERIVATIVES

Only the Step 2 product was prepared.

TESTING

Water Permeability

Water permeability was determined at 38�C for 24 hours using a 50 mm thick film inaccordance with the ASTM E96E standard. Testing results are provided in Table 1.

NOTES

1. Linemann [1] prepared polydimethylketene by the Friedel-Craft cationicpolymerization of dimethylketene using AlBr3.

2. The Step 2 product containing up to 30mol% ether content was effective as anoxygen barrier under high relative humidity and used in pipes, bottles, andcontainers by Egret [2].

References

1. R. Linemann et al., US Patent 7,105,615 (September 12, 2006)2. H. Egret et al., US Patent 6,793,995 (September 21, 2004), US Patent 6,528,135 (September 21, 2004),

and US Patent 6,528,135 (March 4, 2003)

TABLE 1. Water permeability testing results of selected polymers usingthe ASTM E96E standard.

Material Water Permeability (g/m2 24 h)

Step 2 product 6

High-density polyethylene 3Polypropylene 5Low-density polyethylene 5Polyvinyl chloride 18Poly(ethylene-co-vinyl alcohol) [32mol% ethylene] 35Polyaniline 50

Notes 117

F. Thermally Stable

Title: Polyaryleneetherketone Phosphine OxideCompositions Incorporating Cycloaliphatic Unitsfor Use as Polymeric Binders in Thermal ControlCoatings and Method for Synthesizing Same

Author: T. D. Dang et al., US Patent 7,208,551 (April 24, 2007)Assignee: University of Dayton (Dayton, OH)

SIGNIFICANCE

The use of polymers as thermal control coatings in space environments is desirable,since they provide significant weight reduction, goodmechanical strength, and exhibitthermal and thermooxidative stability. There still remains a need, however, for coatingsthat resist degradation by ultraviolet radiation and atomic oxygen. This investigationaddresses that need using polyaryleneetherketone phosphine oxide materials.

REACTION

a

HO

O

O

OH

Cl

O

O

Cl O

O

H3CO

OCH3

O

OPO

i ii

O

O

HO

OH

iii

Not isolated

118

i: 4,9-Diamantanedicarboxylic acid, thionyl chloride, aluminum chloride, anisoleii: Pyridine hydrogen chlorideiii: 4,40-Difluorotriphenylphosphine oxide, potassium carbonate, DMAc, toluene

EXPERIMENTAL

1. Preparation of 4,9-bis(4-Methoxybenzoyl)Diamantane

4,9-Diamantanedicarboxylic acid and excess thionyl chloride were refluxed until aclear solution was obtained and then concentrated. The crude 4,9-diamantanedi-carboxylic acid chloride (0.0211 mole) was slowly added to a chilled solution ofAlCl3 (6.75 g) and anisole (22.8 g), and the mixture was stirred overnight at ambienttemperature. The product was precipitated by pouring into 0.1M aqueous HCl, thenstirred, filtered, and the solid further stirred in methanol to remove unreactedanisole. The white solid was re-crystallized from a mixture of 700ml toluene and100ml THF and the product was isolated in 72% yield, MP¼ 213–214�C.

2. Preparation of 4,9-bis(4-Hydroxybenzoyl)Diamantane

A round-bottomed flask was charged with the Step 1 product (0.0285mol) and excesspyridine hydrochloride (0.2850mol), thenheated for 3 hours at 225�Cand cooled. Thereaction mixture was poured into 40ml of concentrated HCl diluted with 200ml ofwater, and a precipitate formed. The solid was isolated, dried, then dissolved in THFwith hexane slowly added until the solution became slightly turbid. The solution wasnext slowly cooled, and the product was isolated in 57% yield, MP¼ 313–315�C.

3. Preparation of 4,9-Diamantane-Based PolyaryleneetherketoneTriphenylphosphine Oxide

Areactionvessel equippedwith aDean–Stark trapwaschargedwith theStep2product(1.3212 g), 4,40-difluorotriphenylphosphine oxide (0.9689 g), potassium carbonate(1.022 g), 7.2ml DMAc, and 15ml of toluene and then refluxed for at least 4 hours.After removal of the azeotrope and toluene, the mixture was refluxed at 165�C for anadditional 16 hours. The polymer was precipitated in water, shredded in a blender,filtered, dried, and the product was isolated in 92% yield.

Experimental 119

DERIVATIVES

NOTE

Resins prepared by Timberlake [1] consisting of benzoguanamine-modified phenol-formaldehyde or melamine-phenol-formaldehyde resins were treated with tris(4-methoxyphenyl)phosphine oxide to prepare coatings in printed circuit boards.Isomeric mixtures of tris(2-hydroxyphenyl)-phosphine oxide compounds were alsoconverted into resins by Brennan [2] by reacting with tris(4-methoxy-phenyl)phos-phine oxide derivatives.

References

1. L.D. Timberlake et al., US Patent 7,202,311 (April 10, 2007) and US Patent 7,201,957 (April 10, 2007)2. D.J. Brennan et al., US Patent 6,740,732 (May 25, 2004) and US Patent 6,969,756 (November 29, 2005)

TABLE 1. Selected polyaryleneetherketone phosphine oxide derivatives preparedaccording to the current invention and corresponding viscosities at 30�C.

Entry Structure

PolymerConcentration

(g/25mlCCl3H)

[Z](dl/g)

Step 1product

O

OPO

n

0.0632 0.27

7

O

O

O

O

P

O n

0.25 1.18

11O

O

O

O

PO

n

0.25 0.38

120 Polyaryleneetherketone Phosphine Oxide Compositions Incorporating Cycloaliphatic Units

G. Vapor Deposition of Polymers

Title: Functionalization of Porous Materialsby Vacuum Deposition of Polymers

Author: M. G. Mikhael et al., US Patent 7,157,117 (January 2, 2007)Assignee: Sigma Laboratories of Arizona, LLC (Tucson, AZ)

SIGNIFICANCE

Vapor deposition has been used to prepare fibers such as woven and nonwovensynthetic and natural fibers having hydrophobic/oleophobic and biocide properties.This process entails flash evaporationof a perfluoroacrylatemonomer and its radiationcuring in a vacuum chamber onto a selected fiber surface.

REACTION

...

O F2C CF3

... ...O

F2C CF3

i

aNote 1

b

b b > 5

a...

i: Perfluoroacrylate

121

EXPERIMENTAL

Preparation of Polypropylene-g-Perfluoroacrylate Nonwoven Fabricwith a Hydrophobic/Oleophobic Repellent Surface

A perfluoroacrylate monomer was flash evaporated at 100 millitorr and exposed topolypropylene fibers pretreated in a plasma field within one second while the fabricwas traveling at 50m/min. The condensed monomer layer was then cured in-line byelectron beam radiation within 100 milliseconds resulting in a 0.1 mm perfluoroa-crylate coating on the material surface. The product had an adequate repellency forboth water and oil and a surface energy of 27 dyne/cm.

DERIVATIVES

NOTES

1. Color changing sensing coatings were prepared in the current invention using amixture of phenolphthaleine and perfluoroacrylate monomer; heat-sensingcoatings were prepared by grafting 4-pentyl-4-cyanobiphenyl; and strawberryodor smelling coatings were prepared by coating a surface with 4-(2,6,6-trimethyl-1-cyclohexen-1-yl)-3-buten-2-one.

2. In an earlier investigation by the author [1], 0.3 to 0.8 m coatings of polyethyleneand poly(a-methylstyrene) solid oligomers having Mn’s of roughly 4000 and1300 daltons, respectively, were vapor deposited onto a polyester surface at1� 10�4 to 1� 10�5 torr at 300�C.

3. Affinito [2] vapor coated hexanediol diacrylate, trimethylolpropane triacrylate,and tripropyleneglycol diacrylate liquid monomers at roughly 80�C and1� 10�4 torr onto polyethylene terephtholate and then radiation polymerizedthe surface using electron beam radiation.

TABLE 1. Water/alcohol and oil repellency testing of fabrics modified withperfluoroacrylate monomer to confer a hydrophobic/oleophobic repellent surface.

Water/Alcohol Repellency TestOil Repellency Test

Fabric Sample Unwashed 10 Wash Cycles Unwashed 10 Wash Cycles

Cotton Control 1 1 1 1Treated 6 4 5 3

Polyester*1 Control 3 3 1 1Treated 6 5 6 4

Nylon*2 Control 3 3 1 1Treated 6 5 6 4

Note: Higher testing values are preferred. Surface energies of fabrics were not provided by author.*1Polyester not specified.*2Nylon not specified.

122 Functionalization of Porous Materials by Vacuum Deposition of Polymers

4. Cured coatings having dielectric dissipation factors < 0.05 at 24�C at 600Hz onconductorswere prepared byKrongauz [3] by radiation curing a surface coatingcontaining hydroxyl-terminated hydrogenated 1,2- and 1,4-polybutadiene,isophorone diisocyanate, and hydroxyethylacrylate.

5. Bilodeau [4] prepared barriers consisting of radiation cured N-vinyl-2-pyrro-lidone and N-vinylcaprolactam that were impervious to migratory componentsin autmotive tires.

References

1. M.G. Mikhael et al., US Patent 7,005,161 (February 28, 2006)2. J.D. Affinito, US Patent 7,112,351 (September 26, 2006)3. V.V. Krongauz et al., US Patent 7,109,253 (September 19, 2006)4. W.L. Bilodeau et al., US Patent 7,141,285 (November 28, 2006)

Notes 123

H. Succinic Anhydride Derivatives

Title: Light Absorbent Agent Polymer for OrganicAnti-reflective Coating and Preparation Methodand Organic Anti-reflective Coating CompositionComprising the Same

Author: J.-c. Jung et al., US Patent 7,033,729 (April 25, 2006)Assignee: Hynix Semiconductor, Inc. (Kyungki-do, KR)

SIGNIFICANCE

In the fabrication process of ultra-fine patterns for photoresists using ArF light source(193 nm), few organic or inorganic anti-reflective coating currently exist. This artaddresses this need using poly(maleic anhydride-co-4-dihydro-1,4-methano-naph-thalene-5,8-diol) diacetate crosslinked with poly(styrene-co-vinyl dimethylacetal).

REACTION

a b

OO O OO O

OOO O

i Organic anti-reflective material

ii

Note 1

i: 4-Dihydro-1,4-methano-naphthalene-5,8-diol diacetate, propylene glycol methy-lether acetate, 2,20-azobis isobutyronitrile

ii: Poly(styrene-co-vinyl dimethylacetal), propylene glycol methylether acetate,methyl 3-methoxy propionate, 2-heptanone, THF, 2-hydroxycyclo-pentyl-1-tri-fluoromethylsulfonic acid

124

EXPERIMENTAL

1. Preparation of Light-Absorbing Polymer Agent

A reaction vessel was charged with maleic anhydride (20 g), 1,4-dihydro-1,4-metha-no-naphthalene-5,8-diol diacetate (26 g), and propylene glycol methylether acetate(26 g), and then treated with 2,20-azobissobutyronitrile (0.5 g). The mixture wasreacted at 65�C for 7 hours, concentrated, precipitated in water, washed with diethylether, and the product was isolated in 40% yield, Mw of roughly 7000 daltons.

2. Preparation of Organic Anti-reflective Coating Composition

The Step 1 product (1 g) and poly(styrene-co-vinyl dimethylacetal) (0.4 g) weredissolved in a mixture comprising propylene glycol methylether acetate (4 g), methyl3-methoxy propionate, 2-heptanone (10 g), and THF (7 g). The solution was thentreated with 2-hydroxycyclo-pentyl-1-trifluoromethylsulfonic acid (0.1 g), filtered,and the product was isolated.

3. Preparation of Organic Anti-reflective Coating and Photoresist Pattern

The Step 2 product was spin-coated onto a silicone wafer and baked for 2 minutes at215�C. Thereafter the anti-reflective mixture was coated with a Keum Ho petroleumphotosensitive agent and baked for 90 seconds 110�C. After these processes thematerial was exposed to a light source bymeans of ASML/900 scanner apparatus andbaked an additional 90 minutes at 130�C. The exposed wafer was developed using anaqueous solution of 2.38% tetramethyl-ammonium hydroxide.

DERIVATIVES


NOTES

1. The Step 2 crosslinking agent, poly(styrene-co-vinyl dimethylacetal), (I), isillustrated below.

O O

a b

(I)

Notes 125

2. An additional Step 1 light absorbing polymer agent, (II), was prepared by theauthor [1] in a subsequent investigation and used as an organic anti-reflectivecoating.

OO O

OHHO

O Oa b

(II)

3. Compositions for an anti-reflective light-absorbing layer using diazoquinones,(III), were prepared by Yoon [2] and used in forming patterns in semiconductordevices.

a

OO

O

N2

OO CO2H

(III)

4. Lee [3] prepared organic anti-reflective polymer coatings consisting of poly-vinyl phosphoric acid and poly(vinyl acetate-co-ethylene).

126 Light Absorbent Agent Polymer for Organic Anti-reflective Coating and Preparation Method

5. Anti-reflective polymer coatings, (IV), prepared by the author [4] were used informing ultra-fine patterns of photoresist for photolithography.

O NO O O O

CH2

NO OO OO

a b

a b

(IV)

References

1. J.-c. Jung et al., US Patent Application, 2005-0084798 (April 21, 2005), US Patent 7,205,089 (April 17,2007), and US Patent Application, 2006-0004161 (January 5, 2006)

2. S.-w. Yoon et al., US Patent 6,838,223 (January 4, 2005)3. G.-s. Lee et al., US Patent 7,198,887 (April 3, 2007)4. J.-c. Jung et al., US Patent 7,186,496 (March 6, 2007)

Notes 127

V. COSMETICS

Title: Water-Soluble or Water-Dispersible GraftPolymers, Their Preparation and Use

Author: S. N. Kim et al., US Patent 6,992,161 (January 31, 2006)Assignee: BASF Aktiengesellschaft (Ludwigshafen, DE)

SIGNIFICANCE

Urethane and polyurea segments have been introduced into a polymer containingpolyesters, polyethers, and casein. When blended into hair spray formulationscontaining upto 5wt% solids, enhanced curl retention and flexural strength resulted.

REACTION

O OHN

OO O

O O O

O

OO

20 4 6 20

HN

O

NH

HNCasein

O

HN O

OCO2H

CO2H

i a

i: Isophthalic acid, adipic acid, hexanediol, polyethylene glycol, dimethylolpropanoicacid, isophorone dissocyanate, triethanolamine, casein, 2-amino-2-methylpropanol

EXPERIMENTAL

1. Preparation of Polyethylene Glycol Graft Copolymer

A reaction kettlewas charged with polyesterdiol (0.5mol;Mw 1000 daltons; preparedfrom isophthalic acid, adipic acid and hexanediol), polyethylene glycol (0.05mol;MW¼ 1500 daltons), and dimethylolpropanoic acid (1.25mol) dissolved in methylethyl ketone. The mixture was heated to 80�C. When the reaction was completed the


129

mixture temperature was lowered to 50�C and isophorone diisocyanate (1.9mol) wasadded dropwise. At an internal temperature of 90�C the reaction mixture was stirreduntil the isocyanate group content remained constant. Thereafter the reactionmixturewas cooled to ambient temperature and treated dropwise with 15% casein (116.5 g)dissolved in triethanolamine, and next stirred until isocyanate groups were no longerdetectable. The mixture was then treated with water and the product was neutralizedwith 2-amino-2-methylpropanol. The solution was concentrated, and the product wasobtained by spray drying under vacuum at �80�C.

Hair Spray Formulation

Flexural Strength and Curl Retention

NOTES

1. Polyurethanes containing polytetrahydrofuran, diethylene glycol, stearyl alco-hol, and hexamethylene diisocyanate were prepared by Meffert [1] and used inhair compositions.

2. Alkali-swellable polymer compositions consisting of acrylic acid, methylmethacrylate, behenyl methacrylate, lauryl methacrylate, and sodium laurylsulfate were prepared by Tamareselvy [2] and used as a hair rheology modifierand as a hair setting agent.

TABLE 1. Hand pump spray formulation witha volatile organic compounds content of 55%.

Component Charge (wt%)

Step 1 product (Solids content) 5Water 40Ethanol 55Fragrance/surfactant q.s

TABLE 2. Hair spray formulations of selected casein-containing Step 1 products andtheir effect on curl retention and flexural strength.

EntryPolyesterdiol

(mol)PEG E1500

(mol)DMPA(mol)

MDEA(mol)

IPDI(mol)

Casein(wt%)

CurlRetention

(%)

FlexuralStrength(cN)

3 1 0.1 — — — 50 51 3124 1 0.1 2.5 — 3.8 10 65 3566 0.9 0.1 2.5 0.1 3.8 5 73 452

130 Water-Soluble or Water-Dispersible Graft Polymers, Their Preparation and Use

3. Rollat [3] prepared acrylate terpolymers consisting of 2-ethylhexyl acrylate,isobornyl acrylate, acrylic acid, and methacrylic acid, 55, 50, 2.5, 2.5 parts,respectively, that were useful in hair styling compositions.

4. Polymers consisting of t-butyl acrylate, methacrylic acid, sodium ether dodecylsulfate, and n-dodecylthiol were prepared by Drohmann [4] and used inhairsprays.

References

1. H. Meffert et al., US Patent 7,019,061 (March 28, 2006)2. K. Tamareselvy et al., US Patent 7,153,496 (December 26, 2006)3. I. Rollat et al., US Patent 7,122,175 (October 17, 2006) and US Patent 7,048,916 (May 23, 2006)4. C. Drohmann et al., US Patent 7,147,842 (December 12, 2006)

Notes 131

VI. DENTAL

A. Cement

Title: (Meth)Acrylate-Substituted IminooxidiazineDione Derivatives

Author: N. Moszner et al., US Patent 7,078,446 (July 18, 2006)Assignee: Ivoclar Vivadent AG (Schaan, LI)

SIGNIFICANCE

UV-curable dental cement composites consisting of 20% asymmetrical 1,3,5-oxadiazine-2,4-dione trimethacrylate derivatives have been prepared that have lowershear viscosities than their symmetric triazole counterpart. This property is particu-larly needed for preparing “flowable” pre-cured cement paste.

REACTION

O

O

O N

NCOOCN

NCO O

O

O N

NH

NH

O

O

O

O

ONH

O

O

O

O

O

O

O

6

66

6

66 iNote 1

i: 2-Hydroxylethyl methacrylate, 2,2,6,6-tetramethyl-piperidine-1-oxyl, hydroqui-none monomethylether, dibutyltin dioctoate, CH2Cl2


133

EXPERIMENTAL

Preparation of 3,5-bis(6-(6-Hexyl Carbamate-Methacrylate)-6-[(6-HexylCarbamate-Methacrylate)Imino]-1,3,5-Oxadiazine-2,4-Dione

3,5-bis(6-Isocyanato-hexyl)-6-[(6-isocyanato-hexyl)imino]-1,3,5-oxadiazine-2,4-dione (0.1mol) was added dropwise at ambient temperature to a solution containing2-hydroxylethyl methacrylate (0.3mol), 2,2,6,6-tetramethyl-piperidine-1-oxyl(12mg), hydroquinone monomethylether (25mg), and dibutyltin dioctoate (0.2 g)dissolved in 100ml of CH2Cl2 and then stirred for 20 hours. Next the reactionmixturewaswashed twicewith 100ml of 1.0MNaOHand three timeswith 100ml of saturatedbrine.TheorganicphasewasdriedwithNa2SO4andconcentrated, and theproductwasisolated in 67% yield.

DERIVATIVES

TABLE 1. Viscosity of UV-curable dental composites containing 20% experimentalassymmetric additives or a symmetric reference.

Entry StructurePaste Shear

Viscosity (Pas)

1

O

O

O N

NH

NH

O

OO

O

ONH

O

O

O

O

OO

O

6

66 2.21

SymmetricalReference

N

N

N

O

O

NH

NH

O

OO

O

ONH

O

O

O

O

OO

O

6

66

O3.36

IR (ATR; cm�1): 3368 (w), 2930 (m), 2858 (w), 1785 (w), 1682 (s), 1522 (m), 1458 (s), and 11631H-NMR (CDCl3): d 1.35 (br, 12H, CH2), 1.51 (br, 6H, CH2), 1.63 (br, 6H, CH2), 1.94 (s, 9H, CH3), 3.17 and

3.34 (t, sat. 6H,CH2N), 3.84 (t, 6H, CH2N), 4.31 (br, 12H, CH2O), 5.02 5.03 (br, 3H, NH), 5.59and 6.13 (2s, each 3H, .dbd.CH2) ppm

134 (Meth)Acrylate-Substituted Iminooxidiazine Dione Derivatives

Table 1. (Continued )

Entry StructurePaste Shear

Viscosity (Pas)

2

O

O

O N

NH

NH

O

OO

NH

O

O

6

66

O

O

O

O

O

OO

O

OO

O OO O

2.20

SymmetricalReference N

O

O

NH

NH

O

OO

NH

O

O

6

66

O

O

O

O

O

OO

O

OO

O OO O

O

2.79

Note: The remainder of the composit consisted of 80 wt% filler consisting of barium- aluminum-boronsilicate glass powder, silicon dioxide-zirconium dioxide, and ytterbium fluoride. For dental compositeslower viscosities are preferred because of their flowability.

Derivatives 135

NOTES

1. The preparation of the triisocyanate Step 1 reagent is described by Richter [1].

2. In an earlier investigation by the author [2] di-amides, (I) and (II), wereprepared and used in dental adhesive composites. Materials based on acryl-ic-ester phosphonic acids, (III) and (IV), and used in dental cements were alsoprepared by the author [3].

N N

O ONH

OO

HN

NH

OO

O HN

O)II()I(

O

O

OPOH

OOH

O

OO

O

OP

OH

OOH

OP

HOO

HO

(III) (IV)

3. In a subsequent investigation by the author [4] photopolymerizable bis-acylphosphine oxides, (V), effective as Norrish type I cleavage agents at400 to 500 nm, were prepared and used as self-conditioning dental fixingcements. Self-etching dental materials such as adhesives, coating materials,and composites consisting of (meth)acrylamide phosphates, (VI), were alsoprepared by the author [5] and used in restorative dentistry.

P

OO O

O O

(V)

O

N

O

N

POH

O

OH

O(VI)

136 (Meth)Acrylate-Substituted Iminooxidiazine Dione Derivatives

4. Polymerizable cyclopropyl acrylates, (VII), were prepared by the author [5]and used as components in dental cements and filling materials.

O O

O O

CO2C2H5 C2H5O2CO

O

O

O

(VII)

References

1. F.L. Richter et al., US Patent 5,914,383 (January 22, 1999)2. N. Moszner et al., US Patent 6,953,832 (October 11, 2005)3. N. Moszner et al., US Patent 6,953,832 (October 11, 2005) and US Patent 6,900,251 (May 31, 2005)4. N. Moszner et al., US Patent Application 2007-0027229 (February 1, 2007)5. N. Moszner et al., US Patent Application 2006-0178469 (August 10, 2006)

Notes 137

B. Dental Composites

Title: (Meth)Acrylic Ester Compound and Use Thereof

Author: A. Otsuji et al., US Patent Application 2007-0078198 (April 5, 2007)Assignee: Mitsui Chemicals, Inc. (Tokyo, JP)

SIGNIFICANCE

Diacrylatemonomers havebeenprepared that are photocurable invisible light and thathave small polymerization shrinkage and high X-ray contrast properties. Whenpolymerized with 0.01 to 0.04 mm glass powder, these dental composites were easilymachined into artificial teeth.

REACTION

O OO O

O OO OO OO O

ClCl

O OO OO OO O

Note 1

i ii

O OO OOH OH

iii

i: 4-Phenylphenol, sodium hydroxide, DMAc

138

ii: 3-Chloropropionic acid chloride, DMAciii: Acetone, triethyl amine

EXPERIMENTAL

1. Preparation of 1,3-di-[2-Hydroxyl-3-(4-Phenylphenoxy)-1-Propoxy]Benzene

A reactor was charged with 4-phenylphenol (0.40mol), NaOH (0.53 g), and DMAc(40 g) and then treated with the dropwise addition of a solution of resorcin diglycidylether (0.20mol) in DMAc (40 g). The mixture was stirred for 6 hours at 100�C anddiluted with 200 g of methanol/water, 1:1. Crystals that precipitated were collected,dried, and the product was isolated in 97% yield as a colorless powder.

2. Preparation of 1,3-di-[2-(Chloropropionic Acid Ester)-3-(4-Phenylphenoxy)-1-Propoxy]Benzene

The Step 1 product (0.10mol) was dissolved in DMAc (60 g) and treated with thedropwise addition of 3-chloropropionic acid chloride (0.36 mole) at 60�C for over 60minutes. The mixture was stirred for 4 hours at 60�C and cooled to ambienttemperature. It was poured into ice water, extracted with of toluene (250 g), andwashed with 3% aqueous NaHCO3. The organic layer was repeatedly washed withwater until it was neutral and concentrated, and the product was isolated in 95% yieldas a colorless, transparent, and viscous liquid.

3. Preparation of 1,3-di-[2-(Acrylic Ester)-3-(4-Phenylphenoxy)-1-Propoxy]Benzene

The Step 2 product (0.10mol) was dissolved in acetone (100 g) and treatedwith triethylamine (0.36mol) at 5�C for over 1 hour and then stirred for 2 hours. The mix-turetemperature was warmed to ambient temperature and extracted with 200 g apiecetoluene and water. The organic portion was isolated and treated with 5% hydro-chloric acid, washed repeatedly with water until it was chloride free, and then concen-trated. The residuewaspurified by silicagel columnchromatographyusing toluene, andthe product was isolated in 80% yield as a colorless and transparent liquid.

1H-NMR (CDCl3) d 4.20–4.30 (m, 8H), 5.50–5.60 (m, 2H), 5.85 (d, 2H), 6.10–6.20 (m, 2H), 6.45 (d, 2H),6.50–6.60 (m, 3H), 6.90–7.60 (m, 19H)

FD-MS (m/z); 670 (Mþ)

Experimental 139

DERIVATIVES

O OO OO OO O

O OO OO OO O

O OO OO OO O

NOTES

1. Experimental dental fillers were cured by irradiation with visible rays for 60seconds using a visible ray irradiator.

2. Nakamura [1] prepared UV-curable acyclic esters of 1,3-dithiolane, (I), for useas dental composites.

aS

SO

O

O

O (I)

a = 2 – 4

3. Crosslinkable polyhedral oligomeric silsesquioxane, (II), prepared by Jin [2]were used as dental composites in restorative applications, especially in crownand bridge materials.

140 (Meth)Acrylic Ester Compound and Use Thereof

Si

SI

Si

Si

Si

Si

SiR

R

OYR

ROY

R

OYR

R

O

O

O

OO

O

O

O

(II)

R = C1 – C9Y= acrylate

4. Methacrylate-substituted asymmetric trimers consisting of iminooxidiazinedione derivatives, (III), were prepared by Moszner [3] that had excellentmechanical properties and were used as dental cements.

N

O

N

O N

O

NH

NH

O

O

O

O

OO

O

O

NH

OO

O

O6

66

(III)

5. Heilmann [4] prepared a dental material from the co-oligomerization of i-octylacrylate and methacryloyloxyethylcarbamoyl-ethylmethylketonoxime, (IV).The copolymer had a Mn of roughly 21,000 daltons and a shrinkage of lessthan 2% after thermal curing.

ONH

ON

O

O

(IV)

6. Metathesis-curable compositions of polyethylene glycol monomers, (V), usingruthenium derivatives, (VI), were prepared by Angeletakis [5] and used asdental impression materials and orthodontic appliances.

Notes 141

OO

OO

O

O

O

O

O

O

O

O

8

RuCl

Cl

NNMesityl Mesityl

(V)

(VI)

References

1. M. Nakamura et al., US Patent 6,835,844 (December 28, 2004)2. S. Jin et al., US Patent 7,160,941 (January 9, 2007)3. N. Moszner et al., US Patent 7,078,446 (July 18, 2006)4. S.M. Heilmann et al., US Patent 7,074,858 (July 11, 2006) and US Patent 7,015,286 (March 21, 2006)5. C. Angeletakis et al., US Patent 7,001,590 (February 21, 2006)

142 (Meth)Acrylic Ester Compound and Use Thereof

VII. ELECTROACTIVE

A. Charge Transport Materials

Title: Hole Transport Polymers and Devices Madewith Such Polymers

Author: G. D. Jaycox et al., US Patent 7,205,366 (April 17, 2007)Assignee: E.I. du Pont de Nemours and Company (Wilmington, DE)

SIGNIFICANCE

Manyelectroluminescentmaterials havepoor charge transport properties. The presentinvention is directed to polymeric agents containing grafted naphthalene or pyrene,which makes then effective as both hole transport and electroluminescent agents.

REACTION

OCH3O OCH3O O O

OH

i

OCH3O O O

a b a bii

O

NH

O

i: 2-Hydroxyethyl methacrylate, Vazo� 52, 2,20-azobis(2,4-dimethyl pentanenitrile), acetone

ii: 1,10-Carbonyldiimidazole, 1-(1-naphthyl)ethylamine, THF


143

EXPERIMENTAL

1. Preparation of Poly(Methyl Methacrylate-co-2-HydroxyethylMethacrylate)

A container was charged with a solution of Vazo� 52 catalyst and 2,20-azobis(2,4-dimethyl pentane nitrile) (4.5 g) dissolved in acetone (600 g); a second container wascharged with methyl methacrylate (540 g) and 2-hydroxyethyl methacrylate (180 g).The first and second containers were uniformly fed into a reactor for 330 and 240minutes, respectively, and then refluxed for 1 hour. After standardworkup the productwas isolated in100%yield, having aMnof30,308daltons,Mwof93,195daltons, and aPDI of 3.07.

2. Preparation of Poly(MethylMethacrylate-co-Ethyl-(Naphthyl Carbamate)-Methacrylate)

A reactor was charged with the Step 1 product (20 g), THF (445 g), and 1,10-carbonyldiimidazole (7.50 g) and then stirred for 1 hour at ambient temperature. Themixture was treated with the dropwise addition of 1-(1-naphthyl)ethylamine (7.9 g)dissolved in THF (67 g) over 20 minutes and then stirred for 48 hours at ambienttemperature. Themixturewas concentrated to one-third its volume and precipitated in200ml water. The residue was extracted five times with 200ml of water, ground in ablender and dried, and the product isolated was in 84% yield.

DERIVATIVES

A pyrene polyamide derivative, (I), was also prepared.

a

HN

HN

O O

HN O

(I)

1H-NMR (DMSO-d6) d 6.7–8.1 (aromatic protons for pendant naphthylene group); ratio of aromatic Haliphatic H¼ 0.20 (theoretical¼ 0.19)

UV-Vis (DMSO) lmax 305 nm

144 Hole Transport Polymers and Devices Made with Such Polymers

NOTES

1. By incorporating ethynyl functions into existing 1,3,4-oxadiazole-containingelectroluminescent electron hole transport dyes, (II), Roberts [1] increased thedevice operating lifetime by inhibiting oxadiazole aggregation. Tokarski [2]prepared azine derivatives, (III), that were also effective as hole transport agents.

C4H9

C4H9

NN

O

t-C4H9

ON

N

C4H9

C4H9

t-C4H9

(II)

SS S

HO

ON

N

NOH

O

N

(III)

2. Electroluminescent polymeric 1,3,4-oxadiazole-containing agents, (IV), pre-pared by Roberts [3] were also effective as electron hole transport agents.

a

NN

O

C8H17 C8H17C8H17 C8H17

OC8H17

(IV)

Notes 145

3. Electron hole transport composites consisting of poly(aniline-co-2-acrylami-do-2-methyl-propanesulfonic acid), (V), and silicon nanoparticles wereprepared by Hsu [4] and then used to prepare light-emitting diodes andelectrodes for thin film field effect transistors.

HN

NHO

SO3H(V)

a b

4. Tamao [5] prepared a light-emitting material effective as a charge transportagent containing boron, (VI), which was used as a luminescent element.

B

C8H17O OC8H17

(VI)

a

References

1. R.R. Roberts et al., US Patent 7,192,657 (March 20, 2007)2. Z. Tokarski et al., US Patent 7,189,482 (March 13, 2007)3. R.R. Roberts et al., US Patent 7,094,902 (August 22, 2006)4. C.-H. Hsu et al., US Patent 7,189,771 (March 13, 2007)5. K. Tamao et al., US Patent 7,157,154 (January 2, 2007)

146 Hole Transport Polymers and Devices Made with Such Polymers

Title: Acrylic Polymer and Charge Transport Material

Author: H. Ishizawa et al., US Patent 7,012,123 (March 14, 2006)Assignee: Sekisvi Chemical Co., Ltd. (Osaka, JP)

SIGNIFICANCE

Isotactic and syndiotactic poly(9-fluorenylmethacrylate)s havebeen prepared that areeffective as hole mobility charge transport materials and as electrical conductors ofcharge transport materials.

REACTION

a

OH O

O

OO

iii

Isotactic and syndiotactic prepared

i: Benzene, triethylamine, methacryloyl chlorideii: THF, t-butyllithiun

EXPERIMENTAL

1. Preparation of 9-Fluorenyl Methacrylate

A 200ml reaction flask charged with 9-fluorenol (11mmol),180ml of benzene, andtriethylamine (13.75mmol) was cooled to 6�C and then treatedwith the slow additionof methacryloyl chloride (13.75mmol). Thereafter the mixturewas stirred at ambienttemperature for 24 hours. The solutionwaswashedwithwater and saturatedNaHCO3,and the organic layer was isolated, dried with MgSO4, and concentrated. The residue

147

was purified by column chromatography using benzene, and the product was isolatedin 40% yield as white solid, MP¼ 61�C.

2. Preparation of Syndiotactic Poly(9-Fluorenyl Methacrylate)

A25ml reaction tubewas charged with the Step 1 product (0.687mmol), dissolved in3.2ml of THF, and then cooled to �78�C and treated with 0.07ml of 1.36M t-BuLi(0.095mmol). The mixture reacted at �78�C and was quenched with 2ml ofmethanol. The solution was precipitated in 30ml of methanol and isolated. Theprecipitate was dissolved in 30ml hexane, filtered, and concentrated, and 0.147 gproduct was isolated having a Mn of 2600 daltons with a PDI of 1.25.

DERIVATIVES

The isotactic derivative was also prepared

TESTING

1. Measurement of Hole Mobility of Charge Transport Material(TOF Method)

A CH2Cl2 solution consisting of 10wt% of the Step 2 product and 1wt% of 2,4,7-trinitrofluorene malononitrile as dopant was prepared and cast onto an ITO glasssubstrate, dried; a 1 mm filmwas isolated. Aluminumwas thenvacuum deposited ontothe film to a thickness of 1000C forming a 5� 5mm aluminum electrode. Holetransfer time was measured by applying a voltage of 5V to the electrode whilesimultaneously exposing it to a pulse laser beam at 337 nm.

Hole mobility testing results are provided in Table 1.

2. Electrical Conductivity of Charge Transport Material

The film prepared abovewas evaluated for electrical conductivity at an interelectrodedistance of 90 mm. Testing results are provided in Table 1.

TABLE 1. Hole mobility and electrical conductivity for syndiotactic and isotacticpoly(9-fluorenyl methacrylate).

Entry Hole mobility (cm2V�1 s�1) Electrical Conductivity (S/cm)

Syndiotactic 1.02� 10�4 1.13� 10�5

Isotactic 8.02� 10�4 5.13� 10�5

1H-NMR (CDCl3) d 7.696 (2H, d), 7.580 (2H, d), 7.427 (2H, t), 7.306 (2H, t), 6.868 (1H, s), 6.166 (1H, s),5.621 (1H, s) and 2.015 (3H,s)

1H-NMR (CDCl3) d 6.988 7.501 (8H, m), 6.322 (1H, s), 2.108 (1.79H, s), 1.127 (2.9H, s)

148 Acrylic Polymer and Charge Transport Material

NOTES

1. Electroactive fluorene copolymers, (I), were prepared by Uckert [1] using 2,7-diiodo-9,9-di-2-ethylhexyl fluorine. This product was used as a component inlight-emitting diodes.

aN

C6H13

C8H17 C8H17

(I)

2. Chen [2] prepared electroluminescent conjugated polymers, (II), containingphosphorescent components that were used as light-emitting diodes. Boronanalogues, (III), prepared by Tamao [3] were also used as light-emitting diodecomponents.

a

a

NN

(II)

B

SS

(III)

References

1. F.P. Uckert et al., US Patent 7,220,820 (May 22, 2007), US Patent 7,214,763 (May 8, 2007), and USPatent 7,211,643 (May 1, 2007)

2. S.-A. Chen et al., US Patent 7,220,819 (May 22, 2007)3. K. Tamao et al., US Patent 7,157,154 (January 2, 2007)

Notes 149

B. Dielectric Materials

Title: Thermosetting Aromatic Dielectric Material

Author: J. Economy et al., US Patent 7,211,642 (May 1, 2007)Assignee: The Board of Trustees of the University of Illinois (Urbana, IL)

SIGNIFICANCE

Although minimization in integrated circuits allows for faster device operation,propagation delays increase with increasing numbers of interconnects. To addressthis problem, lower dielectric constant materials have been prepared.

150

REACTION

OHO O

O

O

O

O

O O

O

O

O

O

a

i ii

i: Benzenetricarboxylic acid chloride, pyridine, CH2Cl2ii: 3-Diethynyl benzene, phenylacetylene, copper(I) chloride, oxygen, acetone,

pyridine

EXPERIMENTAL

1. Preparation of tris-(3-Ethynyl-Phenyl)Trimesate

A reaction flask was chargedwith 3-ethynyl phenol (0.017mol), 5ml of pyridine, and20ml of CH2Cl2 and treatedwith the dropwise addition of 1,3,5-benzenetricarboxylicacid chloride (0.0055mol) dissolved in 10ml of CH2Cl2 and refluxed for 6 hours at45�C.The resulting yellow solutionwaswashed 3 times apiecewith 20ml of 1MHCl,1MNaOH, andwater. Themixturewas then driedwithNa2SO4, filtered, concentrated,and the product was isolated as a yellow powder in 58% yield.

Experimental 151

2. Preparation of Poly[3-Diethynyl Benzene-co-(tris-(3-Ethynyl-Phenyl)Trimesate)]

A reactor was charged with CuCl (0.0135mol) and 67ml acetone and then slowlyheated with stirring to 30�C and treated with 0.83ml of acetone/pyridine, 1:1. Theslurry was stirred for 10 minutes until oxygen bubbled through the mixture turningthe light green slurry dark green. The flow of O2 was continued throughout the rest ofthe reaction.

In a separate vessel, amixture consisting of 3-diethynyl benzene (14.27mmol), theStep 1 product (1.59mmol), phenylacetylene (0.111mol), and 0.83ml of the acetone/pyridine mixture in 40ml of acetone was added to this vessel in a single portion.Heating was removed, an additional 5ml of the acetone/pyridine was added over aperiod of 30 minutes, and the temperature was kept below 45�C via an ice bath. Afterthe acetone/pyridine addition was completed, the reaction temperature was keptbetween30�Cand40�Cfor 12hours in the dark. The reactionmixturewas precipitatedin 400ml of methanol containing 11ml of 12M HCl, filtered, and washed withmethanol. The light yellow paste was dissolved in 50ml of CCl3H, washed 3 timesapiece with 10ml 10% HCl and then water, dried with MgSO4, filtered, andconcentrated. The residue was dissolved in 20ml of CCl3H and then re-precipitatedfrom 600ml of methanol. The mixture was re-filtered, washed with methanol, anddried, and 1.19 g of product was isolated as a white powder.

DERIVATIVES

A second derivative was also prepared as shown below.

a

O OO O

NOTES

1. Low dielectric constant compositions consisting of adamantyl, (I), and diada-mantyl derivatives with a porogen consisting of polyacenaphthylene homopoly-mer were prepared by Li [1] and used as substrate materials in microchips,

1H-NMR d 9.2 (m, 3H), 7.2 7.5 (m, 12H)FTIR (cm�1) 3300 ethynyl C–H stretch, 1750 C¼O

152 Thermosetting Aromatic Dielectric Material

multichip modules, laminated circuit boards, and printed boards. Relatedadamantly and diadamantyl derivatives were prepared by Lau [2].

(I)

2. A low dielectric constant composition consisting of poly(divinylsiloxanebis-benzocyclobutene) having aMw of roughly 50,000 daltons and poly(propyleneglycol) biscinnamate having a Mw of roughly 2200 daltons, was prepared byBruza [3] and used in electronic applications such as integrated circuits,multichip modules, and flat panel display devices.

3. You [4] prepared porous thermoset dielectric materials having low dielectricconstants which were used in electronic component manufacture with cross-linked polymeric porogen particles as provided in Table 2.

4. Pore-generating materials, particularly b-cyclodextrins, were used by Lyu [5]with silsesquioxane derivatives to prepare low dielectric constant materials.

TABLE 1. Components used in preparing porogen particles which werecompatible with the B-staged benzocyclobutene dielectric materials aftercrosslinking with 10% trimethylol-propane triacrylate.

Entry Monomer A Monomer B Ratio A/B

A Styrene N-Vinylpyrrolidone 45/45B N-Vinylpyrrolidone — —D Styrene Vinylanisole 45/45G Styrene Vinylanisole 80/10

Notes 153

References

1. B. Li et al., US Patent 7,141,188 (November 28, 2006), US Patent 7,060,204 (July 13, 2006), andUS Patent 6,740,685 (May 25, 2004)

2. K. Lau et al., US Patent 6,987,147 (January 17, 2006)3. K.J. Bruza et al., US Patent 7,109,249 (September 19, 2006)4. Y. You et al., US Patent 6,998,148 (February 14, 2006)5. Y.Y. Lyu et al., US Patent 7,169,477 (January 30, 2007)

154 Thermosetting Aromatic Dielectric Material

C. Donor-Acceptor Complexes

Title: Polyester Having p-Conjugated Groupin Side Chain and Charge Transporting MaterialUsing the Same

Author: T. Nakano, US Patent 7,235,620 (June 26, 2007)Assignee: Japan Science and Technology Corporation (Saitama, JP)

SIGNIFICANCE

Beginning with 9-fluorene carboxylic acid, high molecular weight poly(9-hydroxymethyl-9-fluorene carboxylic acid) has been prepared by the homopolymerization of9-hydroxymethyl-9-fluorene carboxylic acid using trifluoro methanesulfonate asthe catalyst. This polymeric agent readily formed donor-acceptor complexes with1,3-dinitrobenzene and is suitable as a charge transport material.

REACTION

aCO2HHO2C OH OO

O

i ii

i: THF, paraformaldehyde, CH2Cl2, butyl lithiumii: THF, methanol, tin(II), trifluoromethanesulfonate, diazomethane

155

EXPERIMENTAL

1. Preparation of 9-Hydroxymethyl-9-Fluorene Carboxylic Acid

A reactor was charged with 9-fluorene carboxylic acid (23.7 mmol) and 300ml ofTHF and then cooled to �78�C and treated with 41.0ml of 1.6M butyl lithiumsolution in hexane. The mixture was stirred for 30 minutes, treated with parafor-maldehyde (75.0mmol) dissolved in 100ml of THF at�78�C, and stirred 13 hoursat ambient temperature. Water was then added, the solution extracted with diethylether, and the pH of the aqueous layer lowered to 2 using 1M hydrochloric acid. Themixture was re-extracted with CCl3H, and the organic layer dried using anhydrousMgSO4. The low-boiling fraction was distilled under reduced pressure and 4.21 g ofresidue isolated. The CH2Cl2-insoluble fraction was collected, and the productisolated in 80.5% yield.

2. Preparation of Poly(9-Hydroxymethyl-9-Fluorene Carboxylic Acid)

The Step 1 product (0.21 mmol) and (CF3SO3)2Sn (0.9mg) were introduced into areaction vessel; the mixture was shaken until uniform then heated for 3 hours at180�C. The mixture was then separated by decantation into THF where 47.1mgdissolved and 2.20mg was insoluble. The THF-soluble portion was then re-dissolved in 3ml THF and treated with diazomethane dissolved in 1ml diethylether and stirred for 5 hours at ambient temperature. The mixture was concentratedand the residue divided into a methanol-soluble part (8.10mg) and methanol-insoluble part (34.9mg). The methanol-insoluble part was divided into a THF-soluble part (14.19mg) and a THF-insoluble part (20.64mg). The part that wasinsoluble in methanol but soluble in THF was identified as the product with a Mn ofroughly 1.0� 105 daltons.

DERIVATIVES

9-Hydroxy-9-fluorene carboxylic acid was also prepared.

HO2C OH

1H-NMR (CDCl3) d: 7.78 (d, J¼ 7.5, 2H), 7.67 (d, J¼ 7.5, 2H), 7.46 (dd, J¼ 7.0, 2H), 7.54 (dd, J¼ 8.0,2H), 4.02(s, 4H).

156 Polyester Having p-Conjugated Group in Side Chain and Charge Transporting Material

TESTING

Donor-Acceptor Testing

The Step 2 product (2.98mg) and 1,3-dinitrobenzene (1.80mg) were dissolved in10ml of THF and then diluted 100 times. This stock solution was used for absorptionspectrummeasurements in a 10mm quartz cell at ambient temperature. The intensitywas 0.140 at 242 nm,which changed to 0.108 after the addition of 1,3-dinitrobenzene.By changing the 1,3-dinitrobenzene concentration from 2.5� 10�5M and 5.0� 10�5

M at 242 nm, the absorption intensity changed from to 0.077 and 0.059, respectively.This hypochromic effect demonstrated that the fluorene ring of the polymer and 1,3-dinitrobenzene formed a stacked complex.

NOTES

1. Donor-acceptor fluorene complexes were also prepared by Ishizawa [1] usingthe poly(9-fluorenyl methacrylate), (I), substrate.

a

OO

(I)

2. Fluorene monomers, (II), previously prepared by the author [2] then polymer-ized and, had a light emission peak at 400 nm, which was different from thepolymer light emission peak wave length of 305 nm.

(II)

References

1. H. Ishizawa et al., US Patent 7,012,123 (March 14, 2006)2. T. Nakano et al., US Patent Application 2004-0132963 (July 8, 2004)

Notes 157

D. Electroconductive

Title: Halogenated Thiophene Monomer forthe Preparation of Regioregular Polythiophenes

Author: C. Werner et al., US Patent 7,262,264 (August 28, 2007)Assignee: Honeywell International, Inc. (Morristown, NJ)

SIGNIFICANCE

Poly(3-hexyl)thiophene has been prepared in 93.5% head-to-tail regioregularity byreacting 5-bromo-2-chloro-3-hexylthiophene with magnesium, t-butylmagnesiumchloride, 1,2-bis(diphenylphosphino)ethane nickel(II) chloride, and triethylpho-sphite. Potential applications for these conducting polymers include field-effecttransistors, sensors, capacitor coatings, battery electrodes, and light-emitting diodes.

REACTION

aS

C6H13

Br ClS

C6H13

iNote 1

i: 2-Methyltetrahydrofuran, magnesium, t-butylmagnesium chloride, triethylpho-sphite, 1,2- bis(diphenylphosphino)ethane nickel(II) chloride

158

EXPERIMENTAL

Preparation of Poly(3-Hexyl)Thiophene with a 93.5%

5-Bromo-2-chloro-3-hexylthiophene (0.0355mol) was added over a period of 30minutes to a mixture consisting of 75ml of 2-methyltetrahydrofuran, magnesium(0.0355mol), and0.15ml of 1M t-butylmagnesiumchloride solution inTHFat 60�C to70�C. The mixture was stirred for 90 minutes at 70�C. It was then cooled to 60�C andtreated with a suspension of 1,2-bis(diphenylphosphino)ethane nickel(II) chloride(0.177mmol) in 12.5ml of 2-methyltetrahydrofuran for over 30 minutes. The mixturewas stirred an additional 3 hours at 80�C and further treated with triethylphosphite(3mmol) and stirred for 30minutes at 80�C.Themixturewas then concentrated and theresidue dissolved in 10ml of toluene. This solution was poured into 100ml of EtOAc,which created a suspension, and the suspensionwas stirred for 30minutes at 80�C.Thecooled suspension was filtered, the residuewashed twicewith 20ml of EtOAc, and theproduct isolated in 81% yield having a Mn of 19,543 daltons with a Tm of 224�C.

DERIVATIVES

Only the Step 1 derivative was prepared.

NOTES

1. Poly(3-dodecylthiophene) having an 99% regiospecificitywas prepared in 80%yield byMcCullough [1] using 2,5-dibromo-3-dodecylthiophenewith catalyticamounts of 1,3-diphenylphosphinopropane nickel(II) chloride. In a subsequentinvestigation by Koller [2], regiospecificity exceeding 90% for poly(3-hexyl)thiophene was obtained using 2,5-di-bromo-3-hexylthiophene with catalyticamounts of 1,3-diphenylphosphinopropane nickel(II) chloride.

2. Leclerc [3] prepared regioregular and water soluble polythiophenes by oxidiz-ing thiophene derivatives with iron (III) chloride which were then used asoptical and electrochemical detectors of double-stranded oligonucleotides.

aS

O

N(C2H5)3

S

O

N(C2H5)3

i

++

i: Dimethyl ether, iron (III) Chloride

UV (CHCl3): max¼ 450.79 nm; film: 521, 550, 602 nm

Notes 159

3. Regioregular poly(5,50-(4,40-dihexyl-2,20-bithiazole)), (I), was prepared byCurtis [4] and used in electronic applications such as LED’s, rechargeablebatteries, and electrolytic capacitors.

S

N

N

S

C6H13

C6H13(I)

n

References

1. R.D. McCullough et al., US Patent 6,166,172 (December 26, 2000)2. G. Koller et al., US Patent Application 2005-0080219 (April 14, 2005)3. M. Leclerc et al., US Patent 7,083,928 (August 1, 2006)4. D.M. Curtis et al., US Patent 5,536,808 (July 16, 1996)

160 Halogenated Thiophene Monomer for the Preparation of Regioregular Polythiophenes

Title: Electrically Conductive Polymeric Biomaterials,the Process for Their Preparation and Use in Biomedicaland Health Care Fields

Author: S. Panero et al., US Patent 7,253,152 (August 7, 2007)Assignee: Fidia Advanced Biopolymers, s.r.l. (Abano Terme, IT)

SIGNIFICANCE

Polypyrrole composite biomaterials having electrically conductive properties havebeen prepared using hyaluronic acid or its sodium salt by galvanostatic and potentio-static methods. These agents are useful for preparing medical devices such as nerveand bone regeneration materials.

REACTION

a

HN

HN

iNote 1

EXPERIMENTAL

Preparation of Polypyrrole Using Hyaluronic Acid

Conductive polymer films based on polypyrrole and hyaluronic acidwere synthesizedusingboth agalvanostaticmethod––byapplying current at a constant intensity rangingbetween 0.5 and 10mA for periods varying between 60 and 150 minutes––and apotentiostatic method with the constant potentials ranging between 0.3 and 0.75V

161

versus SCE. The first methodwas the preferredmethod, however, because it producedfilms with even surfaces, thereby reducing reaction times. Polymer films weresynthesized in aqueous solutions using concentrations of pyrrole varying frombetween 0.05M and 0.3M and concentrations of hyaluronic acid or sodium hyalur-onate varying from between 0.9M and 5M.

POLYMERIZATION SCOPING

NOTES

1. Oxidized polypyrrole, (I), was used by Shastri [1] to induce biological activitieswithin stem cells by electromagnetic stimulation.

HN

NH

HN

NH

... ...

(I)

2. Hyaluronic acid succinylate, (II), was prepared by Rivarossa [2] by reactingsuccinic anhydride with sodium hyaluronate and the material used in eithervenous and arterial vascular anastomoses. This included creating a physicalhemostatic barrier to prevent scar tissue formation or to prevent post surgicaladherence of the vessels to the surrounding tissues. Laredo [3] prepared

TABLE 1. Effect of experimental conditions on the film thickness of polypyrrole.

EntryPyrrole(M)

HyaluronicAcid (mg/ml) Synthetic Method

Film Thickness(mm)

1 0.1 2 Potentiostatic 0.33V¼ 720mV vs. SCE, 0.19C

2 0.1 2 Galvanostatic 4.2Total charge! 1C

3 0.1 2 Galvanostatic 8.4Total charge! 5C

4 0.1 2 Galvanostatic 18Total charge! 6.24C

5 0.2 4 Galvanostatic 12Total charge! 6C

162 Electrically Conductive Polymeric Biomaterials

musculoskeletal tissue repair agents consisting of tetraalkylammonium bromidehyaluronic acid salts, (III).

OO

OHO

NH

O

OHHO

OHO

(III)

a

ON(C4H9)4

OO

OHO

NH

O

OHHO

O

O

OH

(II)

CO2H

a

O

3. Heteroatom biodegradable and electrically conducting polymers, (IV), effec-tive for tissue engineering applications were prepared by Schmidt [4] and usedin spinal cord regeneration, wound healing, and bone repair.

a

HN

S

HN

OO

O

O O

O O O

(IV)

References

1. V. Shastri et al., US Patent 6,569,654 (May 27, 2003)2. A. Rivarossa et al., US Patent 7,202,230 (April 10, 2007)3. W.R. Laredo et al., US Patent 7,091,191 (August 15, 2006)4. C.E. Schmidt et al., US Patent 6,696,575 (February 24, 2004)

Notes 163

Title: Dibenzodiazocine Polymers

Author: V. J. Lee et al., US Patent 7,238,771 (July 3, 2007)Assignee: Solvay Advanced Polymers, L.L.C. (Alpharetta, GA)

SIGNIFICANCE

Polydibenzodiazocine materials have been prepared by polymerization of dibenzoyl-benzidine derivatives using toluene sulfonic acid These agents are useful aselectrically conducting artificial muscles.

REACTION

a

NO2

Br

ON

NH2

Br

O

NH2 O

NH2 O

N

N

i iiiii

iv

Br

i: THF, methanol, potassium hydroxide, phenylacetonitrileii: Acetic acid, iron

164

iii: bis(1,5-Cyclooctadiene)nickel(0), DMF, hydrochloric acidiv: Toluene sulfonic acid monohydrate, 1,3-dichlorobenzene

EXPERIMENTAL

1. Preparation of Heterocyclic Intermediate

A glass reactor was charged with 4-bromonitrobenzene (0.126mol) dissolved in300ml ofTHF/methanol, 1:2, respectively, and then treatedwith potassiumhydroxide(2.64mol), phenylacetonitrile (0.126mol), and 300ml of methanol at 0�C. Themixture was stirred for 4.5 hours at 0�C poured into 1 liter of water. The resultingprecipitate was collected by filtration, and purified by re-crystallization usingmethanol, and the product was isolated in 59.4% yield.

2. Preparation of 5-Bromo-2-Aminobenzophenone

The Step 1 product (0.10mol) was dissolved in 200ml of acetic acid at 80�C andthen treated with 50ml of water and iron powder (0.5mol) in 10 portions over atwo-hour period. The mixture was stirred at 80�C for an additional hour and thencooled to ambient temperature. It was diluted with 1 liter of diethyl ether andextracted with 1 liter of water. The organic layer was separated, dried, concen-trated, and re-crystallized from methanol, and the product was isolated in 81%yield.

3. Preparation of 3,30-Dibenzoylbenzidine

A slurry of bis(1,5-cyclooctadiene)nickel(0) (81.5mmol) in 200ml of DMF wasadded to the Step 2 product (54mmol) in 150ml of DMF. The mixture was stirred for15 minutes at the ambient temperature, 90 minutes at 42�C, and then poured into500mlof2%aqueoushydrochloric acid. Itwas extractedwithCH2Cl2, and theorganiclayer was filtered, dried, and concentrated. The residue was purified by chromatogra-phy, and the product was isolated in 50% yield.

4. Preparation of Polydibenzodiazocine

A round-bottomed flask fitted with a Dean–Stark trap was charged with the Step 3product (5 mmol), toluene sulfonic acid monohydrate (1 mmol), and 20ml of1,3-dichlorobenzene and then refluxed 2 hours. The mixture was cooled toambient temperature, neutralized with 0.5ml of triethylamine, precipitated in75ml of methanol, dried, and 0.77 g of product was isolated having a Mn of 12,000daltons.

Experimental 165

DERIVATIVES

NOTES

1. Mono- and dibendodiazocine analogues, (I) and (II), were previously preparedby Milkowski [1] and Johnson [2], respectively, and used in pharmaceuticalapplications.

NH

HN

(II)

N N

N

N Cl

Cl

(I)

TABLE 1. Step 4 polydibenzodiazocine derivatives prepared accordingto the present invention and corresponding yields and number averagemolecular weights.

Entry Structure Yield (%) Mn (daltons)

2

aN

NO10 29,000 and 5,000,000

(bimodal)

5

aN

N

O

91 90,000

16

a

N

N

O

54 61,000

166 Dibenzodiazocine Polymers

2. Electroactive polymer and rolled electroactive polymers having dielectricconstants between 2.5 and about 12 were used by Kornbluh [3] and Rosenthal[4], respectively, to prepare artificial muscles.

References

1. W. Milkowski et al., US Patent 4,243,585 (January 6, 1981)2. R.A. Johnson et al., US Patent 4,447,607 (May 8, 1984)3. R.D. Kornbluh et al., US Patent 7,211,937 (May 1, 2007)4. M.A. Rosenthal et al., US Patent 7,233,097 (June 19, 2007)

Notes 167

Title: Redox-Active Polymer and ElectrodeComprising the Same

Author: T. Mitani et al., US Patent 7,214,762 (May 8, 2007)Assignee: Japan Science and Technology Agency (Kawaguchi-shi, JP)

SIGNIFICANCE

A new high-energy density battery consisting of a redox-active polymer has beenprepared that is effective at low temperatures. The polymer was prepared by thecondensation of N,N0-1,4-phenylene-bis-thiourea with phenylene-1,4-diisothiocya-nate and is suitable as a cathode for secondary lithium batteries.

REACTION

aa

H2N NH

S

HN NH2

SH2N N

SN NH2

S

NH

N

SN

HN

SNH

S

HN

S

i ii

iii

N N

SN N

SN

SN

S N

Note 1

i: NMP, ethanol, benzyl chlorideii: Phenylene-1,4-diisothiocyanate, THF, benzeneiii: Oxidant (unspecified)

168

EXPERIMENTAL

1. Preparation of N,N0-1,4-Phenylene-bis-Thiourea-S,S0-Benzyl Ether

A reaction flask charged with N,N0-1,4-phenylene-bis-thiourea (230mg) was dis-solved in a mixed solution of 4ml apiece NMP and ethanol and then treated withbenzyl chloride (270mg)and refluxed for 30minutes.The solutionwas cooled, treatedwith a solutionof10mlwater containingNaOH(80mg), and then extractedwith40mlof diethyl ether. The extractwas driedwithMgSO4, filtered, concentrated, and 400mgof product were isolated.

2. Preparation of S-Benzylized Poly(Phenyl-2,4-Dithiobiuret)

The Step 1 product (406mg)was dissolved in 10ml apiece THF and benzene and thentreated with phenylene-1,4-diisothiocyanate (200mg) dissolved in 5ml apiece THFand benzene. This mixture was refluxed for 3 days and filtered, the solid rinsed withacetone, and 100mg of product isolated.

3. Preparation of Poly(1,2,4-Dithiazolium-Diaminobenzene)

TheStep 3 productwas prepared by reacting the Step 2 productwith anwith oxidant orelectrochemically.

DERIVATIVES


NOTES

1. A sample electrode was prepared by grinding the polymeric Step 2 product in amortar with acetylene black and then adding polyvinylidene fluoride andmixing with DMF. The mixture was next printed on a titanium foil and heatedfor 3 hours at 80�C.

2. High-energy density batteries having superior stability were preparedMorioka[1] using polynitroxyl radicals components, (I). Sulfur, (II), and boron, (III),free radical analogues prepared by Bannai [2] were also effective as secondarybattery components.

N N

OO ..n

(I)

S

S B..

(II) (III)

Notes 169

3. Kofinas [3] prepared a polymeric nanoscale solid-state battery system, (IV),consisting of electrochemical cells connected in series, that was used as asecondary battery.

NCo

N

OO

t-C4H9 t-C4H9

OO

O OH

O O

Li(IV)

a b c

4. Indole trimer, (V), prepared by Nabuto [4] was used as an electrode componentin an electrochemical cell.

NH

NH

NH

(V)

5. Nakanishi [5] prepared siloxane-modified cyclic carbonates, (VI), that whencombined with a nonaqueous solvent and an electrolyte salt formed a non-aqueous electrolytic solution that was used to construct a secondary batteryhaving improved temperature and cycle properties.

SiO

SiO

Si10

(VI)

O

OO

170 Redox-Active Polymer and Electrode Comprising the Same

References

1. Y. Morioka et al., US Patent 7,122,277 (October 17, 2006)2. Y. Bannai et al., US Patent 7,045,248 (May 16, 2006)3. P. Kofinas et al., US Patent 7,063,918 (January 20, 2006)4. T. Nobuta et al., US Patent Application 2007-0095656 (May 3, 2007)5. T. Nakanishi et al., US Patent Application 2007-0059597 (March 15, 2007)

Notes 171

Title: Use of Sulphonic, Phosphonic and PhosphoricAcids as Dopants for Polyaniline and for ConductivePolyaniline-Based Composite Materials

Author: A. Pron et al., US Patent 7,101,495 (September 5, 2006)Assignee: Commissariat A L’Energie Atomique (Paris, FR)

SIGNIFICANCE

Polyaniline in the emeraldine base state doped with di(butoxyethoxyethyl) ester ofsulphosuccinic acid had high film conductivity and an elongation at break of 195%.This high flexibility is particularly needed for elastomer coatings to impart elasticityon conductive materials.

172

REACTION

NH2

HN

N

N

OH

OH

O

O

HO3S

O

O

O

O

HO3S OO

OO

Intermediate

HN

N

NO

O

O

O

SO3HOO

OO

Dopant Polyaniline

i

ii iii

a

a

i: Lithium chloride, hydrochloric acid, ethanol, ammonium persulfate, iron (II)chloride

ii: 2-(2-Butoxy-ethoxy)ethanol, wateriii: 2,2-Dichloroacetic acid

EXPERIMENTAL

1. Preparation of Polyaniline (Emeraldine Base)

A mixture at�27�C consisting of freshly distilled aniline (0.1097mol), 85ml of 3MHCl, 95ml of ethanol, and LiCl (16 g) was treated with ammonium persulphate(0.0274mol), 60ml of 2MHCl, andLiCl (8 g) also at�27�C.Themixturewas reactedfor roughly 2 hours while the potential of the reaction mixture was controlled by astandard calomel electrode. It was then treated with FeCl2 (0.0183mol), LiCl (5 g),and 50ml of 2M HCl. After an additional hour the reaction was terminated, and thepolymer could be isolated by either filtration or by centrifuging. It was then washedwithdistilledwater, dried, andconverted to the emeraldine salt using2MHCl.This saltwas then converted to the emeraldine base by treatment with 2 liter of 0.3M aqueous

Experimental 173

ammonia solution for 48 hours. The product was washed with 5 liter of distilled waterfollowed by 2 liter of methanol and then dried. The fractions with low molecularweights were removed by extracting the polymer with chloroform in a Soxhletapparatus. The intrinsic viscosity of the emeraldine base as prepared was 2.5 dl/gin a 0.1 wt% solution in 96% sulphuric acid.

2. Preparation Di(Butoxyethoxyethyl) Ester of Sulphosuccinic Acid Dopant

A 70 wt% aqueous solution of sulphosuccinic acid (50.5mmol) was mixed with 2-(2-butoxy- ethoxy)ethanol (151.5mmol) at 110�C under a constant stream of nitrogen.The material was dried under vacuum at 70�C, and the product was isolated.

3. Preparation of a Self-supported and Drawable Film of Doped Polyaniline

The Step 1 product (111mg) and the Step 2 product (302mg) were mixed in 2,2-dichloroacetic acid (22.2 g) and stirreduntil no further changewas observed in theUV-Vis-NIR spectrum. Self-supported films were prepared by pouring about 1ml onto apolypropylene substrate and removing the solvent by evaporation at 45�C. The filmwas detached from its substrate and dried under vacuum; the film’s thickness was onthe order of 20 to 30 mM.

The film’s conductivity was measured at 90 S/cm by the 4-contact method atambient temperature. The manually drawn film exhibited an elongation at break of195% at ambient temperature.

DERIVATIVES

NOTES

1. Olinga [1] prepared and used the aromatic diester dopant, (I), with polyanilineand prepared flexible films having film conductivities between 100 to 200S/cm.

TABLE 1. Effect of selected dopants on the film conductivity and elongation at breakfor polyaniline (emeraldine base).

DopantElongation atBreak (%)

Film Conductivity(S/cm)

Sulphosuccinic acid, di(2-ethylhexyl) ester 36 115Camphorsulphonic acid 2 2302-Acrylamido-2-methyl-1-propanesulphonic acid, 115 90.5Sulphosuccinic acid, di(butoxyethyl) ester 195 125

Note: All doping was conducted in 2,2-dichloroacetic acid with 20 to 30mM films prepared on apolypropylene substrate.

174 Use of Sulphonic, Phosphonic and Phosphoric Acids as Dopants

Nanotubes using lignosulfonic acid-doped polyaniline were prepared by Vis-wanathan [2].

O

O

O

O

C2H5

C2H5

HO3S

(I)

2. Wang [3] prepared chiral polyaniline by amidating with the chiral dopant acid,(1R)–[�]–camphor sulfonic acid, (II), which was used in nanomaterials havinglengths of between 1 to 5 microns. When Wang [4] polymerized either anilineD- or L-tartrate, the corresponding water-soluble polyaniline derivative wasisolated. The derivatives were readily doped with ammonium hydroxide(green) or hydrochloric acid (blue). Water-soluble polyaniline was also pre-pared by Angelopoulos [5] by polymerizing aniline in the presence of thepolymeric dopant, polystyrene sulfonic acid.

a

O3SO

NH

HN

NH

(II)

3. Lee [6] observed that when polyaniline or polypyrrole were N-functionalizedwith N-t-butoxy carbonyl, these materials displayed enhanced physical andmechanical properties with higher solubility and electrical conductivity thanthe corresponding nonfunctionalized counterparts.

Notes 175

References

1. T. Olinga et al., US Patent 7,014,794 (March 21, 2006)2. T. Viswanathan et al., US Patent 7,063,808 (June 20, 2006)3. H.-L. Wang et al., US Patent 7,074,887 (July 11, 2006)4. H-L. Wang et al., US Patent 7,074,887 (July 11, 2006)5. M. Angelopoulos et al., US Patent 7,166,241 (January 23, 2007)6. S.-H. Lee et al., US Patent 7,067,229 (June 27, 2006)

176 Use of Sulphonic, Phosphonic and Phosphoric Acids as Dopants

Title: 3,4-Alkylenedioxy-Thiophene Copolymers

Author: B. Groenendaal et al., US Patent 6,995,223 (February 7, 2006)Assignee: Agfa-Gevaert (Mortsel, BE)

SIGNIFICANCE

An aqueous dispersion consisting of polyethylene glycol containing a (2,3-dihydro-thieno[3,4-b][1,4]dioxin-2-yl)-methanol terminus has been prepared. This materialexhibited electrical conductivities, visible light transmittances, and goodprocessability.

REACTION

a

S

OO

HO2C CO2H

OH

S

OO

OH

S

OO

O

O

iiiNote 1,2 Note 3

i: DMAc, copper (II) dichromate, quinolineii: p-Toluenesulfonyl chloride, pyridine, polyethylene oxide, hydrochloric acid

EXPERIMENTAL

1. Preparation of (2,3-Dihydro-Thieno[3,4-b][1,4]Dioxin-2-yl)-Methanol

A reactionvessel was chargedwith 2-hydroxymethyl-2, 3-dihydro-thieno[3,4-b][1,4]dioxine-5,7-dicarboxylic acid (0.184mol) dissolved in 500mlDMAcand then treatedwith copper dichromate (8.6 g) and 15 drops of quinoline. Thismixturewas stirred for2 hours at 150�C and cooled to the ambient temperature. It was poured into EtOAc,and the catalyst was removed by filtration. The filtrate was washed with acidic waterand brine, then concentrated, and the product was isolated by distillation at 115�C to120�C at 0.05mmHg.

177

2. Preparation of Polyethylene Oxide Substituted (2,3-Dihydro-Thieno[3,4-b][1,4]Dioxin-2-yl)-Methanol

p-Toluenesulfonyl chloride (44mmol) was dissolved in 20ml of pyridine and treateddropwisewithmexthoypolyethylene oxide (Mw¼ 750 daltons; 20mmol) dissolved in30ml of pyridine. Themixturewas stirred for 2 hours at 25�C to 30�C and poured intoice-watercontaininghydrochloricacid.ThisaqueousphasewasextractedwithCH2Cl2,afterwhich the combined organic fractionswerewashedwith 1Mof sodiumhydrogencarbonate solution. Final purification was done by column chromatography usingCH2Cl2/ethanol and polyethylene oxide tosylate isolated. The Step 1 product(5.8mmol) was dissolved into 25ml of THF and treated with sodium hydride(0.25 g) while stirring for 30 minutes and further treated with methoxypolyethyleneoxide tosylate (5.3 g). The mixture refluxed for 2 hours, cooled to the ambienttemperature, and poured into ice-water containing a few drops of concentratedhydrochloric acid. This mixture was extracted using CH2Cl2, and combined extractswere washed with a 1M aqueous solution of sodium hydrogen carbonate and brine,dried, and concentrated. The residue was purified by column chromatography usingCH2Cl2/methanol, 95:5, respectively, and the product was isolated.

DERIVATIVES

The following derivatives were prepared:

S

OO

O

O3

S

OO

O

CO2H

S

OO

O

SO3Na

NOTES

1. Urethane derivatives, (I), of the Step 1 product were prepared by Reuter [1] andused in optical signal processing.

S

OO

O

NH

O

C4H9

(I)

178 3,4-Alkylenedioxy-Thiophene Copolymers

2. Additional Step 1 decarboxylation transformation methods are provided byReynolds [2].

3. Poly(3,4-alkylenedioxythiophenedioxide), (II), derivatives were prepared bythe author [3] and used as an electroconductive layer in a light-emitting diode.

a

SO2

OO

O

O

(II)

4. Tahon [4] prepared poly(3,4-alkoxythiophene), (III), derivatives to enhance theconductivity in nonaqueous printing. The process for preparing aqueous andnonaqueous solution dispersions of this agent are described by Louwet [5].

aS

OO

(III)

References

1. K. Reuter et al., US Patent 6,852,831 (February 8, 2005)2. J.R. Reynolds et al., US Patent 6,425,966 (March 11, 2004)3. B. Groenendaal et al., US Patent 6,927,298 (August 9, 2005) and US Patent 7,105,620 (September 12,

2006)4. J.-P. Tahon et al., US Patent 7,223,357 (May 29, 2007) and US Patent 7,122,130 (October 17, 2006)5. F. Louwet et al., US Patent 6,425,966 (May 23, 2006)

Notes 179

E. Electroluminescence

Title: Electroactive Polymer, Device Made Therefromand Method

Author: K. E. Litz et al., US Patent 7,217,774 (May 15, 2007)Assignee: General Electric Company (Niskayuna, NY)

SIGNIFICANCE

High and low molecular weight electroactive polymers containing pendant 2-(7-benzothiazolyl-9,90-dioctylfluorene) units have been prepared. These materials dis-play electroluminescent properties that are useful in electronic devices.

REACTION

a

C8H17

C8H17

SN

Br Br

C8H17 C8H17

OHC Br

C8H17 C8H17

Br

C8H17 C8H17

S

N

C8H17 C8H17

S

N

iii

iiiiv

Note 1

i: Butyl lithium, THF, dimethylformamideii: 2-Aminothiophenol, dimethyl sulfoxide

180

iii: Cesium fluoride, tris(dibenzylideneacetone)dipalladium, tri-t-butylphosphine,tributyl(vinyl)-stannane, tetraglyme, toluene

iv: Benzoyl peroxide, benzene

EXPERIMENTAL

1. Preparation of 2-Bromo-7-Formyl-9,90-Dioctylfluorene

Butyl lithium (0.116mol) was added dropwise to a solution of 2,7-dibromo-9,90-dioctylfluorene (0.0918mol) in 200ml of THF at �78�C over 45 minutes and thenstirred for an additional 30minutes. Themixturewas treatedwith dimethylformamide(0.1539mol) at �78�C, warmed to ambient temperature over 4 hours, and concen-trated. The yellow residue was dissolved in 130ml of hexanes/xylenes, 10:3, respec-tively, and then quenched with 5ml 20% hydrochloric acid. After separating from theaqueous fraction, the organic layer was neutralized with NaHCO3, filtered, dried overMgSO4, and decolorized with activated carbon (10 g). The final solution was filteredand concentrated, yielding a colorless solid with a faint greenish hue. The lightgreenishcolorwas removedbysuspension inmethanol, and theproductwas isolated in83% yield as a colorless microcrystalline solid with MP¼ 48–50�C.

2. Preparation of 2-Bromo-7-Benzothiazolyl-9,90-Dioctylfluorene

The Step 1 product (0.0603mol) and 2-aminothiophenol (0.0693mol) was dissolvedin 80ml of dimethyl sulfoxide and heated for 1 hour at 198�C and then quenched bypouring into 100ml of cold water. The aqueous layer was decanted from the brightyellow oil and extracted twice with 25ml of pentane. The organic layers werecombined and quenched with 20ml of 20% acetic acid. The layers were separatedand the acidic solution extracted twicewith 25ml pentane. The organic fractions werecombined and neutralized by washing twice with 100ml of saturated NaHCO3

solution. The basic solution was extracted twice with 25ml of pentane, and theorganic fractions were combined and dried over MgSO4. The mixture was decolor-ized with activated carbon, leaving a bright yellow solution. The solution wasthen concentrated and a yellow residue purified by column chromatography usingalumina with xylenes/cyclohexane, 4:1, respectively, followed by re-crystalliza-tion in methanol. The product was isolated in 53% yield as a colorless crystallinesolid with MP¼ 79–81�C.

3. Preparation of 2-Vinyl-7-Benzothiazolyl-9,90-Dioctylfluorene

Amixture consisting of the Step 2 product (0.0083mol), cesium fluoride (0.0175mol),tris(dibenzylideneacetone)dipalladium (0.041mmol), tri-t-butylphosphine (0.123mmol), and tributyl(vinyl)stannane (0.0087mol) was dissolved in a mixture oftetraglyme (6 g) and 7ml of toluene and then heated for 14 hours at 90�C in a sealed30-ml vial. Once cooled to ambient temperature, a blue-green precipitate formed,

Experimental 181

which was extracted with 20ml of diethyl ether and filtered. The filtrate wasdecolorized with activated charcoal (2.0 g) and dried using 4A

�molecular sieves

(2.0 g). The solution was then concentrated, and the residual oil was added dropwiseinto dry acetonitrile leaving a bright yellow solid. The bright yellow solidwas extractedtwice with 10ml of diethyl ether leaving an insoluble white solid. The ether extractwas concentrated, and the product was isolated in 61% yield in greater than 95%purity.

4. Preparation of Poly(2-Vinyl-7-Benzothiazolyl-9,90-Dioctylfluorene)

The Step 3 product (0.2 g) was combined with benzoyl peroxide (2.8mg) in 1ml ofbenzene, and the mixture was heated to 66�C overnight. The polymer was thenprecipitated by pouring into methanol, filtered, and vacuum dried. The product wasisolated as a solid with aMw of 8600 daltons,Mn of 5100 daltons, and a polydispersityindex of 1.68.

DERIVATIVES

Poly(styrene-co-2-vinyl-7-benzothiazolyl-9,90-dioctylfluorene) was also prepared.

C8H17

C8H17

SN

ba

1. Electrical Activity Testing

Fluorescence quantum yields were determined using coumarin 540 in EtOAc as areference. UV absorption maxima were determined in chloroform; HOMO andLUMO values were determined by cyclic voltammetry in acetonitrile/tetrabutylam-monium fluoroborate solution. Optical and electrical properties of each derivative areprovided in Table 1.

182 Electroactive Polymer, Device Made Therefrom and Method

NOTES

1. Chen [1] prepared imidazole-fused phenanthroline derivatives, (I), that wereeffective as organic light-emitting devices.

N

N

N

N

(I)

2. A highly efficient green light-emitting electroluminescent devicewas preparedby Brunner [2] using a carbazole trimer as the charge-transporting conjugateddonor, (II). The corresponding electroactive polymeric carbazole, (III), waspreviously prepared by Leclerc [3].

NN N

OCH3

OCH3H3CO

(II)

TABLE 1. Summary of electroactive properties of poly(2-vinyl-7-benzothiazolyl-9,90-dioctylfluorene) and poly(styrene-co-2-vinyl-7-benzothiazoly-9,90-dioctyl-fluorene).

Polymer Homo Polymer Styrene Copolymer

Lamda (abs), nm 362 422Lamda (PL), nm 403 425HOMO, eV 6.02 5.9LUMO, ev 3.08 2.63E gap, eV 2.94 3.27Quantum yield, % 59 97Mw (daltons) 8,600 114,600PDI 2.01 2.3

Note: Although both derivatives exhibited good blue luminescence, quantum yield differences wereobserved.

Notes 183

aN

C8H17

(III)

3. Fryd [4] prepared organic emitting materials consisting of polymeric-metalcomplex salts, (IV). Their preparation is illustrated in below.

4N O

O

F3C

F3C

O

EuO

F3C

F3C

NH+Eu(NO3)3

(IV)

............

............

4. Electroluminescent polymers containing grafted 1,3,4-oxadiazoles, (V), wereprepared by Roberts [5] and were significantly red-shifted from the corre-sponding monomer. These agents were used in making organic light-emittingdiodes.

O N

N

OC8H17

15

(V)

References

1. J.P. Chen et al., US Patent 7,179,542 (February 20, 2007)2. K. Brunner et al., US Patent Application 20060051611 (March 9, 2006)3. M. Leclerc et al., US Patent 6,833,432 (December 21, 2004)4. M. Fryd et al., US Patent 7,060,372 (June 13, 2006) and US Patent 6,869,693 (March 22, 2005)5. R.R. Roberts et al., US Patent 7,094,902 (August 22, 2006)

184 Electroactive Polymer, Device Made Therefrom and Method

Title: Polymers and Oligomers, Their Synthesis, andElectronic Devices Incorporating the Same

Author: A. J. Epstein et al., US Patent 7,071,290 (July 4, 2006)Assignee: The Ohio State University (Columbus, OH)

SIGNIFICANCE

Conjugated and nonconjugated block copolymers and oligomers have been preparedthat have electroluminescing properties. The materials consist of polyaromatics andheteroaromatics and were prepared in a single synthetic step.

REACTION

O O

OCH3

OHC

OCH3

H3CO

CHO

H3CO

O O

OCH3

O

OCH3

H3CO

H3CO N

OCH3

OCH3

66 i

a

i: 1,4-Pyridylylenebis(triphenylphosphonium), THF, potassium t-butoxide

EXPERIMENTAL

1. Preparation of Polyaromatic Ether Containing a Conjugated Pyridine

To a stirred solution containing the dialdehyde (1.12mmol) and 1,4-pyridylylenebis(triphenyl-phosphonium) (1.12mmol) dissolved in 150ml ofTHFwas addeddropwise10ml of 2M potassium t-butoxide dissolved in THF, and the mixture refluxed 2 hours.The solution was then concentrated and the residue dissolved in CCl3H. The polymerwas precipitated in methanol and purified by Soxhlet extraction with methanol for12 hours. The purified polymer was isolated in 92% yield as a light-yellow solid.

1H-NMR (CDCl3) d 1.4 (m, 4H), 1.6 (t, 4H), 3.7 (s, 12H), 3.9 (t, 4H), 6.7 (s, 4H), 7.0 (t, 1H), 7.1 (d, 4H), 7.5(d, 2H).

185

DERIVATIVES

TABLE 1. Product conversions for selected electroluminescing polyaromaticand heteroaromatic polymer agents.

Entry Structure Yield (%)

2

a

6 O O

OCH3

O

H3CO

H3CO NOCH3

OCH3

H3CO

90

13

aOCH3

OCH3

OCH3

H3CO

H3CO

H3CO

OO6 88

14

aOCH3

OCH3

H3CO

OO6

90

15

a

OCH3

H3CO

OO6

90

16

aOCH3

OCH3

H3CO

H3CO

OO6

88

Note: H-NMR characterization data provided by the author.

186 Polymers and Oligomers, Their Synthesis, and Electronic Devices Incorporating the Same

NOTES

1. In an earlier investigation by the author [1] electroluminescing polymerswere designed to remain in a de-aggregated state to prevent the redshifting.This was achieved by incorporating rotaxanes into experimental polymericagents, (I).

TABLE 2. Step 1 product yields for conjugated monomeric analogues effectiveas electroluminescing agents.


4

N

N 59

5

N

NOCH3

H3CO

49

6 N

N

52

10

N

NOCH3

H3CO

46

12 50

Note: H-NMR characterization data provided by author.

Notes 187

(H2CCH2O)6

(I)

Rotaxane

2. Biphenyl derivatives consisting of both carbazole, (II), and indolyl componentswere prepared by Takiguchi [2] and used as light-emitting agents; tricarbazoletriphenylamine derivatives, (III), prepared by Iwakuma [3] were also effectiveas light-emitting agents.

N N

(II)

N

N N

N

(III)

3. Okada [4] determined that polymer materials having an arylamine repeatingunit containing p-conjugation on its main chain, (IV), had excellent lumi-nous properties and were particularly useful as organic electroluminescenceelements.

N

C6H13

S S

(IV)

a

188 Polymers and Oligomers, Their Synthesis, and Electronic Devices Incorporating the Same

4. Polymers containing benzotriazole repeating units, (V), which had high glasstransition temperatures and good thermal stability, were fabricated into coat-ings and films by Rogers [5] and used in electroluminescent devices.

C8H17 C8H17

H3COC8H17 C8H17

(V)

a

5. Egawa [6] prepared light-emitting stilbene derivatives, (VI), having a largeenergy gap suitable for use as a host material in a light-emitting layer.

a

a

(VI)

References

1. A.J. Epstein et al., US Patent 6,962,757 (November 8, 2005)2. T. Takiguchi et al., US Patent Application 2007-0057250 (March 15, 2007)3. T. Iwakuma et al., US Patent Application 2007-0054151 (March 8, 2007)4. T. Okada et al., US Patent Application 2007-0048637 (March 1, 2007)5. J. Rogers et al., US Patent Application 2007-0043204 (February 22, 2007) and US Patent Application

2005-0175856 (August 11, 2005)6. M. Egawa et al., US Patent Application 2007-0100180 (May 3, 2007)

Notes 189

Title: Process for Preparing Poly(Arylene Ethers)with Pendant Crosslinkable Groups

Author: B. Chen et al., US Patent 7,038,004 (May 2, 2006)Assignee: Lumera Corporation (Bothell, WA)

SIGNIFICANCE

Two crosslinkable perfluorinated bisphenol A polymeric derivatives having nonlinearoptical chromophores containing thiophene have been prepared. Both crosslinkedpolymers had higher Tg’s and greater mechanical stability than their noncrosslinkedanalogues and were used as light-emitting diodes.

190

REACTION

F5 F5

F5 F4

O

O

F4

F5

F5 F4

O

O

F4

F5 OH

Oa

i

F5 F4

O

O

F4

F5 O

Oa

O

O

F3

Not isolated

N

O

O

O

O

F3

F3

S

C4H9O OC4H9

S O

NC NC

CN

ii

iii

Crosslinked polymer

Chromophore

C4H9O OC4H9

Note 1

i: 4,40-(1-Phenyl ethylidene)-bisphenol A, potassium carbonate, DMAc, 3,5-dihydroxybenzylalcohol

ii: N-Methylpyrrolidone, 4-trifluoro-vinyloxybenzoyl chloride, pyridineiii: Cyclopentanone

Reaction 191

EXPERIMENTAL

1. Preparation of Poly(4,40-(1-Phenyl Ethylidene-Bisphenol-4,40-Di(perfluorobiphenyl)-co-3,5-Dihydroxy-Benzyl Alcohol)

A glass reactor was charged with decafluorobiphenyl (0.3mol), 4,40-(1-phenylethylidene)-bisphenol (0.15mol), K2CO3 (26 g), and 400ml of DMAc and thenheated to 120�C for 20 hours. The temperature was lowered to 105�C over 1 hourand the mixture treated with 3,5-dihydroxy-benzylalcohol (0.15mol) and K2CO3

(20 g).Over a 3-hour period the temperaturewas increased to 115�Cwhere it remainedfor 1 hour. Themixturewas hot filtered through a frit and the frit washedwith 50ml ofTHF. The solution was cooled to ambient temperature and precipitated into a mixtureof 750ml of methanol and 200ml of water in a blender. The solid was re-dissolved in250ml of THFwhere it formed aviscous solution thatwas re-precipitated in a solutionof 500ml of methanol and 200ml of water. The solid was then collected and air-driedon the frit for over 5 hours. It was further dried at 80�C at 87 torr on a rotary evaporatorfor 5 hours and the product isolated as a fine white powder in 30% yield.

2. Preparation of Poly(4,40-(1-Phenyl Ethylidene-Bisphenol-4,40-Di(perfluorobiphenyl)-co-3,5-Dihydroxy-1-Benzyl (4-TrifluorovinyloxyBenzoate)

A reaction vessel was charged with 350ml of N-methylpyrrolidone, the Step 1product (44.3 g), and 100ml of pyridine and then stirred at ambient temperature forone hour and treated with of 4-trifluorovinyloxybenzoyl chloride (0.085mol). Thismixture was stirred for 20 hours when the solution color changed from light yellowto brown. The mixture was precipitated by pouring into 500ml of methanol and200ml of water in a blender. The solid was isolated by filtering through a glass fritwhere a reasonable amount of emulsified polymer formed in the filtrate, suggestinga degree of polymer fractionation. The collected solid was washed with 2 liters ofmethanol and dried on a glass frit in air for 48 hours. The solid was dissolved in250ml of THF and precipitated in 750ml of methanol and 200ml of water in ablender. The solid was re-filtered and re-washed with 2 liters of methanol and airdried on the frit for 4 hours. It was re-dissolved in 250ml of THF and re-precipitatedin a solution of 750ml of methanol and 200ml of water in a blender, the processbeing repeated once; 40.0 g of product were isolated as a white powder.

3. Preparation of the Crosslinked Polymer Containing a Chromophore

A30wt% solution of the chromophorewasmixedwith the Step 2 product dissolved incyclopentanone and then spin-coated onto 200 glass wafers coated with indium tinoxide; thewafer soft baked at 100�C. A corona voltage of 5 kVwas applied to the filmwhile it was heated to 220�C for 10minutes.While at this temperature the voltagewas

192 Process for Preparing Poly(Arylene Ethers) with Pendant Crosslinkable Groups

increased to 5.5 kV, 6.5 kV, and 7.5 kV for 15, 23, and 30 minutes, respectively. After40 minutes the wafer was cooled to ambient temperature under the 7.5 kV field. Theproduct was then isolated and had a r33 of 24 pm/V measured at 1310 nm using theTeng–Man method.

DERIVATIVES

One additional Step 2 crosslinkable polymer, (I), was prepared.

F5 F4

O

F3CCF3

O

F4

F5 O

Oa

O

O

F3(I)

NOTES

1. The preparation of the Step 3 crosslinking nonlinear optical chromophore co-reagent is described by Huang [1]. Additional crosslinkable luminescentagents, (I) are provided below, (I).

N

O

O

O

O

F3

F3

S

C4H9O OC4H9

S R

C4H9O OC4H9

H2C

O

NH

CH2

NC CNNC

CN

NCCN

CH2

R =

(I)

Notes 193

2. Poly(acrylic acid-co-butylmethacrylate) functionalized with cyclometalatedluminescent complexes, (II), were prepared by Fryd [2] and used as highefficiency organic light-emitting devices.

F

Ir

CF3

O

O

O O

OOn-C4H9

(II)

a b

3. Tamao [3] prepared a polymeric light-emitting agent consisting of poly(3,7-dibromo-5-(2,4,6-triisopropylphenyl)-2,8-dioctyloxy-5H-dibenzo(b,d)borole),(III),whichwas used in electronic devices or as a charge transportmaterial. Poly(9,9-di-(4-t-butyldimethylsilyloxy-phenyl)fluorene-2,70-diyl), (IV), was pre-pared by Woo [4] and used as a light-emitting diode having the potential forsubsequent crosslinking.

B

C8H17O OC8H17

i-C3H8 i-C3H8

i-C3H8

(III)

O O

SISi

t-C4H9 t-C4H9

aa

(IV)

4. O’Neill [5] and Inbasekaran [6] prepared photopolymerizable and crosslink-able luminescent monomers, (V), and (VI), respectively, which were used aslight emitters in displays, backlights, and electronic equipment.

194 Process for Preparing Poly(Arylene Ethers) with Pendant Crosslinkable Groups

C3H7 C3H7

S

S

O O

OO

O O

(V)

O O

N N

(VI)

References

1. D. Huang et al., US Patent 6,995,884 (February 7, 2006) and, US Patent 7,019,453 (March 28, 2006)2. M. Fryd et al., US Patent 7,060,372 (June 13, 2006)3. K. Tamao et al., US Patent 7,157,154 (January 2, 2007)4. E.P. Woo et al., US Patent 6,900,285 (May 31, 2005) and US Patent 6,605,373 (August 12, 2003)5. M. O’Neill et al., US Patent 7,199,167 (April 3, 2007)6. M. Inbasekaran et al., US Patent Application 2007-0063191 (March 22, 2007)

Notes 195

F. Semiconductors

Title: Mono-, Oligo-, and Polythieno[2,3-b]Thiophenes

Author: M. Heeney et al., US Patent 7,183,418 (February 27, 2007)Assignee: Merck Patent Gesellschaft (Darmstadt, DE)

SIGNIFICANCE

Polymers having a central core consisting of [2,3-b]-thienothiophene were preparedhaving a Mn> 6000 daltons and Mw> 9000 daltons and used as semiconductors orcharge transport materials in electronic devices. By varying the aromatic or aliphaticcontent of this material, a lmax between 380 and 462 nm was obtained.

REACTION

S SHO2C CO2H

S SBr Br

S S

S SC8H17 C8H17

S S

S SC8H17 C8H17

iii iii

a

i: NMP, N-bromosuccinimideii: THF, Rieke zinc, 2,5-dibromo-3,4-dimethylthieno[2,3-b]thiophene, [1,10-bis

(diphenyl-phosphino)ferrocene]palladium(II) chlorideiii: Ferric chloride, CCl3H

196

EXPERIMENTAL

1. Preparation of 2,5-Dibromo-3,4-Dimethylthieno[2,3-b]Thiophene

A solution of 3,4-dimethylthieno[2,3-b]thiophene-2,5-dicarboxylic acid (0.11mol)dissolved in 800ml of NMP and 50ml of water was treated with the portionwiseaddition of N-bromosuccinimide (0.25mol) for over 30 minutes. The mixture wasstirred for 16 hours at ambient temperature and then poured into 1 liter of water.The resultant precipitate was dried, the residue purified by flash chromatographyover silica using petrol, and the product isolated in 77% yield.

2. Preparation of 2,5-bis(3-Octylthiophen-2-yl)-3,4-Dimethylthieno[2,3-b]Thiophene

The Step 1 product (14.5mmol) dissolved in 20ml of THF was treated with Riekezinc (17mmol) at �78�C, stirred 16 hours at ambient temperature. With the stirringstopped, the solution was allowed to settle for 2 hours, whereupon the solution wastransferred by cannula into a flask containing 2,5-dibromo-3,4-dimethylthieno[2,3-b]thiophene (3.9mmol), 50ml of THF, and [1,10-bis(diphenylphosphino)ferrocene]palladium(II) chloride (64mg) at 0�C. The mixture was warmed to ambienttemperature for over 30 minutes and refluxed for 24 hours. The reaction wascooled and quenched with 5% hydrochloric acid and then extracted 3 times with50ml of EtOAc. Combined extracts were washed with brine, dried using Na2SO4,and concentrated. The residue was purified by flash chromatography over silica withpetrol-followed by reverse, phase chromatography using CH3CN/THF, 2:1, respec-tively, and the product was isolated in 72% yield as a colorless oil.

3. Preparation of Poly(2,5-bis(3-Octylthiophen-2-Yl)-3,4-Dimethylthieno[2,3-B]thiophene)

The Step 2 product (1.28mmol) dissolved in 20ml CCl3H was treated with thedropwise addition of ferric chloride (6. 2mmol) dissolved in 100ml CCl3H. Asteady stream of nitrogen was passed through the solution to remove HCl formedduring the reaction as it stirred 18 hours at ambient temperature. The mixturewas then poured into 500ml methanol and stirred for 30 minutes, filtered, andthe precipitate washed with water and methanol. The yellow precipitate was stirredin 16M of NH4OH for 60 minutes then filtered and dried. The solid was Soxhletextracted with methanol, iso-hexane, and acetone. The material was then dissolvedin CCl3H, re-precipitated in methanol, dried, and the product isolated.

Mn (GPC)¼ 17,000 daltonsMw (GPC)¼ 20,000 daltonslmax¼ 380 nm

M/Z: 556 (Mþ)Elemental analysis: Found C, 69.1%, H, 7.6%

Calc. for C32H44S4C, 69.0; H 8.0

Experimental 197

DERIVATIVES

NOTES

1. Methods for preparing polymeric selenophene analogues of the current inventionusing selenophene-2,5-diyl derivatives have been proposed Tierney [1].

2. Copolymers of 9-H,H-fluorene and thiophene, (I), were prepared by the author[2] and used as charge transport materials in electronic devices.

SS

(I)

a

3. Poly(3,30-dialkyl-2,20:502-terthiophene) derivatives, (II), prepared by McCul-loch [3] were also effective in electronic components as charge transportmaterials and semiconducters.

TABLE 1. Selected poly(thieno[2,3-b]thiophene) derivatives and correspondingphysical properties.

Entry StructureMn

(daltons)Mw

(daltons) lmax (nm)

2

S S

S S

C8H17 C8H17

a

9,000 22,000 380

4

aS

SC8H17

SSC8H17

6,400 9,400 414

5

aS

SC12H25

SSC12H25

14,000 22,000 414

6

aS S

S

C6H13

13,000 40,000 462

1H- and 13C-NMR for intermediates supplied by author.

198 Mono-, Oligo-, and Polythieno[2,3-b]Thiophenes

aS

S S

R R

R = CH3 - C8H17

(II)4. Crosslinkable mesogenic azulenes, (III) and (IV), prepared by Farrand [4], and

anthracenyl, (V), and tetracenyl, (VI), thiophenes, prepared byGerlach [5], wereused as semiconductors and charge transport agents in electronic devices.

SS

SS

SS

SS

O(CH2)6O2CCH=CH2H2C=HCCO2(H2C)6O

(VI)

O(CH2)6O2CCH=CH2

(III)

H2C=HCCO2(H2C)6O

(IV)

(V)

5. Trimeric thiophenes attached to a core-shell structure, (VII), were prepared byKirchmeyer [6] and used as semiconductors.

T

TT T T

T

T

T

T

T

S

S

SC10H21T =

(VII)

Notes 199

References

1. S. Tierney et al., US Patent Application 2007-0045592 (March 1, 2007)2. M. Heeney et al., US Patent 7,126,013 (October 24, 2006)3. I. McCulloch et al., US Patent 6,953,957 (October 11, 2005)4. L.D. Farrand et al., US Patent 7,115,755 (October 3, 2006)5. C.P. Gerlach,US Patent 6,998,068 (February 14, 2006)6. S. Kirchmeyer et al., US Patent 7,078,724 (July 18, 2006)

200 Mono-, Oligo-, and Polythieno[2,3-b]Thiophenes

Title: Poly(Arylene Ether) Dielectrics

Author: C. Lim et al., US Patent 7,166,250 (January 23, 2007)Assignee: Chartered Semiconductor Manufacturing Ltd. (Singapore, SG)

SIGNIFICANCE

Three polyarylene ethers having aMn> 10,500with dielectric constants of around 2.5were prepared and used as low k dielectric layers in electronic applications.

Polyarylene ethers were prepared using the Ullmann ether synthesis and had Td ‘sin air of at least 310�C.

REACTION

OHHO OOS S

ai

Note 1

i: Benzophenone, toluene, sodium hydroxide, 2,5-dibromo-thiophene, copper(I)chloride, acetic acid, methanol

EXPERIMENTAL

1. Preparation of Poly(Arylene Ether)

The Ullmann ether catalyst was prepared by charging a 50-ml flask with copper(l)chloride (0.61mmol) and 0.6ml of quinoline and then stirring at 25�C for 48 hours. Amixture consisting of 9,9-bis(4-hydroxyphenyl)fluorene (2.86mmol), benzophenone(5 g), and about 3ml of toluene was charged to a 50-ml three-necked round bottomflask fitted with a distillation apparatus and heated to 60�C. The mixture was treated

201

with aqueous sodium hydroxide (5.72mmol) and water azeotroped by vacuumdistillation at an elevated temperature and then cooled. After re-heating to 80�C themixture was treated with 2,5-dibromo-thiophene (2.86mmol) and further heated to180�C and treatedwith 0.6ml of the Ullmann ether catalyst. Heating was continued at180�C for 17 to 24 hours, and the mixture was next treated with a single portion of0.02 gdrycopper(I) chloridepowder.Themixture temperaturewas increased to190�Cfor 24 hours, treated with 0.3 g of 2-bromothiophene, and stirred an additional hour. Itwas cooled to 100�C, treated with roughly 5.5ml of toluene, and precipitated in asolution of acetic acid and methanol. The polymer was Soxhlet extracted for 24 hoursusing methanol, acetone, and chloroform. The polymer was dissolved in a minimumamount of chloroform, re-precipitated in 100ml of methanol, and the product wasisolated.

DERIVATIVES

NOTES

1. Additional derivatives of the current invention were prepared by the author [1]in a subsequent investigation.

TABLE 1. Summary of physical and dielectric properties of selected poly(aryleneethers) prepared using the Ullmann ether catalyst.

Entry StructureMn

(daltons)

Td(�C)(air)

Td(�C)(N2)

Tg(�C)

e(100 kHz)

1

OOS S a

25,000 310 355 312 �2.43

2

OOaN

N

11,000 345 325 214 �2.65

3

OOaN

N

32,000 450 450 227 �2.35

202 Poly(Arylene Ether) Dielectrics

2. Terahara [2] utilized the Ullmann ether catalyst of the current invention toprepare poly(arylene ethers), (I), for use as a component in fuel cells.

OO

n

(I)

3. Bai [3] surface modified polymeric low dielectric constant gate insulator filmsconsisting of polystyrene/polyacrylate block copolymers, (II), having ane� 4.6. Perfluoroether acyl oligothiophenes, (III), prepared by Gerlach [4]were also effective as low dielectric constant gate insulators.

OONH

O

O

ONNC

CN

a

b c

(II)

S

R1

O

R1

O

(III)

R1 a

aCF2(CF2CF2CF2O)3CF3 5

CF(CF3)CF2OCF(CF3)OCF3 6

4. Low dielectric constant gate insulators were prepared by Kelley [5] consistingof poly(stryene-co-vinyl phosphonic acid) and having termini consisting ofeither trimethyloxysilyl- or phosphinic acid.

5. Weber [6] devised a method for repairing porous low k dielectric films bysealing with polydentate ligands, such as ethylene diamine tetraacetic.

6. Burgoyne [7] prepared polyarylene ethers containing grafted furfuryl, (IV), thatcrosslinked at low temperatures and were useful as dielectric or super high

Notes 203

aperture enhancing materials with high glass transition temperatures and lowmoisture uptake.

O O O O

HO

O

a b a:b =2:1

(IV)

References

1. C. Lim et al., US. Patent 7,179,879 (February 20, 2007)2. A. Terahara et al., US. Patent 7,081,497 (July 25, 2006)3. F. Bai et al., US. Patent 7,098,525 (August 29, 2006)4. C.P. Gerlach et al., US. Patent 7,151,276 (December 19, 2006)5. T.W. Kelley et al., US. Patent 6,946,676 (September 20, 2005)6. F. Weber et al., US. Patent 7,163,900 (January 16, 2007)7. W.F. BurgoyneJr. et al., US Patent 7,179,878 (February 20, 2007)

204 Poly(Arylene Ether) Dielectrics

Title: Polythiophenes and Devices

Author: B. S. Ong et al., US Patent 7,141,644 (November 28, 2006)Assignee: Xerox Corporation (Stamford, CT)

SIGNIFICANCE

Mechanically durable and structurally flexible polythiophene derivatives have beenprepared that are useful as semiconducters in thin film field effect transistors and aresoluble in chlorobenzene. Materials prepared from these agents have a bandgapbetween 1.5 and 3.0 eV that enhance their function as film transistors.

REACTION

S Br SS

SS

SS

SS

a

i ii

i: THF, magnesium, 1,3-bis(diphenylphosphino]dichloronickel(II), 5,50-dibromo-2,20-dithiophene, hydrochloric acid

ii: Ferric chloride, CCl3H

205

EXPERIMENTAL

1. Preparation 5,50-Bis(3-Dodecyl-2-Thienyl)-2,20-Dithiophene

A solution of 2-bromo-3-dodecylthiophene (34.92mmol) dissolved in 40ml ofanhydrous THF was slowly added over a period of 20 minutes to a mechanicallystirred suspension of magnesium turnings (51.83mmol) in 10ml of THF under aninert argon atmosphere. The mixture was stirred at ambient temperature for 2 hoursand then at 50�C for 20 minutes before cooling down to ambient temperature. Thismixture was added by cannula to 5,50-dibromo-2,20-dithiophene (13.88mmol) and1,3-bis(diphenylphosphino)dichloronickel (II) (0.35mmol) in 80ml of THF andrefluxed for 48 hours. The reaction mixture was then diluted with 200ml of EtOAc,washed twice with water and 5% HCl, dried with Na2SO4, and concentrated.The dark brown syrupy residue was purified by column chromatography on silicagel, and the product was isolated in 55% yield as a yellow crystalline solid,MP¼ 58.9�C.

2. Preparation of Poly[5,50-bis(3-Dodecyl-2-Thienyl)-2,20-Dithiophene]

A solution of the Step 1 product (0.75mmol) in 7ml of CCl3H was slowly added to astirred mixture of FeCl3 (2.47mmol) in 3ml of CCl3H and heated to 50�C for 1 hourand then to 40�C for 24 hours. After the polymerization, the mixture was dilutedwith 20ml of toluene and washed three times with water. The separated organicphase was stirred with 200ml of 7.5% NH4OH, washed three times with water, andpoured into methanol to precipitate the crude polythiophene. The residue waspurified by Soxhlet extraction with methanol, hexane, and chlorobenzene, and theproduct was isolated with a Mw¼ 27,300 daltons and Mn¼ 16,900 daltons.

DERIVATIVES

Only poly[5,50-bis(3-dodecyl-2-thienyl)-2,20-dithiophene] in varying molecularweights was prepared.

Testing Results

Thin film transistor devices were fabricated by spin coating using a 1% solutionof the selected polythiophene dissolved in chlorobenzene and drying in vacuo at80�C for 20 hours. No precautions were taken to exclude oxygen, moisture, orlight during device fabrication. From transistors with dimensions of 5000� 60m, electrical properties were determined as summarized in Table 1.

1H NMR (CDCl3) d 7.18 (d, J¼ 5.4Hz, 2H), 7.13 (d, J¼ 3.6Hz, 2H), 7.02 (d, J¼ 3.6Hz, 2H), 6.94 (d,J¼ 5.4Hz, 2H), 2.78 (t, 4H), 1.65 (q, 1.65, 4H), 1.28 (bs, 36H), 0.88 (m, 6H)

206 Polythiophenes and Devices

TABLE

1.Effecto

fpoly[5,50-bis(3-dod

ecyl-2-thienyl)-2,20-dithiophene]of

varyingmolecularweigh

tsof

thecurrentinv

ention

onmob

ility

andcurrenton

/offratiowhen

spin

casted

onto

thin

film

tran

sistor

devices.

Step

2Produ

ctM

w(M

n)

(daltons)

Reactions/Purifications

Con

dition

sMob

ility(cm

2/V

. s)

InitialCurrent

On/OffRatio

Current

On/Off

after5Days

3890

(380

0)25

� C(24ho

urs);precipitated

from

CH3OH

0.9–

2.0�10

�41.2�10

3––

14,900

(900

0)40

� C(1

hour);25

� (48

hours);extracted

withtoluene

2.0–

3.1�10

�42.2–

4.7�10

3––

14,900

(900

0)Thendevice

annealed

at13

5�C10

minutes

14,000

(11,40

0)

40� C

(1ho

ur);25

� C(24ho

urs);

extractedwithCH3OH,hexane,and

chlorobenzene50

� C(1

hour);then

40� C

.

1.1–

3.4�10

�34.5–

9.0�10

40.7–

1.1�10

4

1.9–

8.7�10

�35.0–

8.5�10

51.1–

2.5�10

5

27,300

(16,90

0)50

� C(1

hour)then

40� C

(24ho

urs);

extractedwithCH3OH,hexane,and

chlorobenzene

0.9–

2.0�10

�21.0–

5.1�10

61.9–

3.2�10

5

207

NOTES

1. In earlier investigations by the author [1] polythiophene analogues containingphenylene, (I), were prepared and used as semiconducters in thin film fieldeffect transistors.

SS

SS

BrBr

SS

SS

ai

(I)

i: 1,4-Benzenebis(pinacolboronate), toluene, Aliquot 336, tetrakis(triphenyl-phosphine)-palladium

2. Sotzing [2] prepared intrinsically conducting water-borne dispersions of poly(thieno[3,4-b]thiophene) homopolymer, (II), and copolymers of thieno[3,4-b]thiophene and 3,4-ethylenedioxythiophene, (III), for electroactive applicationsincluding electrochromic displays, optically transparent electrodes, and anti-static coatings.

S

S

S

S

S

S

S

S

S

S

S

OO

S SS

O

O

a

b

a

b

(II) (III)


3. Groenendaal [3] prepared water soluble 4-(2,3-dihydro thieno[3,4-b)][1,4]dioxin-2-yl-methoxy)-butane-1-sulfonic acid sodium salt, (IV), and copoly-mers with poly(styrenesulphonic acid) having a Mw of 290,000 daltons thatwere used in electroconductive devices.

S

OO

O

SO3Na

(IV)

4. Additional polythiophene p-conjugated polymer precursors were prepared byReuter [4], (V), and Groenendaal [5], (VI), and used in electroconductivedevices as semiconductors.

SS

OO

OO

HO

OH(V)

S

OO

(VI)

R R = C8H17 C10, H21 C12, H25

5. Kirchmeyer [6] prepared linear organic thiophenephenylene oligomers, (VII),that were effective as semiconductor coatings.

SS

S SS

SC10H21

C10H21

(VII)

Notes 209

6. Regioregular intriniscally conducting mono-, di-, and triblock moderate mo-lecular weight polythiophenes containing awell-defined terminus, (VIII), wereprepared byMcCullough [7] and used in thin field-effect transitor applications.

SS

OHH

46

(VIII)

References

1. B.S. Ong et al., US Patent 7,132,500 (November 7, 2006) and US Patent 7,132,682 (November 7, 2006)2. G.A. Sotzing,US Patent 7,125,479 (October 24, 2006), US Patent Application 2005-0124784

(June 9, 2005), and US Patent Application 2004-0010115 (January 15, 2004)3. B. Groenendaal et al., US Patent 7,105,620 (September 12, 2006)4. K. Reuter, US Patent 7,102,016 (September 5, 2006)5. B. Groenendaal et al., US Patent 7,094,865 (August 22, 2006)6. S. Kirchmeyer et al., US Patent 7,199,251 (April 3, 2007)7. R.D. McCullough et al., US Patent 7,098,294 (August 29, 2006)


Title: Mono-, Oligo- and Polymers ComprisingFluorene and Aryl Groups

Author: M. Heeney et al., US Patent 7,126,013 (October 24, 2006)Assignee: Merck Patent GmbH (Darmstadt, DE)

SIGNIFICANCE

Polymers and elastomers comprising at least one 9-H,H-fluorene group and at leastone arylene group have been prepared. These materials are suitable for use assemiconductors or charge transport materials in optical, electrooptical, or electronicdevices, including field-effect transistors, electroluminescent, photovoltaic, andsensor devices.

REACTION

Br Br B B

O

O O

O

S

C12H25

S

S

C12H25

C12H25

S

S

C12H25

C12H25

Br

Br

S

S

C12H25

C12H25

Intermediate

a

i

ii iii ivIntermediate

i: Bis(pinacolato)diboron, potassium acetate, dichlorobis(tricyclohexylphosphine)palladium(II), 4-dioxane

ii: BuLi, tetramethylethylenediamine, copper(II) chlorideiii: N-Bromosuccinimide, CCl3H, acetic acidiv: Tetrakis(triphenylphosphine)palladium, Aliquat 336, toluene, sodium carbonate

211

EXPERIMENTAL

1. Preparation of 2,7-Bis(4,4,5,5-Tetramethyl-1,3,2-Dioxaborolan-2-yl)-Fluorene

A flask was charged with 2,7-dibromofluorene (17.73mmol), bis(pinacolato)dibor-on (44.33mmol), potassium acetate (5.22 g, 53.20mmol), dichlorobis(tricyclohex-ylphosphine)-palladium(II) (0.61mmol), and 150ml of 1,4-dioxane and stirred at100�C for 24 hours. The reaction mixture was quenched with 100ml of water andextracted twice with 200ml of CCl3H. Combined extracts were washed with 100mlof water, dried with Na2SO4, and concentrated. The residue was purified by columnchromatography using CH2Cl2, and the product was isolated as a white solid in 76%yield.

2. Preparation of 4,40-Didodecyl-2,20-Bithiophene

A solution of 3-dodecylthiophene (39.61mmol) in 40ml of THF at ambienttemperature was treated dropwise with 18ml of 2.5M BuLi in hexanes(45.00mmol) and 6.8 ml of tetramethylethylenediamine (45.06mmol) and refluxed1 hour. The mixture was cooled to �78�C and treated with copper(II) chloride(47.53mmol) in a single portion. It was then stirred at ambient temperature for 18hours and refluxed for 6 hours. The mixture was acidified with dilute hydrochloricacid and extracted twice with 200ml of diethyl ether. Combined extracts werewashed with 100ml of water and dried with Na2SO4 and concentrated. The residuewas purified by column chromatography using petroleum ether 40 60, re-crystal-lized from diethyl ether at�78�C, and the product was isolated as a yellow solid in38% yield.

3. Preparation of 5,50-Dibromo-4,40-Didodecyl-2,20-Bithiophene

Avessel containing the Step 2 product (1.49mmol) dissolved in 5ml apiece of CCl3Handglacial acetic acidwas treated portionwisewithN-bromosuccinimide (2.98mmol)and stirredovernight before beingpoured intowater and extracted twicewith 250mlofCH2Cl2.Combinedextractswerewashed twicewith100mlofwater andconcentrated.The residue was purified by column chromatography using petroleum ether, and theproduct was isolated as a yellow solid in 100% yield.

1H-NMR (CDCl3, 300MHz) d 6.97 (2H, s), 6.76 (2H, s), 2.56 (4H, t,3J.sub.HH¼ 8.0Hz), 1.61 (4H, m),1.20 1.40 (36H, br), 0.88 (6H, t, .sup.3J.sub.HH¼ 7.0Hz)

13C-NMR (CDCl3, 75MHz) d 44.0, 137.4, 124.8, 118.7, 32.0, 30.6, 30.4, 29.7, 29.6, 29.5, 29.4, 29.3, 22.7,14.2

1H-NMR (CDCl3, 300MHz) d 6.77 (2H, s), 2.51 (4H, t, .sup.3J.sub.HH¼ 8.0Hz), 1.57 (4H, m), 1.20 1.40(36H, br), 0.88 (6H, t, sup.3J.sub.HH¼ 7.0Hz)

13C-NMR (CDCl3, 75MHz) d 142.8, 136.0, 124.3, 107.0, 31.8, 29.5, 29.4, 29.2, 29.0, 22.6

212 Mono-, Oligo- and Polymers Comprising Fluorene and Aryl Groups

4. Preparation of Poly(4,40-Didodecyl-2,20-Bithiophene-alt-Fluorene)

A flask was charged with the Step 1 (1.44mmol) and Step 3 (1.44mmol) products,tetrakis-(triphenylphosphine)palladium(0) 0.03mmol), Aliquat 336 (0.25 g), and20ml toluene and then treated with 2.5ml of 2M aqueous Na2CO3. The mixturewas refluxed for 48 hours and precipitated by pouring into 400ml of methanol. Thepolymer was collected and washed with water followed by methanol and then dried.The dried polymer was Soxhlet extracted for 16 hours with methanol and six hours byiso-hexane. The polymer was re-dissolved in hot CCl3H and precipitated in 400mlmethanol and dried; the product was isolated as a green solid in 78% yield.

DERIVATIVES

TABLE 1. Selected bisthiophene-fluorene copolymers and monomer preparedaccording to the current invention.

Entry StructureTm(�C)

Tg(�C)

MS(m/e)

1S

S

C6H13

C6H13 a

122 199 —

3

a

C6H13 C6H13

>300 — —

4S

OO

O

SO

OO

— — 768(MþOH)

Note: Extensive 1H- and 13C-NMR for all entries provided by author.

Tm¼ 130�CTg¼ 160�CTd¼ 360�CMn¼ 32,000 daltons (bimodal)Mw¼ 137,000 daltonsAbsorbance (lmax CDCl3)¼ 405 nm1H-NMR (CDCl3, 300MHz) d 7.84 (2H, d, .sup.3J.sub.HH¼ 8.0Hz), 7.66 (2H, s), 7.51 (2H, d, .sup.3J.sub.

HH¼ 8.0Hz), 7.11 (2H, s), 4.02 (2H, s), 2.71 (4H, br), 1.67 (4H, br), 0.95 1.40 (36H, br), 0.87(6H, br)

Derivatives 213

NOTES

1. Conjugated polyazulene derivatives, (I) and (II), prepared by Farrand [1] wereuseful as components in optical, electro-optical, and electronic devices.

a

a

(I)

(II)

2. Jubran [2] and Tokarski [3] prepared photoreceptors comprising an electricallyconductive substrate and a photoconductive element consisting of phenothia-zines, (III) and (IV), and carbazole, (V), derivatives, respectively.

N

S

R

NN

OHS S S N

OH N

N

S

R

(III)

N

SNN

OHS S N

OH N

N

S

(IV)

N

S

N

R = CH3, C2H5

N

OH

NN

O

(V)

214 Mono-, Oligo- and Polymers Comprising Fluorene and Aryl Groups

3. Perfluoroacyl oligomeric thiophene derivatives, (VI), prepared by Gerlach [4]were effective as n-channel semiconductor thin film layers in electronicdevices.

S

O O

O

CF3

O

CF3

CF2

C3F7O CF2

OC3F7

CF3 CF3

(VI)

5

References

1. L.D. Farrand et al., US Patent 7,034,174 (April 25, 2006)2. N. Jubran et al., US Patent 7,169,520 (January 30, 2007)3. Z. Tokarski et al., US Patent 7,166,400 (January 23, 2007)4. C.P. Gerlach et al., US Patent 7,211,679 (May 1, 2007)

Notes 215

VIII. ENERGETIC POLYMERS

Title: Glycidyl Dinitropropyl Formal, Poly(GlycidylDinitropropyl Formal), and PreparationMethod Thereof

Author: J. S. Kim et al., US Patent 7,208,637 (April 24, 2007)Assignee: Agency for Defense of Korea (Daejeon, KR)

SIGNIFICANCE

An energetic polyether containing grafted gem-nitro’s has been prepared having adecomposition temperature of 200 �C or higher. This polymeric agent is useful as astable energetic binder for insensitive and high-performance explosives.

REACTION

a

OHNO2O2N

O ONO2O2N

O ONO2O2NO

OOO

O

O

NO2

NO2

iiiiii

i: Formaldehyde, allyl alcohol, CH2Cl2, boron trifluoride etherateii: CCl3H, 3-chloroperbenzoic acidiii: 1,4-Butandiol, boron trifluoride etherate, CH2Cl2


217

EXPERIMENTAL

1. Preparation Allyl Dinitropropyl Formal

A reactor was charged with 2,2-dinitropropanol (0.1mol), formaldehyde (0.11mol),allyl alcohol (0.3mol), and CH2Cl2 (40 g) and treated with the slow addition of borontrifluoride etherate (0.3mol) at 5�C. After the addition the mixture was stirred at 5�Cfor 40minutes. Thereafter 100ml ofwaterwas slowly added to themixture,whichwasthen stirred and the aqueous component discarded. The organic layer was washed 3timeswithNaOH, oncewithwater, oncewith brine, and againwithwater. The organicphase was then dried, concentrated, and the product was isolated in 73% yield.

2. Preparation of Glycidyl Dinitropropyl Formal

TheStep1product (0.15mol) andCCl3H (400 g)were charged into a flask then treatedwith 3-chloroperbenzoic acid (0.18mol) over 30 minutes. After the addition wascomplete, the mixture was refluxed for 3 hours, cooled to ambient temperature, andstirred an additional 12hours. Themixturewas cooled to 0�C, filtered, and the solutionwas washed twice with 5% sodium sulfite and with 5% sodium hydroxide. Thesolutionwas nextwashedwith brine, dried, concentrated, and the productwas isolatedin 92% yield.

3. Preparation of Poly(Glycidyl Dinitropropyl Formal)

1,4-Butandiol (2mmol) was added to boron trifluoride etherate (1 mmol) andvacuum purified for 2 hours to remove diethyl ether. This mixture was then treatedwith CH2Cl2 (12 g) and the slow addition of the Step 2 product (50mmol) dissolvedin CH2Cl2 over 3 hours. The mixture was reacted an additional 30 minutes andwashed with 50ml of water, 30ml of CH2Cl2, and three times with 50ml of brine. Itwas dried using MgSO4 and then precipitated in 20ml ethanol. The polymer wasnext heated to 80�C at 1mmHg for 5 hours to purify, and the product isolated in 90%yield. The product had a Mw of 2,200 daltons, a polydispersity index of 1.12, ahydroxyl group of 0.621 eq/kg, a Tg of �23�C, and a decomposition temperaturegreater than 200�C.

DERIVATIVES


1HNMR(CDCl3) d 2.17(s, 3H), 2.60(t, 1H), 2.78(t, 1H), 3.1(m, 1H), 3.8(m, 1H), 4.3(s, 2H), 4.7(s, 2H)

218 Glycidyl Dinitropropyl Formal, Poly(Glycidyl Dinitropropyl Formal), and Preparation

NOTES

1. In an earlier investigation by the author [1] poly(glycidyl dinitropropylcarbonate), (I), was prepared and used as an energetic binder for insensitiveand high-performance explosives.

O

O

O

NO2

O

NO2

(I)

a

2. Sanderson [2] prepared the energetic thermoplastic elastomer poly(3,3-bis(azidomethyl)-oxetane), (II), for use as a binder for a propellant, explosive, orgas generant for a supplemental restraint system in automobiles. Random blockcopolymers of poly(azidomethyloxirane) and poly(3,3-bis(azidomethyl)oxe-tane), (III), were also prepared by Sanderson [3] using toluene diisocyanate asthe coupling agent.

aO

N3 N3

(II)

OHN

ONH

O

O

N3N3

N3

(III)

a

b

3. Adams [4] prepared energetic fullerenes of the generic formula, C60(NO2)n,where n¼ 1–60, and where at least 10% of the molecule consisted ofnitrogen.

References

1. J.S. Kim et al., US Patent 6,706,849 (March 16, 2004)2. A.J. Sanderson et al., US Patent 7,101,955 (September 5, 2006)3. A.J. Sanderson et al., US Patent Application 2006-0157173 (July 20, 2006)4. C. Adams, US Patent 7,025,840 (April 11, 2006)

Notes 219

Title: Synthesis of Energetic Thermoplastic ElastomersContaining Both Polyoxirane and Polyoxetane Blocks

Author: A. J. Sanderson et al., US Patent 7,101,955 (September 5, 2006)Assignee: Alliant Techsystems, Inc. (Edina, MN)

SIGNIFICANCE

An energetic thermoplastic elastomer consisting of poly(azidomethyloxirane)-b-(3,3- bis(azidomethyl)-oxetane) has been prepared that is suitable for use as a binderfor a propellant, explosive, and/or gas generator. Block seqments were prepared using2,4-diisocyanate toluene.

REACTION

OH

Br

Br

Br

O

N3 N3

O

N3

N3O

HN

NH

O

O

N3

a

b

i ii

i: Tribromoneopentylalcohol, toluene, tetrabutylammonium bromide, sodium hydr-oxide sodium azide

ii: Poly(azidomethyloxirane), dibutyltin dilaurate, toluene-2,4-diisocyanate, CH2Cl2

EXPERIMENTAL

1. Preparation of 3,3-bis(Azidomethyl)Oxetane

A reactor was chargedwith tribromoneopentylalcohol (600 g), 1200ml of toluene andtetrabutylammonium bromide (6 g) then cooled to 12�C and slowly treated with a 40wt% solution of sodium hydroxide (193 g). After 36 hours crude bis(bromomethyl)oxetane was washed with water until the pH was less than 9 and then distilled; theproduct was isolated in 65% yield.

220

2. Preparation of Poly[(Azidomethyloxirane)-b-(3,3-bis(Azidomethyl)-Oxetane)]

In a 250ml round bottom flask poly(azidomethyloxirane) (19.62 g) and the Step 1product (6.63 g) were dissolved in 80ml of CH2Cl2; the solution concentratedsufficiently for the solution to become cloudy. This cloudy solution was then treatedwith 0.12ml of dibutyltin dilaurate and toluene-2,4-diisocyanate (3.11 g). After 4hours, butane-1,4-diol (0.805 g) was added, causing the solution to become steadilymore viscous; after another 18 hours, the solution was too viscous to stir. The mixturewas then diluted with 50ml of CH2Cl2, precipitated, and the product was isolatedhaving a Mn of 28,440 daltons, Mw of 219,500, and a polydispersity index of 7.7.

DERIVATIVES

Poly(nitromethyloxirane)-b-(3,3-bis(azidomethyl)-oxetane) was also prepared.

O

N 3

N 3O

HN

NH

O

O

O 2 N

a

b

NOTES

1. Sanderson [1] and Highsmith [2] prepared glycidyl nitrate and subsequentlyconverted it into polyglycidyl nitrate (I) using calcium hydride and borontrifluoride.

aO

ONO2(I)

Derivatives 221

2. Poly(glycidyl dinitropropyl formal), (II), was prepared byKim [3] and used as aperformance insensitive explosive.

aO

OO

O

O

NO2

NO2(II)

3. The energetic plasticizer, 2,2-dinitro-1,3-propanediol-diformate, (III), pre-pared by Highsmith [4] was used in explosive and propellant compositions.

NO2O 2 NO O H

O

H

O (III)

References

1. A.J. Sanderson et al., US Patent 6,861,501 (March 1, 2005) and US Patent 6,861,501 (May 4, 2004)2. T.K. Highsmith et al., US Patent 6,362,311 (March 26, 2002)3. J.S. Kim et al., US Patent 7,208,637 (April 24, 2007)4. T.K. Highsmith et al., US Patent 6,425,966 (July 30, 2002)

222 Synthesis of Energetic Thermoplastic Elastomers Containing Both Polyoxirane

IX. FIBERS

Title: Rigid-Rod Benzobisazole PolymersIncorporating Naphthalene-1,5-Diyl Structure Units

Author: T. D. Dang et al., US Patent 7,041,779 (May 9, 2006)Assignee: United States of America as Represented by the Secretary of the

Air Force (Washington, DC)

SIGNIFICANCE

Aromatic heterocyclic rigid-rod polymers that have exceptional thermal oxidativestability have been prepared using 1,5-naphthylene dicarboxylic acid and 2,5-diami-no-1,4-benzenedithiol. These heterocyclic rigid-rod polymers materials are useful asprotective garments in ballistic vests and abrasion- and flame-resistant fabrics.

REACTION

CO2H

HO2C

S

N

Na

S

i

Notes 1,2

i: 2,5-Diamino-1,4-benzenedithiol dihydrochloride, polyphosphoric acid, phospho-rous pentoxide


223

EXPERIMENTAL

Preparation of Benzobisthiazole-Naphthalic Fibers

A resin flask was chargedwith naphthalene-1,5-dicarboxylic acid (0.0116mole), 2,5-diamino-1,4-benzenedithiol dihydrochloride (0.0116 moles), and 77% polyphospho-ric acid (20.8 g). The mixture was then dehydrochlorinated over a period of 24 hoursunder a nitrogen flowwhile slowly raising the temperature to 105�C. Themixturewasthen cooled and treated with P2O5 (11.37 g) and heated to 165

�C and the polymeriza-tion reaction proceeded overnight. During this process, stir opalescence characteristicof the anisotropic phase was observed. The mixture was further heated to 180�C for afewhours, and roughly3 gof thepolymer dopewere takenout for fiber spinning.Usingpolarizing optical microscopy a sample of the dope was sealed between two glassslides and found to exhibit optical birefringence; the persistence of the observedoptical texture several days laterwas indicative of lyotropic liquid crystalline behaviorof thematerial. The remaining dopewas precipitated inwater and the fibrous polymershredded in a blender. The polymer was filtered off, Soxhlet extracted with hot waterand dried, and the product was isolated as a dark yellow solid having an intrinsicviscosity of 13.2 dl/g measured in methanesulfonic acid at 30�C.

DERIVATIVES


NOTES

1. The preparation of naphthalene-1,5-dicarboxylic acid is illustrated below.

NH2

NH2

CN

CN

CO2H

CO2H

iii

I

I

iii

i: Hydrochloric acid, sodium nitrite, potassium iodideii: Copper(I) cyanide, sodium cyanide, wateriii: Hydrobromic acid, acetic acid, water

2. The Step 1 product was fabricated into fibers using the continuous dry jet–wetspinning method.

224 Rigid-Rod Benzobisazole Polymers Incorporating Naphthalene-1,5-Diyl Structure Units

3. Kumar [1] demonstrated that the fiber strength of polyphenylenebenzobisthia-zole, (I), increased by using compositions containing carbon nanotubes.

S

N

N

S

(I)

a

4. Rigid-rod compositions consisting of polyphenylene derivatives were used byGoldberg [2] as advanced thermoplastics in preparing orthodontic wire.

5. Bazan [3] prepared conformationally flexible rigid rod cationic conjugatedpolymers, (II), comprising monomers that perturbed the polymer’s ability toform rigid-rod structures, thereby allowing them to form a greater range ofthree-dimensional structures.

c

(H3C)3N N(CH3)3

(H3C)3N N(CH3)3

BrBrBrBrBr

a b

(II)

6. Petschek [4] used heterocyclic rigid-rod polyionomers, including poly(pyr-idinium) salt, (III), and poly(benzimidazole-sulfonate), (IV), for coatingdirectionally onto charged surfaces to impart planar alignment and pre-tilt tothe surfaces.

aaN N

(III)

N

NH

N

HN

SO3

(IV)

Notes 225

References

1. S. Kumar et al., US Patent 6,900,264 (May 31, 2005)2. A.J. Goldberg et al., US Patent 7,186,115 (March 6, 2007)3. G.C. Bazan et al., US Patent 7,144,950 (December 5, 2006) and US Patent Application 2007-0088130

(April 19, 2007)4. R.G. Petschek et al., US Patent 6,942,905 (September 13, 2005)

226 Rigid-Rod Benzobisazole Polymers Incorporating Naphthalene-1,5-Diyl Structure Units

Title: Polybenzazole Fiber and Use Thereof

Author: Y. Abe et al., US Patent Application 2006-0083923 (April 20, 2006)Assignee: Canon Kabushiki Kaisha (Tokyo, JP)

SIGNIFICANCE

Polybenzazole fibers havebeenprepared containingblendedorganicpigments that areheat,moisture, and light resistantwith thermaldecomposition temperatures exceeding200�C.Thesematerials are useful as fibers for high-strength rope, cement/concrete re-inforcers, and bullet proof vests.

REACTION

a

H2N NH2

OHHO

N

O O

Ni

i: Terephthalic acid, polyphosphoric acid

EXPERIMENTAL

Preparation of Poly(p-Phenylenebenzobisoxazole)

Under a stream of nitrogen gas, 4,6-diamino-resorcinol dihydrochloride (334.5 g),terephthalic acid (260.8 g), and polyphosphoric acid (2,078.2 g) were mixed andstirred at 60�C for 30 minutes. The temperature was gradually increased to 135�C for20 hours, 150�C for 5 hours, 170�C for 20 hours, and then the material isolated. Theproduct hadan intrinsic viscosityof 30 dL/g at 30�Cmeasured inmethanesulfonic acid.

DERIVATIVES

Only the single derivative was prepared.

227

TESTING

Filaments were subjected to storage testing at elevated temperatures and highhumidity as well as light exposure testing. Testing results are provided in Table 1.

NOTES

1. Saitoh [1] prepared oriented polybenzazole, (I), films having high strength andhigh elastic modulus and heat and flame resistance.

a

O

N O

N

(I)

2. Kodama [2] prepared high molecular weight polybenzazoles, (I), using iron,(II), phosphate octahydrate as a reaction catalyst.

TABLE 1. Effect of high temperature and humidity and light exposure on poly(p-phenylene-benzobisoxazole) film strength retention containing various dopants.

Entry Dopant

InitialStrength(GPa)

Exposure to 80%Humidity at 80�Cfor 700 hours

Exposure to Lightfrom Xenon Lamp

for 100 hours

FinalStrength(GPa)

Retention(%)

FinalStrength(GPa)

Retention(%)

1 29H,31H-Phthalocyaninate(2-)-N29,N30,N31,N32copper

5.6 5.0 90 4.9 83

4 9,19-Dichloro-5,15-diethyl-5,15-dihydrodiindlo[2,3-c:20,30-n]triphenodiox-azine

5.5 4.8 88 4.5 81

12 Bisbenzimidazo[2,1-b:20,10-I]benzo[1mn][3,8]-phenathroline-8,17-dione

5.8 5.0 87 4.8 82

15 29H,31H-Phthalocyaninate(2-)-N29, N30,N31,N32copper

4.7 4.3 92 4.2 89

228 Polybenzazole Fiber and Use Thereof

3. Polybenzazole block copolymer, (II), prepared by Kodama [3] and containinglight-resisting m- or p-phenylenediamine had a 30% reflectance in the wave-length region of from 450 to 700 nm.

cO

N O

NO

N

a

b

(II)

4. Polybenzazole fibers, (I), prepared byKitagawa [4] had a compression strengthof not less than 0.5GPawhen blendedwith 1% to 15%carbon nanotubes havinga length ofmore than 20 nm andwidth of between 0.5 mm–10 mm. The resultingfibers had high strength, high elastic modulus, and fine fiber structure.

5. Adamantyl benzoxazole pre-polymers, (III) and (IV), were prepared byTakaragi [5] and Nagano [6], respectively, and used to prepare high molecularweight polymers with porous structures that were used in dielectric filmsassociated with semiconductors.

aOH

O

H2N

OH

O

N

(IV)

O OH

OH

O

H2N

OH

O

N

(III)

a

References

1. F. Saitoh et al., US Patent 7,122,617 (October 17, 2006)2. F. Kodama et al., US Patent 6,169,165 (January 2, 2001)3. T. Kodama et al., US Patent 6,818,734 (November 16, 2004)4. T. Kitagawa, US Patent 6,884,506 (April 26, 2005)5. A. Takaragi et al., US Patent Application 2007-0078256 (April 5, 2007)6. S. Nagano et al., US Patent Application 2007-0032556 (February 8, 2007)

Notes 229

X. FLUORINE

A. Critical Polymerization

Title: Process for Producing Fluoropolymer

Author: M. Tsukamoto et al., US Patent 7,173,098 (February 6, 2007)Assignee: Daikin Industries, Ltd. (Osaka, JP)

SIGNIFICANCE

An efficient method for preparing polyvinylidene fluoride by reacting above themonomer critical density and temperature is described.When polyvinylidene fluoridewas prepared in this manner, molecular weights were at least four times greater thanthose noncritically prepared.

REACTION

F

FF2C

i

Notes 1, 2

i: Di-n-propyl peroxydicarbonate

EXPERIMENTAL

Preparation of Polyvinylidene Fluoride

A stainless steel autoclave with an internal volume of 1083ml was chargedwith vinylidene fluoride (542 g) using a high-pressure plunger pump to establisha monomer density of 0.50 g/ml. Using a band heater the reaction temperaturewas raised to 40�C, which provided a reaction pressure of 5.72 MPa. The reaction


231

was then initiated with 6.1 g of 50% di-n-propyl peroxydicarbonate solutionin methanol; the polymerization continued for 1 hour. After venting, unreactedmonomer, 29.5 g of a white-colored product was isolated with Mn¼ 36,080 daltonsand Mw¼ 78,050 daltons.

SCOPING STUDIES

NOTES

1. In subsequent investigations by the author [1] when the Step 1 reaction of thecurrent invention was continued for 120 to 150 minutes, the correspondingpolymer had a Mn of 81,000 daltons and a Mw of 203,000 daltons. Additionalcritical polymerization reaction scoping studies using vinylidene fluoride aredescribed by the author [2].

2. Lee [3] polymerized vinylidene fluoride in supercritical water, namelyTH2O > 374�C and PH2O > 218:2 atm, using either t-butyl peroxyacetate ort-butyl peroxy-2-ethylhexanoate and obtainedMn’s exceeding 1million daltonswith a crystalline content >50%. In an earlier investigation by Lee [4] showed

TABLE 1. The effects of polymerization of vinylidene fluoride for one hour at 318Kat varying reaction pressures.

Entry Monomer (g)

MonomerReaction

Density (g/ml)

ReactionPressure(MPa)

Mn

(daltons)Mw

(daltons)

1 542 0.50 5.72 36, 080 78,0502 639 0.59 6.62 54,900 118,500NoncriticalComparison

314 0.29 5.13 8,560 14,700

Note: Critical parameters for vinylidene fluoride are 4.430 MPa as a critical density and 303.30K as acritical temperature.

TABLE 2. Critical parameters for selected perfluoro monomers.

Monomer Critical Density (g/ml) Critical Temperature (K)

Vinylidene floride 4.430 303.30Hexafluoropropene 2.900 367.10Tetrafluoroethylene 3.940 306.00Chlorotrifluoroethylene 3.960 379.00

Note: Critical parameters for perfluoro solvents were also provided by the author.

232 Process for Producing Fluoropolymer

that when methyl methacrylate and glycidal methacrylate were copolymerizedin supercritical water, a low polydispersed product was obtained.

References

1. M. Tsukamoto et al., US Patent Application 2006-0122347 (June 8, 2006)2. M. Tsukamoto et al., US Patent Application 2005-0043498 (February 24, 2005)3. S. Lee et al., US Patent 7,091,288 (April 15, 2006)

Notes 233

B. High Strength

Title: Fluorinated Terpolymer

Author: S. Kurihara et al., US Patent 7,009,017 (March 7, 2007)Assignee: Unimatec Co., Ltd. (Tokyo, JP)

SIGNIFICANCE

Perfluoro terpolymers consisting of tetrafluoroethylene, perfluoro(ethyl vinyl ether),and perfluoro(propyl vinyl ether) have been free radically prepared to have distin-guished transparency and good mechanical strength at both ambient temperature and372�C. These materials are particularly useful as high-strength moldings.

REACTION

F2C CF2CF2

F2C

CF2

CFCF2

CF

OC2F5

OC3F7

i

a

i: Isobutyryl peroxide, perfluoro-n-heptane, perfluoro(ethyl vinyl ether), perfluoro(propyl vinyl ether

EXPERIMENTAL

Preparation of Poly[Tetrafluoroethylene-co-Perfluoro(Ethyl Vinyl Ether)-co-Perfluoro-(Propyl Vinyl Ether)]

Ahigh-pressure reactorwaschargedwithwater (1200 g), perfluoro-n-heptane (690 g),perfluoro(ethyl vinyl ether) (22 g), perfluoro(propyl vinyl ether)(26 g), and methanol(0.1 g). After the temperature was increased to 30�C, tetrafluoroethylene (160 g) wasadded until a pressure of 0.85 MPa was obtained. The overall monomer ratio

234

of tetrafluoroethylene/perfluoro(ethyl vinyl ether)/perfluoro(propyl vinyl ether) was77/10/13, respectively. The polymerization was initiated with 25 wt% isobutyrylperoxide (4.0 g) dissolved in CClF2CF2CHClF. Since the reaction pressure decreasedwith the reactions progress, additional reagent mixture was added to maintain apressure of 0.85 MPa. Following the addition of these monomers, the mixturecontinued to react until the reaction pressure remained constant and the mixtureaged. Unreacted gases were purged from the reactor at 0.5 MPa, and 231 g of productwas isolated.

REACTION SCOPING

NOTES

1. Functionalized terpolymers, (I), consisting of vinylidene fluoride, hexafluor-opropene, and silyl-modified tetrafluoroethylene were prepared by Chung [1]to increase the reactivity of perfluoropolymers to subsequent chemical modi-fication.

a

F2C

CF2

CFCF2

CF

CF3

HSi

(I)

TABLE 1. Physical properties of perfluoro terpolymers as a function of composition.

Item Sample 1 Sample 3 Sample 5 Sample 9

Composition (wt%)Tetrafluoroethylene 95 72 46 46Perfluoro(ethyl vinyl ether) 2 13 25 39Perfluoro(propyl vinyl ether) 3 15 29 15

Tensile strength at break(372�C;� 103 Pa.s)

11 22 1.4 1.1

Light transittance250 nm (%) 62 95 96 95650 nm (%) 92 96 97 97

Glass transition temperature (�C) 102 43 21 21

Notes 235

2. Perfluoro terpolymerss consisting of tetrafluoroethylene, hexfluoropropylene,and vinylidene fluoride were prepared by Park [2] using electron beamradiation. Perfluoro terpolymers were also prepared by Park [3] using2,5-dimethyl-2,5-di(t-butylperoxy)-hexane.

3. Liquid vulcanizable fluoroelastomers consisting of vinylidene fluoride, per-fluoro(methyl vinyl ether), and tetrafluoroethylene were prepared by Kojima[4] and Park [5] and used for molding materials of low hardness.

4. Elastomers consisting of vinylidene difluoride/hexafluoropropylene or vinyli-dene difluoride/hexafluoropropylene/tetrafluoroethylene elastomers were pre-pared by Hochgesang [6] and cured using 4,40-hexafluoroisopropylidenediphenol.

References

1. T.Z. Chung et al., US Patent 7,045,248 (May 22, 2007)2. E.H. Park et al., US Patent 7,230,038 (June 12, 2007)3. E.H. Park et al., US Patent 7,153,908 (December 26, 2006)4. Y. Kojima et al., US Patent 7,202,299 (April 10, 2007)5. E.H. Park et al., US Patent 7,230,038 (June 12, 2007)6. P.J. Hochgesang et al., US Patent 7,098,270 (August 29, 2006)

236 Fluorinated Terpolymer

C. Low Molecular Weight

Title: Directly Polymerized Low Molecular WeightGranular Polytetrafluoroethylene

Author: R. A. Morgan, US Patent 7,176,265 (February 13, 2007)Assignee: E.I. du Pont de Nemours and Company (Wilmington, DE)

SIGNIFICANCE

Tetrafluoroethylenepolymerized in thepresenceof the chain transfer agent ethanewasused to prepare elastomeric grandular polytetrafluoroethylene. The average reactiontime was roughly 90 minutes and occurred in the absence of the surfactant perfluoro-octanoic acid.

REACTION

FF

F

F

F F

FFia

i: Ethane, ammonium persulfate, water

EXPERIMENTAL

Preparation of Low Molecular Weight Polytetrafluoroethylene

Specific concentrations and reaction parameters are provided in Table 1. All poly-merizationswere carried out in a stainless steel autoclave equippedwith a two-bladed,45� angled flat downdraft agitator mounted on a vertical shaft.

An autoclave was charged with water (21.4 kg) and ammonium persulfatedissolved in water (0.3 to 0.6 kg). The vessel was then purged of air by alternatelypressuring it with tetrafluoroethylene and evacuating. The chain transfer agent was

237

added, and the autoclave heated to 65�C and then pressurized to 1.83MPa withtetrafluoroethylene with an agitator speed at 600 rpm for the reaction. The initiatorsolution was next pumped into the autoclave and sufficient tetrafluoroethyleneadded to maintain a 1.83MPa reaction pressure. The reaction was completed oncethe amount of tetrafluoroethyleneadded was between 6.4 and 8 kg. The autoclavewas dismantled and the product was isolated.

REACTION SCOPING

REACTION SCOPING

TABLE 1. Single-step experimental parameters used in preparing low molecularweight granular polytetrafluoroethylene using either ethane or chloroformas chain transfer agents.

EntryChain TransferAgent*1 (mol%)

AmmoniumPersulfaceInitiator(lb)

PerfluorooctanoicAcid Surfactant

(lb)

TFEAdded(lbs)

ReactionTime(min)

1 CHCl3 (2.0) 0.013 None 14.3 1282 CHCl3 (3.5) 0.019 None 15.9 1323 C2H6 (2.2) 0.033 None 14.1 824 C2H6 (5.4) 0.053 None 14.1 735 C2H6 (5.3) 0.066 0.0048 15.9 1178 C2H6 (3.1) 0.033 None 14.1 9810 C2H6 (0.33) 0.010 None 14.1 6311 C2H6 (0.55) 0.013 None 14.1 74

*1Mol% of gas at the beginning of polymerization

TABLE 2. Physical properties of polytetrafluoroethylene formed in the presenceof chain transfer agents ethane and chloroform.

Particle Size

DSC MeltingPoint (�C)Entry

ViscosityPolymerMelt (Pa.S)

Specific SurfaceArea (m2/g)

AverageSize (mm)

1 7.1� 103 3.58 24.9 1252 3.8� 104 4.24 21.7 1483 1.3� 105 4.35 36.7 2964 7.9� 103 — 25.0 1485 2.0� 103 4.99 12.7 1058 2.4� 104 — 32.8 17610 NA 4.49 830 153511 NA 4.40 649 1535

238 Directly Polymerized Low Molecular Weight Granular Polytetrafluoroethylene

NOTES

1. Albano [1] prepared oligomers consisting of 40% perfluoromethylvinyletherand 60% tetrafluoroethylene using the surfactant CF2ClO(CF2CF(CF3)O)n(CF2O)mCF2COOH where n/m¼ 10 with a Mn � 600 daltons using1,6-diiodoperfluorohexane as the chain transfer agent. In a subsequent investi-gation by Comino [2] perfluoro oligomers were prepared using 1,10-perfluor-odecadiene, (I), as the crosslinking agent.

CF2

(I)

6

2. Perfluoroelastomers prepared by Bish [3] and Hung [4] containing roughly3 wt% of the termonomer perfluoro(8-cyano-5-methyl-3,6-dioxa-1-octene),(II), or N,N0-bis(2-propenyl)-4,40-(hexafluoro-isopropylidene)diphthalimide,(III), respectively, were thermally cured and used as seals in high temperatureautomotive applications.

F2C

FC

O

F2C

CFO

CF2

F2C

CF3

CN

(II)

N

CF3

N

O

O

O

O(III)

CF3

3. Navarrini [5] prepared tetrafluoroethylene/fluorovinyl ether co- and terpo-lymers, (IV), and (V), respectively, that behaved as both plastomers havinggood thermal and mechanical properties at high temperatures and elastomerswith improved properties at low temperatures. Tetrafluoroethylene and non-fluorinated vinyl ether co- and terpolymers were also prepared in theinvestigation.

F2C

CF2

F2C

CF

OF2C

OCF2

CF3

CF

F2C

CF2

F2C

CF

OF2C

OCF2

CF3

O

F2C

CF

OCF2

OF3C

F3C

(IV) (V)

a ba b c

Notes 239

References

1. M. Albano et al., US Patent 7,022,773 (April 4, 2006)2. C. Comino et al., US Patent Application 2005-0282969 (December 22, 2005)3. C.J. Bish et al., US Patent 6,638,999 (October 28, 2003)4. M.H. Hung et al., US Patent 6,794,455 (September 21, 2004)5. W. Navarrini, US Patent 6,963,013 (November 8, 2005)

240 Directly Polymerized Low Molecular Weight Granular Polytetrafluoroethylene

Title: Fluoroelastomers Containing CopolymerizedUnits of Vinyl Esters

Author: M.-H. Hung et al., US Patent Application 2007-0100101 (May 3, 2007)Assignee: Dupont Performance Elastomers, L.L.C. (Wilmington, Del)

SIGNIFICANCE

In order to fully develop physical properties such as tensile strength, elongation, andcompression set, perfluoro elastomersmust be cured. Perfluoro elastomers containingvinyl acetate units were prepared that, when saponified with sodium hydroxide,provide hydroxyl cure sites.

REACTION

F2CCF

OCF3

F2C

CF

OCF3

F2C

CF2

O

O

a b ci

i: Ammonium perfluorononante, disodium phosphate heptahydrate, ammoniumpersulfate, vinyl acetate, tetrafluoroethylene

EXPERIMENTAL

1. Preparation of Poly(Tetrafluorene-co-Perfluoro(Methylvinyl Ether)-co-Vinyl Acetate)

A 1-liter stainless reactor was charged with 450ml of water, ammonium perfluor-ononante (3.0 g), disodium phosphate heptahydrate (2.0 g), ammonium persulfate(0.4 g), and vinyl acetate (5.0 g). The reactor was sealed, treated with tetrafluoroethy-lene (45 g) and perfluoro(methylvinyl ether) (40 g), and heated to 70�C for 8 hours

241

with an agitation speed of 900 rpm. Thereafter the latex was coagulated withsaturated MgSO4 solution, and the precipitate was collected by filtration. The solidwas washed with warm water, dried, and 29.4 g of product were isolated as a whitepolymer. The product had a Tg of 0.2

�C and a composition consisting of TFE/PMVE/VAc, 60.0:32.0:8.0 mol%, respectively.

DERIVATIVES

TABLE 1. Summary of random co-vinyl acetate derivatives prepared by emulsionpolymerization using ammonium persulfate as the free radical initiator.

Entry Polymer*1 Composition Tg (�C)

2 PMVE-VAc 31.7 68.3 233 TFE-TFP-PVAc 63.0:30.4:5.0 —

TFE-TFP-VA 63.0:30.4:1.6 —4 TFE-P-VAc-TFP 63.3:31.8:3.2:1.7 6.95 TFE-PMVE-E-VAc 46.7:27.3:25.2:10.8 �11.1

Note: Vinyl acetate derivatives was saponified using sodium hydroxide.*1E, EthyleneP, PropyleneVA, Polyvinyl alcoholVAc, Vinyl acetatePMVE, Perfluoromethylvinyl etherTFE, TetrafluoroethyleneTFP, 3,3,3-Trifluoropropene

NOTES

1. In an earlier investigation by the author [1] a random polymer consisting ofTFE-VF2-PVME-VAc, 30.4:41.9:27.0:0.7 mol%, respectively, was preparedhaving a Tg of �28.1�C.

2. A copolymer consisting of TFE and 24mol% of perfluoro-3,5-dioxa-1-hep-tene, (I), with a Tg of �21.4�C was prepared by Navarrini [2] that had goodhigh-temperature properties and elastomers with improved low-temperatureproperties when using perfluoropropenylperoxide as the free radical initiator.Arrigoni [3] used perfluoro-3,5-dioxa-1-heptene with vinylidene fluoride and3,3,4,4,5,5,6,6,7,7,8,8-dodecylfluoro-1,10 decadiene, (II), to prepare perfluor-oelastomers with enhanced low-temperature properties.

F3C

F2C

O

F2C

O

FC

CF2(I)

F2C

6(II)

242 Fluoroelastomers Containing Copolymerized Units of Vinyl Esters

3. Perfluoro elastomers having improved low-temperature properties were pre-pared by Grootaert [4] and consisted of TFE-HFP-perfluorocyanopropylperfluorovinyl ether, (III), 65.0:34.2:0.8, respectively,

NC

F2C

CF2

F2C

O

FC

CF2

(III)

References

1. M.-H. Hung et al., US Patent Application 2007-0100099 (May 3, 2007)2. W. Navarrini, US Patent Application 2007-0100100 (May 3, 2007)3. S. Arrigoni et al., US Patent Application 2007-0093625 (April 26, 2007)4. W.M.A. Grootaert et al., US Patent 7,094,839 (April 22, 2006)

Notes 243

D. Low Surface Energy

Title: Amorphous Polyether Glycols Based on bis-Substituted Oxetane and Tetrahydrofuran Monomers

Author: A. A. Malik et al., US Patent 6,998,460 (February 14, 2006)Assignee: Aerojet-General Corporation (Sacramento, CA)

SIGNIFICANCE

Mono- and di-substituted oxetanemonomers containing 2,2,2-trifluoroethoxymethylsubstituents have been prepared. These agents were then used to prepare elastomers,thermoset plastics, and related articles where a very low surface energy was required.

REACTION

O

OO

F3CH2C CH2CF3

O

O OF3CH2C CH2CF3

ii

O

OO

Tosylate Tosylate

i

a

i: DMF, sodium hydride, trifluoroethanol

ii: Trifluoroethanol, boron trifluoride etherate, CH2Cl2

EXPERIMENTAL

1. Preparation of 3,3-bis-(2,2,2-Trifluoroethoxymethyl)Oxetane

Sodium hydride (0.383mol) was suspended in 200ml of DMF, treated with thedropwise addition of trifluoroethanol (0.383mol), and stirred for 30 minutes. Thismixture was further treated with a solution of 3,3-bis-(hydroxymethyl)oxetane di-p-toluenesulfonate (0.073mol) in 50ml of DMF. The mixture was then heated to 75�Cfor 64 hours, poured into water, and extracted twice with CH2Cl2. The combinedextracts were washed with brine, 2% aqueous HCl, water, dried using MgSO4, and

244

concentrated. The residue was purified by bulb-to-bulb distillation at 42�C to 48�C at0.1mm, and the product was isolated in 79% yield as a colorless oil.

2. Preparation of Poly[3,3-bis-(2,2,2-Trifluoroethoxymethyl)Oxetane]

A reaction vessel was charged with a solution of trifluoroethanol (0.058mol) andboron trifluoride etherate (0.81mol) dissolved in 900ml of CH2Cl2 and treated with asolution of the Step 1 product (4.1mol) dissolved in 485ml of CH2Cl2 over 2.5 hours.The mixture was stirred at ambient temperature for 16 hours and then quenched withwater. The organic layer was washed with brine and 2% aqueous HCl, concentrated,and the product was isolated in 91%yield having aDSCmp of 71.7�C, decompositiontemperature >210�C, and a Mn of 27,000 daltons with a PDI of 2.2.

DERIVATIVES

O

O

CH2CF3

O

O

CH2C6F13

O

O

CH2C10F21

NOTES

1. In an earlier investigation by the author [1] the Step 2 product was convertedinto urethanes by reacting with toluene diisocyanate, (I).

aO

O OF3CH2C CH2CF3

HN

ONH

O

OF3CH2C

F3CH2C

(I)

1H NMR d 3.87 (s 4H), 3.87 (q, J¼ 8.8Hz, 4H), 4.46 (s, 4H)13CNMR d 43.69, 68.62 (q, J¼ 35Hz), 73.15, 75.59, 123.87 (q, J¼ 275Hz);19F NMR d �74.6(s)FTIR (KBr, cm�1) 2960 2880, 1360 1080, 995, 840

Notes 245

2. Thermoplastic polyurethane resins were also prepared by the author [2] from4,40-methylene diphenylisocyanate with poly(3,3-bis-(2,2,3,3,4,4,4-hepta-fluorobutoxymethyl)-co-3-(2,2,3,3,4,4,4-heptafluorobutoxymethyl)-3-methy-loxetane) using dibutyltin dilaurate as catalyst and used in low surface energycoating applications

3. Yamamoto [3] prepared perfluoroalkoxymethacrylate, (II), by reacting poly(2-hydroxyethyl methacrylate), (III), with boron trifluoride-diethyl ether com-plex, which was then used to reduce water repellency on surfaces.

O

OO

C8F17

(II)

aO

C8F17

(III)

4. Kaplan [4] prepared fluorochemical release agents, (IV), for use as fluoroe-lastomer fuser component in electrostatographic reproducing equipment.

OSi

O

CF2

F2C

F2CCF2

CF2

F2C

CF3

Sia b

(IV)

References

1. A.A. Malik et al., US Patent 6,417,314 (June 9, 2002)2. A.A. Malik et al., US Patent Application 2006-0135729 (June 22, 2006)3. I. Yamamoto et al., US Patent 7,176,267 (February 13, 2007)4. S. Kaplan et al., US Patent 6,830,819 (December 14, 2004)

246 Amorphous Polyether Glycols Based on bis-Substituted Oxetane and Tetrahydrofuran Monomers

E. Silicon Fluids

Title: Cyclic Siloxane Compounds andMakingMethod

Author: K. Uehara et al., US Patent 7,189,868 (March 13, 2007)Assignee: Shin-Etsu Chemical Co., Ltd. (Tokyo, JP)

SIGNIFICANCE

Cyclic siloxane compounds containing an aliphatic unsaturation component andfluorinated alkylgroupswereprepared ina two-stepprocesswithoverall yields >53%.These polymerizable agents are characterized as having water and oil repellency inaddition to weather, solvent, and chemical resistance.

REACTION

Si

OSi

O

SiO

F3C CF3

F3C

Si

OSi

O

SiO

F3C CF3

F3C

Si

Cl

Cl Si

OSi O

Si

OSiO CF3

CF3

F3C

iiiNotes 1,2

i: Vinylmethyldichlorosilane, hexamethylphosphoric triamide

ii: Water, isooctane

EXPERIMENTAL

1. Preparation of 1-Chloro-1-Methyl-1-Vinylsiloxy-3,5,7-Tris(30,30,30-Trifluoropropyl)-7-Chloro-7-Methylsiloxy-3,5,7-Hexamethylcyclotrisiloxane

A flask was charged with 1,3,5-tris(30,30,30-trifluoropropyl)-1,3,5-hexamethylcyclo-trisiloxane (0.3mol) that hadbeenmelted byheating the solid to40�Cto50�Cand thentreated with vinylmethyldichlorosilane (0.3mol). The mixture was further treatedwith the dropwise addition of hexamethylphosphoric triamide (0.0015mol) and the

247

temperature kept at roughly 50�C for 2 hours. An analysis of the contents by gaschromatography indicated that the product yield was 91%.

2. Preparation of 1-Vinyl-3,5,7-Tris(30,30,30-Trifluoropropyl)-1,3,5,7-Tetramethylcyclotetra-Siloxane

A flask was charged with 162ml of water and slowly treated with the dropwiseaddition of the Step 1 product while the mixture stirred at�10�C. After the addition,themixturewas stirred 30minutes at ambient temperaturewith IRmonitoring until thereaction was complete. The mixture was extracted with 180 g of isooctane and thenwashedwithwater and concentrated under reduced pressure. The residuewas purifiedby distillation at 101�C to 105�Cunder reduced pressure, and 114 g of a liquid fractionproduct was isolated in 68% yield.

DERIVATIVES

SiO

Si OSiO

SiOR CF3

CF3F3C

NOTES

1. Additional polymerizable cyclic siloxane derivatives, (I), were prepared by theauthor [1] in a subsequent investigation.

SiO

Si OSiO

SiO CF3

CF3F3C

O

O

(I)

TABLE 1. Step 1 and 2 product yields of tetramethylcyclotetrasiloxane derivatives.

Entry R Step 1 Yield (%) Step 2 Yield (%)

2 CH2¼C(CH3)CO2CH2CH2CH2 84 643 CF2¼CH2CH2 85 98

1H-NMR (CDCl3) d 0.16 0.17, d, 9H; 0.20, s, 3H; 0.74 0.84, m, 6H; 1.96 2.16, m, 6H; 5.74 6.10, m, 3HMS¼ 554

248 Cyclic Siloxane Compounds and Making Method

2. Cyclic oligosiloxanes were prepared by Shinbo [2] through a disproportion-ation reaction using tri(i-propoxy)aluminum as the catalyst as illustratedbelow.

(H3C)3SiO OSi Si(CH3)3

H

O

SiO Si

O

SiOSiH

HH

H

45

i

i: Tri(i-propoxy)aluminum

3. Kiyomori [3] prepared a monofunctional polymerizable oligosiloxane cage,(II), which improved compatibility with solvents and was also polymerizablewith other monomers.

OSi O

O

(II)Oligosiloxane cage

4. Fluorosilane monomers, (III), prepared by Kinsho [4] were converted into thecorresponding terpolymer, (IV), by reacting with water and acetic acid thenused in resist compositions.

SiC2H5O OC2H5

OC2H5

O

O

O

CF2

CF3

OH

OSi

OO

O

CF2

CF3

OH

OSi

OO

t-C4H9

OSi

O O

(III)

20 30 503/23/23/2

(IV)

5. Through the polymerization of pentamethylcyclopentasiloxane, (V), Kennedy[5] prepared new compositions of matter consisting of poly(cyclosiloxane)network derivatives, (VI), as illustrated below.

Notes 249

O

HSiO

HSi

O

SiHOSi

H

O

SiO Si

O

SiOSi

O

SiO SiH

O

SiOSi

O

SiO Si

O

SiOSi

O

SiO Si

O

SiOSi

O

O

O

O

.....

.....

.....

.....

.....

.....

.....(V)

(VI)

.....

i

i: Platinum divinyl complex, toluene (Karstedt’s system)

6. Molding compositions were prepared by Fehn [6] by curingvinyldimethylsiloxy-terminated polydimethylsiloxane with rhodium(III)acetylacetonate.

References

1. K. Uehara et al., US Patent Application 2006-0264649 (November 23, 2006)2. K. Shinbo et al., US Patent Application 2006-0223963 (October 5, 2006)3. A. Kiyomori et al., US Patent Application 2006-0074213 (April 6, 2006)4. T. Kinsho et al., US Patent Application 2007-0009832 (January 11, 2007)5. J. Kennedy et al., US Patent 7,071,277 (July 4, 2006)6. A. Fehn et al., US Patent Application 2006-0058484 (March 16, 2006)

250 Cyclic Siloxane Compounds and Making Method

F. Surfactants

Title: Fluorinated Organosilicon Compoundsand Fluorochemical Surfactants

Author: H. Yamaguchi et al., US Patent Application 2006-0264596(November 23, 2006)

Assignee: Shin-Etsu Chemical Co., Ltd. (Tokyo, JP)

SIGNIFICANCE

Although fluorochemical surfactants containing perfluoroalkyl carbonyl fluoridescurrently exist in the art, it is difficult to obtain perfluoroalkyl derivatives containingsixormore carbons.Amethod to address this problemusingorganosilicon compoundsis described.

REACTION

O Si (CH2)3

CH3

CH3

OCH2CF

CF3

(OCF2CF)

CF3

F

Si O(H2C)2 Si

CH3

(CH2)3

CH3

(CH2CHO)3CH3

Si((H3C)2HSiO)3

CH2CH2 Si (OSiH(CH3)2)3i

Note 1 0.75

2.252

2

i: Di(perfluoroethylene oxide) allyl ether, toluene, platinum(0) 1,3-divinyl-1,1,3,3-tetramethyldisiloxane, tri(ethylene oxide) allyl ether

EXPERIMENTAL

Preparation of Polysiloxane

Aflaskwas chargedwith a siloxane (85.7 g) and toluene (105.6 g) containing platinum(0) 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (0.18 g; 0.9mg Pt) and heated

251

to 80�C. This mixture was treated with the dropwise addition of di(perfluoroethyleneoxide) allyl ether (125.4 g) and tri(ethylene oxide) allyl ether (147.1g) for over 2 hours.The mixture was then concentrated, and 320.0 g of product were isolated as a palebrown oil.

DERIVATIVES

Derivatives corresponding to the Step 1 product with varying polyether/fluorinecontent are provided in Table 1.

NOTES

1. Structures of the Step 1 co-reagents perfluoropolyether allyl ether, (I), and allylpolyether, (II), are provided below.

F (CFCF2OCF)2

CF3 CF3

CH2OCH2CH=CH2

CH3(CH2CH2O)3OCH2CH=CH2

(I)(II)

2. The surface treatment agent perfluoropolyether-modified silane, (III), wasprepared by the author [1] and had improved water/oil repellency, chemicalresistance, and antifouling properties.

Si

OC2H5

(CH2)3OC2H5O

OC2H5

CH2CF2 (OC2F4)21(OCF2)24OCF2CH2 O(CH2)3 Si

OC2H5

OC2H5

OC2H5

(III)

TABLE 1. Correlation of surface tension and HLB for Step 1 products containingvarying amounts of polyether and fluorine contents.

EntryFluorine

Content (%)Polyether

Content (%) HLBSurface Tension(dynes-cm�1)

1 21.6 26.6 5.3 24.52 24.7 37.3 7.5 23.33 11.5 49.4 9.9 25.14 5.9 56.0 11.2 26.35 27.1 22.2 4.4 23.5

1H-NMR d 0–0.1 (36H, Si–CH3), 0.1-0.2 (16H, Si–CH2–),1.3–1.5 (12H, –CH2–), 3.1 (27H, CH3O–), 3.2–3.5 (72H, –CH2O–)

252 Fluorinated Organosilicon Compounds and Fluorochemical Surfactants

3. Copolymers consisting of N-methyl perfluorooctyl sulfonamidoethylacrylateand 3-trimethyl-silylpropylmethacrylate, (IV), were prepared byDams [2] andused as oil and water repellents.

O ONHO

SO2C8F17

(H3CO)3Si

(IV)

a b

4. The polycondensate of Fomblin� and 3-(trimethoxysilyl)propyl amine pre-pared by Moore [3] was used to provide resistance to water, oil, and stainrepellency to a substrate or fabric. De Dominicis [4] used mono and difunc-tional perfluoropolyether phosphates and amidosilane derivatives as anti-staining agents for ceramic materials.

5. A three-component, (V), (VI), and (VII), curable fluoropolyether useful inrubber compositions and rubber fabrics was prepared by Osowa [5]. Thematerial exhibited solvent resistance, chemical resistance, weather resistance,water and oil repellency, and heat resistance.

Si N CFO

F2C

CFO

CF2

F2C

OCF

O

CF3

CF3

CF2

OCF

CF3

CF3

N

O

Si

(V)

C8F17

Si HSi Si

OSi

a b

3

)IIV()IV(

a + b = 130

References

1. H. Yamaguchi et al., US Patent 7,196,212 (March 27, 2007)2. R.J. Dams, US Patent 7,166,329 (January 23, 2007)3. G.G.I. Moore et al., US Patent 7,097,910 (August 29, 2006)4. M. De Dominicis et al., US Patent 7,045,016 (May 16, 2006)5. Y. Osawa et al., US Patent 6,979,710 (December 27, 2005)

Notes 253

XI. GELS

A. Gelling Agent

Title: Ferrocene-Containing, Organic GellingCompound, and Gel and Cast Film Using the Same

Author: N. Kimizuka et al., US Patent 7,041,842 (May 9, 2006)Assignee: Honda Giken Kogyo Kabushiki Kaisha (Tokyo, JP)

SIGNIFICANCE

Ferrocene compounds and polymers have been used as micelle-forming agents inelectrochemical processes for producing organic films usable in electronic materialssuch as color filters. To increase the concentration of ferrocene in these processes, anferrocene oligomer having gelling properties has been prepared.

REACTION

O NH2

O NH

O HN O

Ot-C4H9

O

HNO

O NH

ONH3 Cl

O

HNO

O NH

ONH

O

HNO

O FeGel

i iiiii

iv

11

11

11

11

11

1111

i: Butyloxycarbonyl-l-glutamic acid, triethylamine, THF, diethyl phospho-rocyanidate

ii: Trifluoroacetic acid


255

iii: CCl3H, triethylamine, ferrocene carboxylic acid, 2-oxo-3-oxazolidinyl)-phos-phinic chloride

iv: Acetonitrile, N-methyl-N0-methoxymethyl-imidazolium bromide

EXPERIMENTAL

1. Preparation of BOC Intermediate

A reaction vessel was charged with 3-lauryloxypropyl-1-amine (17.8 mmol), buty-loxycarbonyl-l-glutamic acid (8.1mmol), and triethylamine (17.8mmol) dissolved in150ml of THF, and then ice-cooled. This mixture was slowly treated with diethylphosphorocyanidate (17.8mmol) and then stirred under ice cooling for 30minutes andat ambient temperature for 3 days. It was concentrated and a pale-yellow oily residueisolated. The residue was dissolved in CCl3H, washed twice apiece with 5% aqueousNaHCO3 and water, and dried using Na2SO4. The solution was filtered, concentratedas a pale-yellow solid after recrystallization in acetone, and the productwas isolated asa colorless powder in 60.2% yield.

2. Preparation of Ammonium Chloride Intermediate

The Step 1 product (4.9 mmol) was dissolved in 100ml of CH2Cl2, treated with 20%trifluoroacetic acid, and stirred overnight at ambient temperature. The mixture wasconcentrated, and an oily residue was isolated. The residue was dissolved in 50ml ofacetone and then treated with 1ml concentrated hydrochloric acid with cooling until aprecipitate was formed. The solid was re-crystallized twice from EtOAc, and theproduct was isolated as a colorless powder in 40.9% yield.

3. Preparation of Ferrocene-Containing Gelling Compound

The Step 2 product (1.58 mmol) and triethylamine (1.8 mmol) were dissolved inCCl3H and treated with water, and then the mixture shaken. The CCl3H phase wasisolated, dried with Na2SO4 and concentrated. The residue was dissolved in CH2Cl2and treatedwith triethylamine (1.8mmol), ferrocene carboxylic acid (1.73mmol), andN,N-bis(2-oxo-3-oxazolidinyl)-phosphinic chloride (1.73 mmol). This mixture wasstirred under ice-cooling for 30 minutes, stirred at ambient temperature 3 days, andthen concentrated. The residue was dissolved in CCl3H, washed with 5% aqueousNaHCO3 and dilute with hydrochloric acid. The mixture was filtered and concentrat-ed, and the residuewas purified by chromatography with silica gel using CCl3H. Fourcomponentswere identified. The first twocomponentswere discarded. The remainingtwo components were separated by silica gel column chromatography using CCl3H/CH3OH, 10/1, respectively, to isolate the gel-forming third component. This compo-nent was then re-crystallized from hexane, and the product was isolated as a pale-yellow solid in 31% yield, MP ¼ 82.1 �C to 83.5 �C.

256 Ferrocene-Containing, Organic Gelling Compound, and Gel and Cast Film Using the Same

4. Preparation of Gel

A 20mM solution of the Step 3 product in acetonitrile and N-methyl-N0-methoxy-methyl-imidazolium bromide was prepared. The mixture was heated and left to standat ambient temperature for 30 minutes. An organogel and ionogel formed that wereobserved using a dark-field optical microscope. The organogel indicated the presenceof microcrystals suggesting that they have an associated fibrous structure or thatcrystals were formed by the slide cover glass; themicron-level fibrous structures werenot observed in the ionogel.

DERIVATIVES


NOTES

1. A supramolecular hydrogel underwent a reversible gel-sol transformation thatwas formed by adding 9,10-dimethoxy-2-anthracenesulfonic acid to an aque-ous dispersion of a cationic amphiphile, (I), as was previously prepared by theauthor [1]. The gel had a network with a bilayer-membrane and a nanofiberstructure.

NH

OHN

OHN

O

NOH

11

11 (I)

2. Sugar-derived gelatinizers, (II), having gel-forming capability in both organicsolvents and water were prepared by Jung [2], and agglomerates were system-atically designed by altering the hydrocarbon tail.

OHO

HO OH

OH

O NH

(II)

3. Eagland [3] demonstrated that in the presence of acid, polyvinylalcoholand poly(4-(4-formylphenylethenyl)-1-methyl)-pyridinium methosulphonate,

Notes 257

(III), formed a hydrogel that could be used to encapsulate water-insolublematerials. Soybean-based materials prerpared by Liu [4] were also effective ashydrogels and used as drug delivery agents.

O OOH OH

N

a

b

(III)

References

1. N. Kimizuka et al., US Patent 6,576,679 (June 10, 2003)2. J.H. Jung et al., US Patent 7,196,178 (March 27, 2007)3. D. Eagland et al., US Patent 7,202,300 (April 10, 2007)4. Z. Liu et al., US Patent Application 2007-0077298 (April 5, 2007)

258 Ferrocene-Containing, Organic Gelling Compound, and Gel and Cast Film Using the Same

B. Hydrogels

Title: Random Block Copolymers

Author: N.B. Graham et al., US Patent 7,241,845 (July 10, 2007)Assignee: Ocutec Limited (Glasgow, GB)

SIGNIFICANCE

A linear urea-urethane block copolymer containing polyethylene oxide and polypro-pylene oxide was prepared by reacting polyethylene glycol and polypropylene glycolwithdicyclohexylmethane4,40-diisocyanateand4,40-diaminodiphenylmethane.Thesematerials are particularly advantageousbecauseof their highmechanical strength in theswollen state.Mechanical property testing indicated that the energyneeded tobreak thecopolymer hydrogel was at least 40% of that of the copolymer in the dry state.

REACTION

O O O OO O NH

O

NH

NH

ONH

O

NH

O

NH

O

O

75 5 n

HO O OH75

i

i: Polyethylene glycol, polypropylene glycol, 4,40-diaminodiphenylmethane, dicy-clohexylmethane 4,40-di-isocyanate, ferric chloride

EXPERIMENTAL

Random Urea-Urethane Copolymer of Polyether Glycol,Polypropylene Glycol, Dicyclohexylmethane 4,40-Diisocyanate,and 4,40-Diaminodiphenylmethane

A reactor was charged with polyethylene glycol having a Mn 5830 daltons andpolypropylene glycol with a Mn 425 daltons and then heated until melted and

259

thoroughly mixed. The mixture was next heated to 95�C to 100�C and treated withanhydrous ferric chloride and stirred until the catalyst dissolved. This mixture wastreatedwith4,40-diaminodiphenylmethane (0.726 g)andagain thoroughlymixeduntilthe solution was homogeneouse; the solution was then posttreated with 12.67mldicyclohexylmethane 4,40-diisocyanate and heated for 2minutes at 90�C.Themixturewas poured into preheated polypropylene test tube molds and placed into an oven at95�C for 20 hours, and the product was isolated.

DERIVATIVES

TABLE 1. Reagent variations in preparing poly(urea-urethane) derivatives usingpolyethylene glycol and polypropylene glycol.

Entry PEG-5380 (wt%) PPG-425 (mol) Diamine (mol) Diisocyanate (mol)

1 10.01 72.0 3.554 80.3204 27.19 21.0 1.310 24.4767 48.34 8.0 0.736 10.2239 63.55 4.0 0.560 5.838

TABLE 2. Equilibrium swelling for selected poly(urea-urethane) derivativesin water at 37�C.

EntryPEG-5380(wt%)

EquilibriumWater Uptake

(pph)Equilibrium Water

Content (%)EquilibriumPPG/Water

1 10.01 21.0 17.36 25.634 27.19 82.0 45.05 59.997 48.34 183.0 64.66 81.749 63.55 298.0 74.87 90.84

TABLE 3. Mechanical properties for water-swollen poly(urea-urethane) derivativesat 37�C.

EntryPEG-5380(wt%)

WaterContent (%)

Young’sModulus(MNm�2)

Energy toBreak Dry

Film (MNm�2)

Energy to BreakSwollen Film(MNm�2)

1 10.01 17.36 0.764 48.719 8.5294 27.19 45.05 0.830 57.626 67.3137 48.34 64.66 1.500 172.934 76.2039 63.55 74.87 0.507 299.697 52.047

260 Random Block Copolymers

NOTES

1. Degradable difunctional poly(ethylene glycol) acrylates, (I), were prepared byHarris [1] and then photolytically converted into hydrogels and used in drugdelivery systems.

CH2=CHCO2-PEO2-O-CH2CO2CH(CH3)CH2CONH-PEO2CCH=CH2

(I)

2. Muller [2] prepared hydrogels that were used in contact lenses with difunc-tional siliconecontaining crosslinkers, (II), with amphiphilic block prepoly-mers. Tetrafunctional crosslinkers, (III), prepared by Lewis [3] were used asbiocompatible coating applications.

NO

SiO

Si N

NH

OOCN NH

O NCO

HN

O

SiO

SiHN

O3 354

(II) (III)

3 3

b b

a

3. Swellable hydrogels, (IV), used for sensor coatings were prepared by VanAntwerp [4] and were capable of water uptake of at least 200% by weight.

NH

HN

HN

O NHO

NH

O

NH

O O

O

NH

Oa

b c

(IV)

References

1. J.M. Harris et al., US Patent 7,214,388 (May 8, 2007), US Patent 7,166,304 (January 23, 2007), and USPatent 7,018,624 (March 28, 2006)

2. B. Muller et al., US Patent 7,091,283 (August 16, 2006)3. A.L. Lecvis et al., US Patent 7,064,174 (June 20, 2006)4. W.P. Van Antwerp et al., US Patent 6,784,274 (August 31, 2004)

Notes 261

Title: (Meth)Acrylic Esters of PolyalkoxylatedTrimethylolpropane

Author: A. Popp et al., US Patent 7,199,211 (April 3, 2007)Assignee: BASF Aktiengesellschaft (Ludwigshafen, DE)

SIGNIFICANCE

Oligomeric agents were prepared by condensing trimethylolpropane with ethyleneand/or propylene oxides and capping with acrylic acid. These materials weresubsequently crosslinked using 2,20-azobisamidinopropane dihydrochloride, whichformed superabsorbent swellable hydrogel addition polymers and were useful ascomponents in diapers or in feminine hygiene products.

REACTION

HO OH

OH

O O

O

OOO

HO

H

OO

H

O O

O

OOOO

OO

O O

O

5

30

5

30

5305

30

5

305 30

Notes 1,2i ii

Superabsorbant hydrogel

i: Potassium hydroxide, ethylene oxide, propylene oxideii: Acrylic acid, sulfuric acid, methylcyclohexane, hydroquinonemonomethyl ether,

triphenyl phosphate, hypophosphorous acid

262

EXPERIMENTAL

1. Preparation of Trimethylolpropane Ethoxylated/propoxylated(TMP-30EO-5PO)

An autoclave was charged with trimethylolpropane (77 g) and 45% aqueous KOH(0.5 g) and then azeotroped at 80�C and 20 mbar. The mixture was next treated withethylene oxide (759 g) at, 45�C to 155�C and reacted at elevated pressure until nofurther change in pressure was observed. The mixture was stirred an additional30 minutes at 150�C and then treated with propylene oxide (167 g) at 120�C to130�C. The reactor was purged, the contents cooled to 60�C, and the catalyst removedby filtration. The product was isolated and consisted of 30-tuply ethoxylated and 5-tuply propoxylated trimethylolpropane.

2. Preparation of Trimethylolpropane Ethoxylated/propoxylated Triacrylate

The Step 1 product (1427 parts) was converted into the corresponding acrylateester by treating with acrylic acid (216 parts), sulfuric acid (5 parts) in methyl-cyclohexane (345 parts), hydroquinone monomethyl ether (3 parts), triphenylphosphite (1 part), and hypophosphorous acid (1 part). The reaction continueduntil 44 parts of water were removed before beginning the vacuum distillation.The residue was purified by filtering through a K300 filter, and the acid numberwas determined. The product viscosity was adjusted to 330 mPas by the additionof 96 parts of acrylic acid, and a colorless product was isolated.

DERIVATIVES

NOTES

1. Step 2 products were subsequently converted into crosslinked superabsorbenthydrogels and used as components in diapers or in feminine hygiene products.The preparation of these superabsorbant hydrogels is described below.

TABLE 1. Properties of hydrogels prepared by free radically polymerizing thecorresponding triacrylate with 2,20-azobisamidinopropane dihydrochloride.

Entry Hydrogel Saponification Index CRC-1*1 (g/g)

1b TMP-15E0 11.6 29.71d TMP-30EO-5PO 4.7 30.11f TMP-5PO-30EO 7.0 29.51g TMP-10PO-50EO 4.1 30.1

*1Centrifuge retention capacity test

Notes 263

Preparation of a Superabsorbent Hydrogel Using Internal Crosslinkers

A reactor containing acrylic acid (305 g), 37.3wt%aqueous sodium acrylate (3204 g),and water (1465 g) was treated with ethoxylated (15 EO) trimethylolpropane tria-crylate (12.2 g), 2,20-azobisamidinopropane dihydrochloride (0.61 g), and sodiumpersulfate (3.05 g). The mixture was purged for 30 minutes and further treated withhydrogen peroxide (0.244 g) dissolved in water (5 g) and ascorbic acid (0.244 g)also dissolved in water (5g). The mixture was then heated in a thermally insulatedtub for about 30 minutes; the temperature at the start of the reaction was 113

�C.

The reaction started after a few minutes and proceeded under adiabatic conditionsuntil the product was isolated and comminuted through a meat grinder equippedwith a 6mm breaker plate. The residue was dried at 80�C under reduced pressureand the produce, was isolated having a sieve fraction of 300 to 600 mm.

2. Additional superabsorbent hydrogel derivatives containing EO/PO ratios otherthan those of the current invention were prepared by the author [1] in asubsequent invention.

3. Smith [2] prepared a series of superabsorbent polymers with high permeabilityconsisting of the reaction product of NaOH, water, acrylic acid, methoxypo-lyethyleneglycol (750), monomethacrylate of trimethylolpropanetriacrylate,TMP-3EO, and hydroxymonoallyl ether-10EO. These materials were useful inthe transportation of liquids in the swollen state.

4. Funk [3] prepared hydrogels with different pH values by reacting 90 parts ofhydrophilic polymeric agents with glacial acrylic acid, water, and penta-erythritol triallyl with 10 parts of acrylic acid, sorbitan monococoate, andallyl methacrylate.

5. Water absorbing polymers consisting of acrylic acid, polyethylene glycolmonoallyl ether acrylate, and polyethylene glycol diacrylate were preparedby Brehm [4] containing interstitial agents such as zeolites high in silicon.

References

1. A. Popp et al., US Patent 7,259,212 (August 21, 2007)2. S.J. Smith et al., US Patent 7,173,086 (February 6, 2007) and US Patent 7,169,843 (January 30, 2007)3. R. Funk et al., US Patent 7,144,957 (December 5, 2006)4. H.G. Brehm et al., US Patent 7,101,946 (September 5, 2006)

264 (Meth)Acrylic Esters of Polyalkoxylated Trimethylolpropane

Title: Prepolymers for Improved Surface Modificationof Contact Lenses

Author: Y.-C. Lai, et al., US Patent 7,176,268 (February 13, 2007)Assignee: Bausch & Lomb, Inc. (Rochester, NY)

SIGNIFICANCE

Fumarate- and fumaramide-containing hydrogels have been prepared with silicone asa co-component that are highly oxygen permeable. These agents are biocompatibleand useful as biomedical devices, particularly as contact lenses.

REACTION

SiO

SiO

SiH

OOHO OH

SiO

SiO

SiOO

I

O O

O

O

HO

O

O

OH

SiO

SiO

SiOO

O O

O

O

O

O

O

OH2N

22

22

22

SiO

SiO

SiOO

O O

O

O

O

O

O

O22a dc

b

ON O N

Not Isolated

i

ii

NH2

3

HN NH

33OO

Note 1

e

3

i: Fumaryl chloride, water

265

ii: Hexanol, N,N-dimethylacrlyamide, Daracure�, tris(hydroxymethyl)aminome-thane, water

EXPERIMENTAL

1. Preparation of Polydimethylsiloxane with Fumaric Acid Termini

A dried 500-ml round bottom flask was charged with bis(a,o-hydroxybutyl poly-dimethylsiloxane) (Mn�1624daltons; 0.0185mol) and fumaryl chloride (0.0418mol)and thenheated to 60�Cfor 2hours and concentrated.The residuewas treatedwith 3mgofwater and 30ml of THF and refluxed until no IR evidence of acid chloride absorptionwas present. Themixturewas next concentrated, the residuedissolved in 200ml diethylether, extracted three times with 50ml, dried with MgSO4, re-concentrated, and theproduct was isolated.

2. Preparation of Hydrogel Films

A mixture consisting of the Step 1 product (32 parts), N,N-dimethylacrylamide (32parts), tris(hydroxymethyl)aminomethane (36parts), hexanol (27parts), andDarocur�

(0.3parts)werecastbetweentwosilane-treatedglassplatesandcuredfor1hourat70�C.The cured films were then released, extracted in isopropanol, and boiled for 4 hours inwater. Hydrogel films were stored in borate buffered saline solution until needed.

DERIVATIVES

TABLE 1. Selected Step 1 hydrogel pre-polymers converted into hydrogels by curingwith tris(hydroxymethyl) aminomethane, hexanol, and DarocurR for 1 hour at 70�C.

Entry Monomer(s)N,N-Dimethylacrylamide:Monomer Ratio (mol)

8 Glycidyl methacrylate 6:19 Octafluoropentyl

methacrylate/glycidylmethacrylate

5.7:1.07:1

10 Octafluoropentylmethacrylate/glycidylmethacrylate

2.85:1.07:1

13 Methacrylic acid 3.60:1

Source: Very limited characterization data supplied by author.

Mn¼ 2001 daltonsMw¼ 3141 daltonsPd¼ 1.57Water content¼ 39%,Modulus¼ 36 g/mm2

Tear strength¼ 13 g/mmOxygen permeability¼ 93 Dk unit

266 Prepolymers for Improved Surface Modification of Contact Lenses

NOTES

1. Additional Step 2 polymer analogues containing hydrophilic arylsiloxy-con-taining macro-monomers, (I), were prepared by Salamone [1].

O OSi

O Si O

OSi

O

O

N

O

3

a

b

a

(I)2. Schmitt [2] prepared high-transparency lens materials by free radical polymer-

ization of methacrylate monomers containing carbamate, (II), and ether, (III),segments. Free radical polymerization of 3-thietanyl derivatives, (IV)–(VI),using UV radiation was prepared byKobayashi [3] and used in the manufactureof high-transparency lens.

OO

HN

O

O

HN O

OO

O

OX

O

XO

O

aa

(II)

(III)

a = 2 – 20X = O, S

S S

S S S S

S S

RS

S

n n = 1,2

(IV)(V)

(VI)

R = CH2NCO CH=CH2

S

Notes 267

3. Polyisocyanates bicyclo[2.2.1]heptane-2,5(6)-diisocyanate, (VII), and tricyclo[5.2.1.0.2,6]-decane-3(4),8(9)-diisocyanate were used by Haseyama [4] toprepare high-transparency polythiourethane, (VIII), lens materials.

HN NH CO S SS

SS CO

OCN NCOn = 1,2

n n

)IIIV()IIV(

4. Thioamino, (IX), and siloxy, (X), crosslinkable prepolymers were prepared byMuller [5] and used in the manufacture of contact lenses.

NH

HN

HN

OO

SHHSNH

O

SiO

Si NH

O

(IX) (X)

n

References

1. J.C. Salamone et al., US Patent Application 2006-0287455 (December 21, 2006), US Patent Application2006-0286147 (December 21, 2006), and US Patent Application 2006-0270749 (November 30, 2006)

2. B. Schmitt et al., US Patent 7,144,954 (December 5, 2006)3. S. Kobayashi et al., US Patent Application 2005-0215757 (September 29, 2005) and US Patent

7,132,501 (November 7, 2006)4. K. Haseyama et al., US Patent Application 2005-0049430 (March 3, 2005)5. B. Muller et al., US Patent 7,091,283 (August 15, 2006)

268 Prepolymers for Improved Surface Modification of Contact Lenses

Title: Preparation of High Molecular WeightPolysuccinimides

Author: C. S. Sikes, US Patent 7,053,170 (May 30, 2006)Assignee: Aquero Company (Eugene, OR)

SIGNIFICANCE

L-Aspartic acid solubilized with hydrochloric was polymerized with 30% polypho-sphoric acid at 180�C to prepare linear polysuccinimides having a Mw of 180,000daltons. When the polysuccinimide was hydrolyzed with dilute sodium hydroxide ana,b-polysodium aspartate hydrogel was generated.

REACTION

H2N

O

OH

HO

O

N

O

O

i HN

HN

O

O

O

OOO Na

Naii

Notes 1,2aa

i: Hydrochloric acid, polyphosphoric acidii: Sodium hydroxide, water

EXPERIMENTAL

1. Preparation of Polysuccinimide

Eleven50-mlbeakerswas chargedwith L-aspartic acid (0.01mol) and solubilizedwith13.3ml of 1M hydrochloric acid (0.013mol) at ambient temperature. The first threebeakerswere treatedwith 0.066ml of polyphosphoric acid (specific gravity�2.0) andthen warmed to 80�C acid. The second three beakers was treated with 0.266mlpolyphosphoric acid; the last four beakerswere treatedwith 0.399 gof polyphosphoricacid. Each solution was dried at 120�C, resulting in clear glassy pucks of intimatemixtures of aspartic acid and the polyphosphoric acid catalyst. The dried materials

269

were then thermally polymerized at 180�C, and aliquots were intermittently removedfrom between 1 to 7 hours. Aliquots were washed with water and centrifuged, theprocess being repeated 3 times, and the products isolated as light powders. Analyticalresults are provided in Table 1.

2. Preparation of a,b-Poly Aspartate Sodium

The Step 1 product was ring-opened bymild alkaline hydrolysis using 1 equivalent of0.1MofNaOHper equivalent of succinimide. The alkaline conditionswere held at pH10 by auto-titration at 80�C in water bath. Under these mild conditions polysucci-nimides were converted to polyaspartates within 1 hour.

REACTION SCOPING

NOTES

1. The procedure for preparing sodiumpolyaspartate by the basic hydrolysis of theStep 1 product using 0.1M, NaOH in this investigation was too vague to beexperimentally useful. Instead the procedure was obtained from a subsequentpublication by the author [1].

2. In a subsequent investigation by the author [1] polysuccinimdes were preparedusing phosphoric, metaphosphoric, and diphosphoric acids.

TABLE 1. Summary of weight average molecular weights from the preparation ofpolysuccinimides using L-aspartic acid using polyphosphoric acid.

L-Aspartic Acid CatalystReaction

Time@ 180�C (h)Mw

(dalton)

None 2 7,400Hydrochloric acid 4 12,000Polyphosphoric acid 7 178,000Hydrochloric acidþ

10% polyphosphoric acid7 12,000

Hydrochloric acidþ20% polyphosphoric acid

7 38,000


3 136,000


4 172,000


6 178,000

270 Preparation of High Molecular Weight Polysuccinimides

3. Poly(succinimide-co-sodium aspartate), (I), was previously prepared [2] by theauthor and used in biodegradable and personal product applications.

aN

HN

OO

ONa

O

O

(I)

b

4. Poly(sodium aspartate-co-asparagine-co-succinimide), (II), was prepared bythe author [3] by hydrolysis of polysuccinimide with ammonium and sodiumhydroxides. A method for preparing branched polysuccinimide derivatives ofthe current investigation was also provided.

a b

HN

HN

N

OOO OH2N

O

O

ONa

(II)

c

5. Swift [4,5] prepared poly(succinimide-co-sodium aspartate) by copolymeriz-ing aspartic acid with monosodium aspartate and polysuccinimide usingL-aspartic acid in supercritical CO2.

6. By initiating the polymerization of aspartic acid with a malimide end cappinginitiator, (III), Swift [6] prepared a functionalized polysuccinimide derivative.

N

O

O

O

O

O

(III)

References

1. C.S. Sikes, US Patent Application 2006-0205918 (September 14, 2006)2. C.S. Sikes et al., US Patent 6,495,658 (December 7, 2002)3. C.S. Sikes, US Patent 7,091,305 (August 15, 2007)4. G. Swift et al., US Patent 6,903,181 (June 7, 2005)5. G. Swift et al., US Patent 6,919,421 (July 19, 2005) and US Patent 6,887,971 (May 3, 2005)6. G. Swift et al., US Patent Application 2006-0211843 (September 21, 2006)

Notes 271

Title: Degradable Crosslinkers and DegradableCrosslinked Hydrogels Comprising Them

Author: H. Zhang et al., US Patent 7,135,593 (November 14, 2006)Assignee: Biosphere Medical, Inc. (Rockland, MA)

SIGNIFICANCE

Base-labile crosslinkering agents consisting of N,N0-(dimethacryloyloxy)alkylamidederivatives were prepared and used in synthesizing degradable crosslinked polymersand hydrogels. The degradation rates of these hydrogelswas controlled by co-reactingthe crosslinking agent with selected acrylamides.

REACTION

Crosslinker Component

H3CO

O

OCH3

O

HN

O

HN

O

HO OH

HN

O

HN

O

O O

O O

i ii

Intermediate

272

Hydrogel Crosslinking

Intermediate

HN

O

HN O

O

O

O

OO O

OH

O O

OH

O

O

OH

a

b c

iii

i: Dimethyl glutarate, hydroxylamine, methanol, ethanolii: Pyridine, DMF, methacryloyl chloride, DMF, chloroform, wateriii: DMF, glycerol, ammonium persulfate, N,N,N,N-tetramethylethylenediamine,

ethanol

EXPERIMENTAL

1. Preparation of Glutaroyl Dihydroxamic Acid

Dimethyl glutarate (0.6mol) was added to 400ml of methanol and treated with anaqueous solution of hydroxylamine (50 wt% in water; 1.34mol). The reaction stirredfor 85 hours at ambient temperature, and the product was precipitated by introducing400ml of ethanol. The precipitate was isolated, and washed three times with ethanol,and vacuum-dried at 40�C for 48 hours; the product was isolated in 66% yield as awhite powder.

2. Preparation of N,N0-Dimethacryloyloxy)glutarylamide

A reactor was charged with the Step 1 product (0.20mol), 50 of ml pyridine, and260mlofDMFand then treated dropwisewithmethacryloyl chloride (0.4mol) dilutedwith 40ml of DMF and stirred 3 hours at ambient temperature. The mixture was nexttreatedwith300mlofCCl3Handpoured into1000mlofvigorously stirringwater.Theorganic phase was washed three times with water, dried overnight using MgSO4, andconcentrated. The residuewas re-crystallized in diethyl ether/hexane, and the productwas isolated in 34% yield.

Experimental 273

3. Preparation of 2-Hydroxyethyl Acrylate Crosslinked Hydrogel

Ina100-mlround-bottomflasktheStep2productwasdissolvedinDMFandtreatedwith2-hydroxyethyl acrylate (2.0 g) followed by glycerol and water (20 g), 1:1. The reactorwas placed in an oil bath kept at 55�C and the polymerization was initiated usingammonium persulfate (50mg) and accelerated with 0.1ml N,N,N,N-tetramethylethy-lenediamine. The hydrogel formed immediately and was immersed in ethanol over-night, washed with ethanol, vacuum-dried for 20 hours, and the product was isolated.

DERIVATIVES

Asummaryofbase-labilecrosslinkingagents isprovidedinTable1.Hydrolyticstabilityof homopolymer and copolymer hydrogels are provided inTables 2 and3, respectively.

NH

O O

NH

OO

O On

TABLE 1. Summary of N,N0-(dimethacryloyloxy)alkylamidederivatives effective as hydrogel crosslinking agents.

Name n

N,N0-Dimethacryloyloxy)malonamide 1N,N0-Dimethacryloyloxy)succinamide 2N,N0-Dimethacryloyloxy)glutarylamide 3N,N0-Dimethacryloyloxy)adipamide 4N,N0-Dimethacryloyloxy)suberoylamide 6

Source: Limited 1H-NMR data supplied by author.

TABLE 2. Degradation times for crosslinkedhomopolymer hydrogels hydrolyzed ina buffer solution at pH 7.4 at 37�C.

Monomer*1 Crosslinker Degration Time

TS N,N0-Dimethacryloyloxy)glutarylamide 22 daysHEA N,N0-Dimethacryloyloxy)glutarylamide 26 daysPEG-macromer N,N0-Dimethacryloyloxy)adipamide 31 daysAA N,N0-Dimethacryloyloxy)glutarylamide 8 hoursNaAA N,N0-Dimethacryloyloxy)adipamide 6 hoursDMA N,N0-Dimethacryloyloxy)adipamide 32 hoursAAm N,N0-Dimethacryloyloxy)adipamide 7 hours

*1TS¼N-[Tris(hydroxymethyl)methyl]acrylamideHEA¼N-(Hydroxymethyl)methacrylamidePEG-macromer¼ Poly(ethylene glycol)-methacrylate, MW � 526 daltonsAA¼Acrylic acidNaAA¼ Sodium acrylateDMA¼N,N-DimethylacrylamideAAm¼Acrylamide

274 Degradable Crosslinkers and Degradable Crosslinked Hydrogels Comprising Them

NOTES

1. Goupil [1] prepared biomedical articles consisting of biodegradable poly(vinylalcohol) hydrogels crosslinked with N-methacrylamidoacetaldehyde dimethylacetal, (I), N-acrylamido-acetaldehyde dimethyl acetal, (II), and 1-(2,2-di-methoxyethyl)-3,4-dimethylpyrrole-2,5-dione, (III).

HN

O

H3CO OCH3

HN

O

H3CO OCH3

N

O

O

OCH3

H3CO

(I) (II) (III)

2. Hubbell [2] prepared biocompatible hydrogels consisting of poly(acrylic acid-b-ethylene oxide) crosslinked with hydrolytically susceptible carbonates, (IV),urethanes, (V), ureas, (VI), ester amides, (VII), and diamides, (VIII).

OX

O

YO

O

O

Y X CrosslinkerIV O O V N O VI N N

TABLE 3. Degradation times for copolymer hydrogels crosslinked with N,N0-dimethacryloyloxy)glutarylamide hydrolyzed in a buffer solution at pH 7.4 at 37�C.

Monomer 1*1 Comonomer*2 Degration Time

HEA, 90% DMA 13 daysHEA 80% DMA 9.5 daysHEA 90% AA 4 daysTS, 90% DMA 7 daysTS, 80% DMA 4 daysTS, 90% AA 23 hoursTS, 80% AA 15 hours

*1HEA¼N-(Hydroxymethyl)methacrylamideTS¼N-[Tris(hydroxymethyl)methyl]acrylamide*2AA¼Acrylic acidDMA¼N,N-Dimethylacrylamide

Notes 275

XY

O

O

Y X CrosslinkerVII N O VIII N N

3. Frechet [3] prepared bioactive microgels by free radical polymerizationof acrylamide with acid-labile crosslinkers such as bisacrylamide 4-methox-ybenzaldehyde acetal, (IX), and bistrifluoroacetamide 4-(3-azidopropylether)benzaldehyde acetal, (X).

HN

O OO

HN

OCH3

O

F3CHN

O OO

HN

O

CF3

O(IX) (X)

N3

4. Hydrolytically unstable polyethylene was prepared by Wilson [4] by copo-lymerizing ethylenewith acid-labile crosslinkers 1-allyloxy-penta-1,4-diene,(XI), tetraallyloxysilane, (XII), or 3,9-divinyl-2,4,8,10-tetraoxaspiro [5,5]undecane, (XIII).

O SiOO

O

O

OO

O O

(XI) (XII) (XIII)

5. Loomis [5] prepared poly(lactide-co-(ethylene oxide-co-propylene oxide-co-lactide) bioresorbable compositions for use in implantable prosthesis.

276 Degradable Crosslinkers and Degradable Crosslinked Hydrogels Comprising Them

References

1. D.W. Goupil et al., US Patent 7,070,809 (July 4, 2006)2. J.A. Hubbell et al., US Patent 6,943,211 (September 13, 2005)3. J.M.J. Frechet et al., US Patent 7,056,901211 (June 6, 2006)4. R.B. Wilson Jr. et al., US Patent 7,037,992 (May 2, 2006)5. G.L. Loomis et al., US Patent Application 2007-0015844 (January 18, 2007) and US Patent 7,109,255

(September 19, 2006)

Notes 277

C. Sol-gel

Title: Thermosensitive Poly(Organophosphazenes),Preparation Method Thereof and InjectableThermosensitive Polyphosphazene HydrogelsUsing the Same

Author: S.-C. Song et al., US Patent 7,259,225 (August 21, 2007)Assignee: Korea Institute of Science and Technology (Seoul, KR)

SIGNIFICANCE

Thermosensitive polyphosphazene polymers have been prepared by reacting poly-dichlorophosphazene with methoxypolyethylene glycol and isoleucineethyl ester.These materials are suitable for use as injectable thermosensitive biodegradable drugdelivering system that have sol-gel behavior near human body temperature.

REACTION

NP

Cl

Cl

N P N P

HN

HN

HN

HNO

O

CH(CH3)CHC2H5

O

CO-lactose

O

O15

a

i

O

Note 1a

i: THF, triethylamine, isoleucineethyl ester hydrogen chloride, ethyl-2-(O-glycyl)lactate ammonium oxalate, poly(aminomethoxyethylene glycol

278

EXPERIMENTAL

1. Preparation of Poly[(Aminomethoxyethyleneglycol)(Isoleucineethylester)-(Ethyl-2-(O-Glycyl)Lactate)] (NP(AMPEG550)0.78(IleOEt)1.18(GlyLacOEt)0.04)

Poly(dichlorophosphazene) (17.26 mmol) was dissolved in THF and then put into adry ice-acetone bath and treated with triethylamine (82.84mmol) and isoleucineethylester hydrogen chloride salt (20.71mmol).After themixturewas stirred for 48hours atambient temperature, it was treated with a solution of ethyl-2-(O-glycyl)lactateammonium oxalate(0.69 mmol) and triethylamine (3.45 mmol) in 50ml acetonitrile,and reacted a further 19 hours in an ice bath. Finally poly(aminomethoxy-ethyleneglycol) (25.89 mmol,Mw�500 daltons) and triethylamine (51.78 mmol) were addedand the mixture was reacted for 48 hours at 50�C. The reaction mixture was filtered,concentrated until a small quantity of solvent remained, and dissolved in THF. Themixture was precipitated by adding excessive hexane and filtered, the process beingrepeated 3 times. The solid was dissolved in a small amount of methanol and dialyzedusingmethanol and distilledwater for 5 days apiece. The product isolated in 58%yieldhad aMw of roughly 27,000 daltons, maximum viscosity of roughly 312.8 Pa-s, and amaximum gel temperature of 43�C.

DERIVATIVES

NOTES

1. Additional biodegradable and thermosensitive polyphosphazenes derivatives,(I), were prepared by the author [1] in an earlier investigation. Thermosensitivecyclotriphosphazene analogues were also prepared by Sohn [2].

TABLE 1. Physical properties of selected polyphosphazenes prepared accordingto the current invention.

Entry FormulaMw

(daltons)

MaxiumViscisity(Pa� s)

Maxium GelTemperature (�C)

1 NP(AMPEG550)0.78(IleOEt)1.18(GlyLacOEt)0.04

27,000 312.8 43

2 NP(AMPEG550)0.70(IleOEt)1.20(GlyLacOEt)0.10

41,000 550.0 39

3 NP(AMPEG550)0.08(IleOEt)1.20 42,000 400.0 404 NP(AMPEG750)0.65(IleOEt)1.35 22,000 680.0 47

Notes 279

N P N P

HN

O

N

HN

OO

R'

O7

g

7

Pa b

OO

7

R R"

cN P N P

HN

NHR

N

HN

NHR

R"

Pd e

NHR'

R' R"

f

R R' R"Gly-Gly-OEt LeuOEt AlaOEt

(I)

2. Multisubsituted linear polyphosphazene polymers, (II), having high ion con-ductivity at ambient temperature were prepared by Allcock [3] and used as gelpolymer electrolytes.

aN P N PO

O

NO

O

PO

O

CF3

CF3

CF3

O

O

O

O

O

O

(II)

3. Copolymers consisting of polyphosphazene norbornene derivatives, (III), wereprepared by Allcock [4] and used as electrically conductive materials, biomed-ical materials, and as compatibilizing agents.

aO PH N PO

O

NO

O

PO

OO

CF3

CF3

CF3

CF3

CF3

(III)

CF3

CF3

280 Thermosensitive Poly(Organophosphazenes)

References

1. S.-C. Song et al., US Patent 6,319,984 (November 20, 2001)2. Y.S. Sohn et al., US Patent 6,417,383 (July 9, 2002)3. H.R. Blankenship et al., US Patent 6,605,237 (August 12, 2003)4. H.R. Allcock et al., US Patent 6,392,008 (May 21, 2002)

Notes 281

XII. IMAGING AGENT

Title: Polymerization Method for the Synthesisof Polypeptide Imaging Agents

Author: B. J. Grimmond et al., US Patent 7,205,385 (April 17, 2007)Assignee: General Electric Company (Niskayuna, NY)

SIGNIFICANCE

Low molecular weight magnetic resonance imaging contrast-enhancing agents arewidely used because they rapidly diffuse into plaques, but they disperse too rapidlyfrom thebodybecause of their lowmolecularweights. The compoundgadolinium (III)diethylenetriaminepentaacetic acid is a typical example. To address this concern,moderate molecular weight polyamino acids have been prepared containing gadolin-ium (III) diethylenetriamine pentaacetic acid that are as effective as imaging agentswhich diffuse at much slower rates through the body.


283

REACTION

O

OH

NH2

BOHN

O

NH2

BOHN

O

HN 4N(C2H5)3DTPA

O

OH

NH2

NH

4N(C2H5)3DTPA

NH2

O

OH

NH2

NH

DTPA Gd(III)Na

NH

NH

DTPA Gd(III)Na

O

O

O

H

HN

NH

OH

O

NH

DTPA.Gd(III).Na

O0.8 0.2

i ii iii

ivv

vi

i: Methanol, 9-borobicyclononane (9-BBN), THFii: Diethylenetriaminepentaacetic acid (DTPA), triethylamine, isobutylchloro-

fomateiii: Ethylene diamine (EDA)iv: Gadolinium (III) chloride (Gd), trisodium citratev: CH2Cl2, triethylamine, triphosgenevi: N-Carboxy anhydride (NCA)-valine, acetone, CH2Cl2

EXPERIMENTAL

1. Preparation of 9-Borobicyclononanelysine Complex

A sample of lysine (1 eq) was stirred in methanol at ambient temperature, slowlytreated with 9-borobicyclononane (9-BBN) (1 eq) in THF, and refluxed for 1 hour at50�C. The clear and colorless mixture was concentrated to give a solid that was re-dissolved in THF at 40�C and then filtered and re-concentrated. The product wasisolated as an off-white solid and used without further purification.

284 Polymerization Method for the Synthesis of Polypeptide Imaging Agents

2. Preparation of 9-BBN-Lysine-Diethylenetriaminepentaacetic Acid

A sample of 0.1M solution diethylenetriaminepentaacetic acid (DTPA) (1 eq) inacetonitrile was treated with triethylamine (5 eq) and degassed for 20 minutes beforeheating for 1 hour at 50 �C. The solution was then cooled to �45�C, treated with thedropwise addition of isobutylchloro-fomate (1.1 eq), and stirred for 1 hour. Thismixture was next treated with the Step 1 product (1 eq) dissolved in acetonitrileand stirred 12 hours at ambient temperature. The solution was concentrated, theresidue re-crystallized fromTHF and diethyl ether, and the product isolated as awhitesolid.

3. Preparation of Lysine-N-�-DTPA

Amixture of theStep 2product (1 eq) inTHFand ethylene diamine (1.1 eq)was heatedfor 10 minutes at 60�C. The solution was then concentrated and the residue washedwith pentanes, re-crystallized from warm THF and diethyl ether, and the productisolated.

4. Preparation of Lysine-N-�-DTPA Gadolinium (III) Sodium (Gd.Na)

A 0.1M aqueous solution of the Step 3 product (1 eq) was added to a pH 6 buffersolution of GdCl3 (1.2 eq) and trisodium citrate (2.4 eq). The mixture was then stirredfor 12 hours and the volume reduced; next it was filtered twice through a Sephadexplug. The volume was further reduced and poured into acetone. Awhite precipitateformed, and the product was isolated after filtration.

5. Preparation of N-Carboxy Anhydride (NCA)-Lysine-N-�-DTPA.Gd.Na

A 0.1M CH2Cl2 solution of the Step 4 product (1 eq) and triethylamine (2 eq) wastreated with triphosgene (0.3 eq) at 0�C. Themixturewas stirred for 1 hour at ambienttemperature and concentrated; the residuewas extracted with EtOAc. The extract wasfiltered was re-concentrated, the residue re-crystallized in CH2Cl2/pentanes, and theproduct was isolated as a white solid.

6. Preparation of Poly(Lysine-N-�-DTPAGd.Na)-(Valine) RandomCopolymer

The Step 5 product (1 eq) and NCA-valine (0.25 eq) were dissolved in CH2Cl2 andacetone, 5:1, respectively, and the mixture was heated to 60 �C. The mixture wasthen treated with triethylamine (0.01 eq) dissolved in CH2Cl2 and heated for 24hours at 60�C. Thereafter the mixturewas treated with 0.01M aqueous hydrochloricacid, and a white solid formed. The solid was washed with acetone, and the productwas isolated.

Experimental 285

DERIVATIVES

Gadolinium-containing poly(lysine) homopolymer, (I), and biotin terpolymer, (II),were also prepared.

H

HN

NH

HN

NH-DTPA.Gd.Na

O

O

OH

NH-Biotin

O

0.66 0.170.17

(II)

HO

HN

H

O

NH-DTPA.Gd.Na

(I)

NOTES

1. Compositions containing complexed gadolinium for enhancing transmem-brane transport, (III), were prepared by Wedeking [1] and used as diagnosticor therapeutic treatment agents.

N N

NNCO2

O2C CO2

Gd

O

NH

NO

CO2H

O

HN

N

N

HN

N

O

H2N

3

(III)

NH

O

HN

O

N N

NNO2C

O2C CO2

3Gd

2. Lauffer [2] prepared gadolinium-containing contrast-enhancing imagingagents, (IV), containing an image-enhancing component and to monitor echemoembolization by magnetic resonance imaging therapy.


NN

NCO2

CO2

CO2

O2C

O2C

O

POO

O

Gd3

(IV)

3. Giovenzana [3] prepared a novel class of multidentate aza ligands, (V), thatformed complexes with gadolinium having particularly favorable stability andrelaxation times.

N N

CO2H

CO2H

CO2HHO2C

HO2C

(V)

4. Ranganathan [4] enhanced the stability of MRI contrast imaging agents byincorporating ascorbic acid, (VI), to diminish oxidation of substituents fromfree radical reactions induced by radionuclide decay.

N N

NNCO2O2C

CO2NH

O

HN

O

OH

O

HO

HO

O

Gd 3

(VI)

Notes 287

References

1. S. Wedeking et al., US Patent 7,175,829 (February 13, 2007) and US Patent 7,147,837 (December 12,2006)

2. R.B. Lauffer et al., US Patent 7,182,934 (February 27, 2007) and US Patent 7,198,776 (April 3, 2007)3. G.B. Giovenzana et al., US Patent 7,186,400 (March 6, 2007)4. R.S. Ranganathan et al., US Patent 7,160,535 (January 9, 2007)


XIII. INK

Title: Process for Preparing Chain ExtendedThermoplastic Guanidinium Polymers

Author: D. Hall et al., US Patent 7,172,274 (February 6, 2007)Assignee: Fujifilm Imaging Colorants Limited (Manchester, GB)

SIGNIFICANCE

A method for preparing guanidinium or biguanidinium pre-polymers and then chainextending them with tetraethyleneglycol diepoxide or isophorone diisocyanate isdescribed. These agents are effective as fixing agents to reduce highlighter smear ofprints prepared by ink jet printing.

REACTION

H2N

NH . HCl

NH2NH

NH

NH

NH

NH

NH

NH

HN

a bH2NNH

HN NH2i

NH

NH

NH

NH

NH

NH

NH

HN

a bHNNH

HN NH

OH HO

O

O

O

O4 4

ii

Note 1

Note 2

i: Hexamethylene diamineii: Water, tetraethyleneglycol diepoxide


289

EXPERIMENTAL

1. Preparation of Polyhexamethyleneguanidine Pre-Polymer

Avessel was charged with guanidine and hydrochloride (200 parts) and hexamethy-lene diamine (292 parts) and heated 4 hours at 120�C and an additional 5 hours at150�C to 170�C. The mixture was cooled and treated with water (400 parts) and thenstirred at 80�C until dissolution occurred. When further cooled to ambient tempera-ture, the solid remain dissolved in water.

2. Preparation of Polyhexamethyleneguanidine with Epoxy Termini

The Step 1 product (51.2 g) was mixed with water (78.83 g) and tetraethyleneglycoldiepoxide (9.8 g) and reacted for 2 hours at 25�C. The prepolymer isolated had aMn of1520 daltons and Mw of 3190 daltons.

SCOPING REACTIONS

NOTE

Polyhexamethyleneguanidine pre-polymers were also chain extended with isophor-one diisocyanate and physical properties provided in Table 2.

TABLE 1. Physical properties of polyhexamethyleneguanidine with epoxy terminiprepared by reacting the Step 1 pre-polymer with tetraethyleneglycol diepoxide.

Entry Epoxide : Prepolymer Ratio Mn Mw

2 0.80 1,970 9,4203 0.95*1 2,330 26,4404 0.60 1,250 2,160

*1Reaction performed in 1,5-pentanediol

TABLE 2. Physical properties of polyhexamethyleneguanidine derivatives preparedby reacting the Step 1 pre-polymer with isophorone diisocyanate.

Entry Isocyanate : Prepolymer Ratio Mn Mw

13 0.60 1,650 82,49014 0.80 1,770 96,12014 0.95 1,800 310,930

Mn¼ 710 daltonsMw¼ 1010 daltonsNH2 termini content¼ 4.7%Amine content¼ 71.5wtTriple substitution¼ 12%

290 Process for Preparing Chain Extended Thermoplastic Guanidinium Polymers

NOTES

1. Ammonolysis of poly(hexamethylene urea), (I), was used by Miyamoto [1] toprepare guanidine polyhexamethyleneguanidine, (II), as illustrated below.Fitzpatrick [2] subsequently converted this material into a polyguanidine ethers,(III), by reacting with 1,2-dibromoethane and 1,4-butanediol.

H2N NH2 OCN NCO NH

NH

O

+666

NH

NH

NH

6

NH3

(I) (II)

H2N NH2 OCN NCO NH

NH

O

+666

NH

NH

NH

6

NH3

(I) (II)

NH

NH

NH

6NH

NH

NH

6

(III)

BrCH2CH2Br

HOCH2CH2CH2CH2OHOO

4 a

aa

2. Imashiro [3] converted p-diphenylmethane diisocyanate, (IV), into the corre-sponding polycarbodiimide, (V), and then postreacted with dibutyl amineforming the corresponding polyguanidine derivative, (VI).

H2COCN NCO

H2CNCN

H2CNC

HN

a

a

N

(IV) (V)

(VI)

i ii

i: THF, 3-methyl-1-phenyl-2-phosphorene-1-oxideii: THF, dibutyl amine

3. Although selected polyamines, (VII), functionalized with guanidine, (VIII),were prepared by Dhal [4] for use in the treatment of gastrointestionaldisorders; their application as a crosslinkable resin was also suggested by theauthor.

aNH2

NHHN

NH2 HCl

NN

NH2 HClHN+

a

(VIII)(VII)

Notes 291

4. Polyamide resin components containing pendant guanidine, (IX), were pre-pared by Rothbard [5] to aid in the delivery of selected biological agents.

3NH

HN

RHO

O

NH

NHH2N

O

NH

NH2HN

O

NH

NHH2N

(IX)

R = Therapeutic agent

References

1. K. Miyamoto et al., US Patent 7,157,534 (September 22, 2002)2. R.J. Fitzpatrick, US Patent 6,955,806 (October 18, 2005)3. Y. Imashiro et al., US Patent 6,225,417 (May 1, 2001)4. P.K. Dhal et al., US Patent 6,294,163 (September 25, 2001)5. J.B. Rothbard et al., US Patent 7,157,534 (July 6, 2004)

292 Process for Preparing Chain Extended Thermoplastic Guanidinium Polymers

XIV. LIQUID CRYSTALS

A. Liquid Crystal Aligner

Title: Diamines, Polyimide Precursors, and PolyimidesProduced by Using the Diamines and Liquid CrystalAligning Agents

Author: K. Hosaka et al., US Patent 7,169,878 (January 30, 2007)Assignee: Nissan Chemical Industries, Ltd. (Tokyo, JP)

SIGNIFICANCE

Poly(amic acids) were prepared by the ambient temperature condensation of 1,2,3,4-cyclobutane tetracarboxylic dianhydride with selected aromatic diamines. When thepoly(amic acids) and liquid crystal alignment agents g-butyrolactone and N-methyl-pyrrolidone were spin-coated and cured onto an inert surface, the polyimide waseffective as a liquid crystal aligner.


293

REACTION

H2N O O NH2

H2N O ONH2

H2N

O2C

CO2

NH2

O

C12H25O

C12H25O....

....

HNNH2

O2C

i

N O ONO

C12H25O

C12H25O....NN

O

O

O

O

O

O

O2C

CO2

CO2ii

N

N

a b

a b

O O

O O

O O

OO

OO

ON

O O

OO

....c

c

i: N-Methylpyrrolidone, 3,5-di-dodecyloxybenzyl-3,5-diamino-benzoatediamine,1,2,3,4-cyclobutane tetracarboxylic dianhydride

ii: N-methylpyrrolidone, g-butyrolactone

EXPERIMENTAL

1. Preparation of Poly(Amic Acid) Intermediate

A reaction flask was charged with 3,5-di-dodecyloxybenzyl-3,5-diamino-benzoate-diamine (0.75 mmol), 1, 2, 2’-bis[4-(4-aminophenoxy)phenyl]propane (4.25 mmol),1,2,3,4-cyclobutane tetracarboxylic dianhydride (5.00 mmol), and N-methylpyrrol-idone (17.69 g) and then stirred at ambient temperature until a 15 wt% solid contentpolyimide precursor solution was obtained.

Viscosity (25�C): 5184MPasMW (GPC): 413,000 daltons

294 Diamines, Polyimide Precursors, and Polyimides

2. Preparation of Mixed Polyimides as Liquid Crystal Aligning Films

The Step 1 product was diluted with N-methylpyrrolidone and g-butyrolactone thenspin-coated on glass substrates having transparent electrodes. Themixturewas heatedat 80�C for 10 minutes and at 180�C or 250�C for 60 minutes to form a uniformpolyimide coating film.

DERIVATIVES

O O

NH2O

C12H25O

C12H25ONH2 H2NH2N

Amine 2Amine 1

H2N NH2

O OC12H25

OC12H25

Amine 3

TESTING

Viscosity and contact angle testing results are provided in Tables 2 and 3, respectively.

TABLE 1. Three amine co-reagents used in reacting with 5.00mmol cyclobutanetetracarboxylic dianhydride.

EntryAmine 1(mmol)

Amine 2(mmol)

Amine 3(mmol)

NMP/cbutyrolactoneAligning

Agents, 8:2 (g)Viscosity*1

(MPas)Mw

(daltons)

4 4.75 0.25 5.00 17.17 7,600 624,0005 2.50 — 2.50 19.35 172*2 41,2006 3.75 1.25 — 18.13 344*3 78,000

Note: Poly(amic acids) were prepared by mixing and stirring reagents at 25�C.*1Measured at 25�C*216% solids*315% solids

TABLE 2. Physical properties of polyimides as liquid crystal aligning films preparedby heating N-methyl-pyrrolidone and c-butyrolactone, 8:2, respectively,with polyamic acids described in Table 1.

Entry Viscosity (MPas) Solid Content (%)

4 24.3 4.105 24.9 3.986 28.2 2.80

Testing 295

TABLE 3. Results of water and methylene/iodine repellency testing of polyimidefilms obtained by reacting 1,2,3,4-cyclobutane tetracarboxylic dianhydride withamines described in Table 1.

Amine 3Contact Angle

Surface EnergyEntry Content (%) Water (�) Methylene/iodine (�) (dyn/cm)

4 50 97.7 56.1 30.850 93.6 52.7 32.8

5 25 93.3 54.5 31.825 91.8 51.5 33.5

6 15 87.9 51.7 33.815 90.756.1 50.9 33.9

NOTES

1. Polyimides containing polyaromatic amines, (I) and (II), were previouslyprepared by the author [1] and used as electronic insulating agents.

H2N

O

HN

OC12H25O

HN

O

NH2

O O

H2N NH2

C12H25O O

(I) (II)

In a subsequent investigation by the author [2] four additional amines,(III)–(VI), were prepared and used to prepared polyimides for coating applica-tions.

H2N NH2

O

OC8H17

A

B

B A Amine III Cyclohexyl Cyclohexyl IV Phenyl Cyclohexyl V Cyclohexyl Phenyl VI Phenyl Phenyl

296 Diamines, Polyimide Precursors, and Polyimides

2. Photo-crosslinkablemalimide (VII) and styryl (VIII) derivativeswere preparedby Nakata [3] and used as liquid crystal aligning agents and liquid crystaldisplay elements.

O O O O

O

6 2R

R

N

O

O

VII

CHCHC6H5VIII

Entry

References

1. K. Hosaka et al., US Patent 6,740,371 (May 25, 2004)2. K. Hosaka et al., US Patent Application 2006-0246230 (November 2, 2006)3. S. Nakata et al., US Patent 7,074,344 (July 11, 2006) and US Patent Application 2004-0009310

(January 15, 2004)

Notes 297

Title: Photosensitive Polyimides for Optical Alignmentof Liquid Crystals

Author: W. M. Gibbons et al., US Patent 7,005,165 (February 28, 2006)Assignee: Elsicon, Inc. (Newark, DE)

SIGNIFICANCE

Polyimides derived from 1,2,3,4-cyclobutanetetracarboxylic dianhydride and sele-cted aromatic diamines have been found effective as photosensitive materials. Thesematerials have applications as liquid crystals aligners, liquid crystal displays, andrelated liquid crystal optical elements. The film preparation uses a noncontactmethodthat can reduce dust and static charge buildup and improve resolution.

REACTION

a

BrHN

N

H2N

NO2

N

H2N

NH2

N

H2N

O

CO2

NH2

CO2

O

N N

O

O

O

O N

i ii viiii

v

i: Methyl amine, methanol, diethyl etherii: 3-Fluoro-4-nitroaniline, triethyl amine, N-methylpyrrolidinoneiii: Tin (II) chloride dihydrate, ethanol, hydrochloric acid, potassium hydroxideiv: 1,2,3,4-Cyclobutanetetracarboxylic dianhydride, N-methylpyrrolidinone)

298

EXPERIMENTAL

1. Preparation of N-(3-Methyl-2-Butenyl)-N-Methyl Amine

A reactor was charged with 4-bromo-2-methyl-2-butene (15.0 g) and then treatedwith 110ml of 40% of aqueous methyl amine, 110ml of diethyl ether, and 50ml ofmethanol. The mixture was extracted, and the extracts were dried over potassiumcarbonate and distilled; 5.25 g of product were isolated, BP¼ 80–89�C.

2. Preparation of 3 [N-(3-Methyl-2-Butenyl)-N-Methyl]Amino-4-Nitroaniline

The Step 1 product was stirred with 3-fluoro-4-nitroaniline (3.12 g), 6.2ml of triethylamine, and 30ml of N-methylpyrrolidinone at 80�C to 85�C for 10 hours and thenextractedwithwater and diethyl ether. The extractwas purified by chromatography onsilica gel; and the product was isolated.

3. Preparation of 1-(3-[N-(3-Methyl-2-Butenyl)-N-Methyl)-2,5-Benzenediamine

The Step 2 product (4.55 g) was treated with tin (II) chloride dihydrate (18.0 g)dissolved in 100ml of ethanol and 16ml of 10M hydrochloric acid and then stirredat ambient temperature for 9 hours. The mixture was basified with chilled 20 wt%potassium hydroxide (160 g), extracted with diethyl ether, and purified bychromatography on silica gel; the product was isolated as a light amber oil.

4. Preparation Polyamic Acids: General Procedure

Amixture of 1,2,3,4-cyclobutanetetracarboxylic dianhydride (0.58mmol), a selecteddiamine (0.58mmol), and 1.25ml ofN-methylpyrrolidinonewere stirred at 18�C for 3hours and then diluted to 5 wt% with c-butyrolactone (3.49 g). The product was usedfor spinning thin films.

5. Preparation of Films: General Procedure

Two 0.9"� 1.2"� 1mm thick soda lime glass substrates containing transparentindium-tin-oxide were spin-coated and cured with the Step 4 product by heating thinfilms in air for 15 minutes at 80�C and for 60 minutes at 200�C.

Experimental 299

DERIVATIVES

NOTES

1. In a subsequent investigation by the author [1] additional Step 5 products, (I)and (II), were prepared and used in liquid crystal alignment layers.

aN N

O

O

O

O (I)

O

O

O

OCH3

O

(II)

TABLE 1. Optical alignment of polyimide compositions derived from 1,2,3,4-cyclobutane-tetracarboxylic dianhydride and selected diamines.

Entry Diamine

LampExposure(J/cm2)

AlignmentQuality

HoldingRatio (75�C) Contrast

4 H2N

NH2

N 10 fair 0.911 10:1

8 H2N

NH2

N 20 good 0.835 179:1

9 H2N

N

NH2 20 fair 0.823 316:1

12 H2N

NH2

N 10 excellent 0.806 82:1

300 Photosensitive Polyimides for Optical Alignment of Liquid Crystals

2. The preparation of other aromatic diamines, (III), useful in preparing photo-sensitive polyimides effective as liquid crystal alignment agents is provided bythe author [2].

NO

C8H17

NH2

H2N

(III)

3. Polyimide esters, (IV), prepared Buchecker [3], containing a photoactive sidechain were used as orientation layers for liquid crystals and in the constructionof both unstructured and structured optical elements.

aN N

O

O

O

O

OO

O

O

H3CO

n-C4H9-O

(IV)

4. Polyimides derived from diamines containing a steroid component, (V), wereprepared by Hiraoka [4] and used as method for producing liquid crystalalignment layers.

O

OH2N

NH2

(V)

Notes 301

References

1. W.M. Gibbons et al., US Patent Application 2006-0051524 (March 9, 2006)2. W.M. Gibbons et al., US Patent 6,713,135 (March 30, 2004) and US Patent 6,380,432 (April 30, 2002)3. R. Buchecker et al., US Patent 6,831,148 (December 14, 2004)4. H. Hiraoka et al., US Patent 6,312,769 (November 6, 2001)

302 Photosensitive Polyimides for Optical Alignment of Liquid Crystals

B. Liquid Crystal Materials

Title: Homopolymers That Exhibit a High Levelof Photo-inducable Birefringence

Author: H. Berneth et al., US Patent 7,214,752 (May 8, 2007)Assignee: Bayer MaterialScience AG (Leverkusen, DE)

SIGNIFICANCE

Homopolymers that are capable of absorbing visible light and that are structured sothat in their thermodynamically stable state they are distended and strongly aniso-metric have been prepared. After absorbing electromagnetic radiation, the side groupformsanangleofat least 30�with the longitudinal axis.Thesematerials are suitable forstorage of optically provided information.

303

REACTION

a

NH2

CN

CN

NH2

NN

NC

CN

HN

NN

NC

CN

O

O

O

O

HN

NN

NC

CN

O

O

O

O

i iiiiiNote 1

i: Nitrosylsulphuric acid, sulfuric acid, anilineii: Dioxane, 4-(2-methacryloyloxy)-ethoxy-benzoic acid chlorideiii: DMF, azobis(isobutyronitrile)

EXPERIMENTAL

1. Preparation of 4-Amino-20,40-Dicyano-Azobenzene

2,4-Dicyanoaniline (31.4 g) was treated with nitrosylsulfuric acid (72 g) at 0�C to 5�Cin 300ml of 50% aqueous sulfuric acid, and the batch was stirred for 1 hour. Thismixture was then slowly poured into a solution of aniline (20.4 g) and urea (4.5 g)dissolved in300mlof50%aqueous sulfuric acid and then stirred for anadditional hourat 0�C to 5�C. Thereafter the reaction mixture pH was raised to 5.5 with sodiumcarbonate.Aprecipitate formed thatwas filtered off under suction,washedwithwater,anddried; 34 gof productwere isolated. Thismaterialwasused in thenext stepwithoutfurther purification.

2. Preparation of Liquid Crystal Monomer

The Step 1 product (27.6 g)was dissolved in 500ml dioxane and added to a solution of4-(2-methacryloyloxy)-ethoxy-benzoic acid chloride (33 g) in 100ml dioxane andthen stirred for 2 hours. The product was precipitated by pouring the solution into2 liters of water, purified by crystallization twice from dioxane, and 30.4 g of orange-red crystals isolated with kmax¼ 404.5 nm (DMF) and a mp¼ 215–217�C.

304 Homopolymers That Exhibit a High Level of Photo-inducable Birefringence

3. Preparation of the Liquid Crystal Homopolymer

The Step 2 product (7.9 g) was polymerized at 70�C in 75ml DMF under argon using2,20-azobis(isobutyronitrile) (0.39 g) for 24 hours. The mixture was filtered, concen-trated, and the residue boiled with methanol to remove unreacted monomer. Thematerial was dried, and 7.18 g amorphous polymer were isolated having a glasstransition temperature of 150�C.

DERIVATIVES

TABLE 1. Selected azo monomers and corresponding melting points and lmax.

Entry Monomer Structure MP (�C)

lmax

(DMF)(nm)

11

HN NN

OOO

O

S

N

NO2

207-208 392

12 N NN

NC

CN

NNO 164 521

13HN N

N N(CH3)2

OOO

O218–220 428

TABLE 2. Light-induced birefringence, Dn, at 250mV at a wavelength of 514 nmusing 0.9 lm thick polymer films.

Entry na Dn l (nm)

11 26,000 0.244 82012 20,800 0.233 63313 27,855;

193800.194 820

Derivatives 305

NOTES

1. Additional azoderivatives were previously prepared by the author [1]

2. Partially hydrogenated polymers derived from norbornene derivatives, [I],prepared by Miyaki [2] were low in birefringence, high in wavelengthdependency birefringence, and excellent in transparency and heat resistance.Additional functionalized norbornene derivatives were prepared by Liaw [3].

N

O

O CO2CH3

(I)

References

1. H. Berneth et al., US Patent 6,875,833 (April 5, 2005) and US Patent 6,441,113 (August 22, 2002)2. N. Miyaki et al., US Patent 7,230,058 (June 12, 2007) and US Patent 6,846,890 (January 25, 2005)3. D.-J. Liaw et al., US Patent 7,045,248 (April 17, 2007)

306 Homopolymers That Exhibit a High Level of Photo-inducable Birefringence

Title: Liquid Crystalline Compound, LiquidCrystalline Composition, and Retardation Film

Author: H. Nishikawa et al., US Patent 7,169,325 (January 30, 2007)Assignee: Fuji Photo Film Co., Ltd. (Minami-Ashigara, JP)

SIGNIFICANCE

Oligomeric phenylacetylene liquid crystalline derivatives capable of exhibiting abiaxial liquid crystal phase have been prepared. When these agents were functiona-lized with the polymerizable group 4-(4-acryloyloxybutyloxy)benzoic acid and thencoated onto an alignment film and polymerized. An optically anisotropic retardationfilm was produced.

307

REACTION

O

O

O

O

O

O

O

O

BrO

O

O

O

TMS

O

O

O

O

TMS

O

O

O

O

O

O

O

O

O

O

O

O

OH

OH

OH

OH

OH

OH

OR1

OR1

OR1

OR1

OR1

OR1

OR2

OR2

OR2

OR2

OR2

OR2

i ii iii

ivv

vi vii

O

O

O

O

O

O

O7 4R1 = R2 =

i: 1,3-Dibromobenzene, triphenylphosphine, bis(triphenylphosphine)palladium(II) dichloride, copper(I) iodide, triethylamine

ii: Trimethylsilyl acetylene, triphenylphosphine, bis(triphenylphosphine)palladi-um(II) dichloride, copper(I) iodide, triethylamine

iii: THF, tetrabutylammonium fluorideiv: 2,6-Dibromo-1,4-diacetoxybenzene, triphenylphosphine, bis(triphenylphosphine)-

palladium(II) dichloride, copper(I) iodidev: THF, methanol, sodium methoxidevi: 4-Octyloxybenzoic acid chloride, THF, diisopropylethylamine, 4-dimethyl-

aminopyridinevii: 4-(4-Acryloyloxybutyloxy)benzoic acid, THF, diisopropylethylamine, 4-dimethyl-

aminopyridine

EXPERIMENTAL

1. Preparation of 1-(2,5 Diacetoxyphenyl)-2-(3-Bromophenyl)Acetylene

A mixture consisting of 2,5 diacetoxyphenylacetylene (3 g), 1,3-dibromobenzene(10 g), triphenylphosphine (58mg), bis(triphenylphosphine)palladium(II) dichloride

308 Liquid Crystalline Compound, Liquid Crystalline Composition, and Retardation Film

(29mg), and copper(I) iodide (10mg) were dissolved in 50ml of triethylamine andthen refluxed for 10 hours under a nitrogen atmosphere. After cooling, water wasadded, and the reaction solution was extracted with EtOAc, washed with saturatedbrine, and concentrated. The residue was purified by column chromatography, and2.8 g of product were isolated.

2. Preparation of 1-(2,5 Diacetoxyphenyl)-2-(3-Trimethylsilylethynylphenyl)Acetylene

A mixture consisting of the Step 1 product (2.1 g), trimethylsilyl acetylene (0.83 g),triphenyl-phosphine (24mg), bis(triphenylphosphine)palladium(II) dichloride(12mg), and copper(I) iodide (4mg) dissolved in 20ml of triethylaminewas refluxedfor 10 hours under a nitrogen atmosphere. After cooling, water was added, and thereaction solution was extracted with EtOAc, washed with saturated brine, andconcentrated. The residue was purified by column chromatography, and 1.5 g ofproduct was isolated.

3. Preparation of 1-(2,5 Diacetoxyphenyl)-2-(3-Ethynylphenyl)Acetylene

The Step 2 product (1.5 g) was dissolved in 200ml of THF, treated with 5ml of 1.0MTHF solution of tetrabutylammonium fluoride, and stirred at ambient temperature for30 minutes. The solution was treated with water, extracted with EtOAc, and washedwith saturated brine. The organic layer was concentrated under reduced pressure andthen purified by column chromatography; 0.9 g of product was isolated.

4. Preparation of 1-[(2,5-Diacetoxyphenyl)-2-[3-(2,5-Diacetoxyphenylethynylphenyl)] Acetylene (Product 4A) and 1-[(2,5-Diacetoxyphenyl)-3-(2,5-Diacetoxyphenylethynylphenyl)]-2-[(2,5-Diacetoxy-phenyl)-3-2,5-Diacetoxyphenylethynylphenyl)] Acetylene (Product 4B)

Amixture consisting of theStep 3 product (0.7 g), 2,6-dibromo-1,4-diacetoxybenzene(0.37 g), triphenylphosphine (10mg), 5mg of bis(triphenylphosphine)-palladium(II)dichloride, and copper(I) iodide (2mg) dissolved in 20ml of triethylamine wasrefluxed for 10 hours under a nitrogen atmosphere. The mixture was cooled and thentreated with water. The solution was extracted with EtOAc, washed with saturatedbrine, and concentrated. The residue was purified by column chromatography, and0.21 g and 0.18 g of products 4A and 4B, respectively, were isolated.

5. Preparation of 1-[(2,5-Dihydroxyphenyl)-3-[2,5-Dihydroxyphenylethynylphenyl)]-2-[(2,5-Dihydroxyphenyl)-3-(2,5-Dihydroxyphenylethynylphenyl)]Acetylene

The Step 4B product (0.18 g) was dissolved in 20ml of THF, treated with 5ml ofmethanol and 0.4ml of sodium methoxide dissolved in 28% methanol, stirred for1 hour at ambient temperature, and neutralized with dilute hydrochloric acid.

Experimental 309

Themixturewas extractedwithEtOAc, concentrated, and 0.12 gof crystalline productwas isolated.

6. Preparation of 1-[(2,5-(4-Octyloxybenzoxy))-3-(2,5-(4-Octyloxybenzoxy)Ethynylphenyl)]-2-[(2,5-(4-Octyloxybenzoxy)-3-(2,5-(4-Octyloxybenzoxy))]Acetylene

The Step 5 product (0.06 g) and 4-octyloxybenzoic acid chloride (0.4 g) weredissolved in 10ml of THF, treated with diisopropylethylamine (0.2 g) and 4-dimethy-laminopyridine (0.01 g), and stirred 12hours at ambient temperature.Waterwas addedto the reaction mixture, and the mixture was extracted with EtOAc. The mixture wasconcentrated and then purified by column chromatography; 0.2 g of the crystallineproduct was isolated.

7. Preparation of 1-[(2,5-(4-(4-Acryloyloxybutyloxy)Benzoxy)-3-(2,5-(4-Acryloyloxybutyl-oxy)-Benzoxy)Ethynylphenyl)]-2-[(2,5-(4-Acryloyloxybutyloxy)Benzoxy)-3-(2,5-(4-Acryloyloxybutyloxy)Benzoxy)]Acetylene

The Step 6 procedurewas repeated using 4-(4-acryloyloxybutyloxy)benzoic acid, andthe product was isolated.

DERIVATIVES

Two additional derivatives, (I), were prepared.

OR

OR

OR

OR

O

O

O

O4R = H;

(I)

BIAXIAL LIQUID CRYSTAL TESTING RESULTS

Step 6 Product

The phase transition temperature of the Step 6 product was examined by observing itstexture through a polarizing microscope. When the temperature was elevated, the

1H-NMR (CDCl3) d (ppm): 1.70 1.90 (12H, m) 1.90 2.00 (12H, m) 3.95 4.30 (24H, m) 5.75 5.80 (6H, m)6.056.20 (6H, m) 6.35 6.50 (6H, m) 6.90 7.00 (12H, m) 7.00 7.50 (16H, m) 8.10 8.25 (12H, m)

1H-NMR (CDCl3) d (ppm): 0.85 0.95 (18H, m) 1.20 1.60 (60H, m) 1.70 1.90 (12H, m) 3.95 4.10 (12H, m)6.90 7.00 (12H, m) 7.00 7.50 (16H, m) 8.10 8.25 (12H, m)


phase changed from crystal phase to isotropic liquid phase in the vicinity of 140�C.When the temperaturewas gradually lowered from 150�C, the phase changed to theNphase in the vicinity of 120�C. Finally, when the temperature was further lowered toambient temperature, the material reverted to crystal phase. As a result this agent wasjudged to be a biaxial liquid crystal.

Step 7 Product

The phase transition temperature of the Step 7 product was also examined using apolarizingmicroscope.When the temperaturewas initially elevated, the crystal phasereverted to isotropic liquid phase in the vicinity of 80�C. Gradually lowering thetemperature from 90�C resulted in an N phase at approximately 60�C. When thetemperature was finally lowered to ambient temperature, the formation of a crystalphase was observed. As a result this agent was judged to be a biaxial liquid crystal.

PREPARATION OF RETARDATION FILM

8A. Formation of Alignment Film

A polyvinyl alcohol containing 5% glutaraldehyde was dissolved in sufficientmethanol/water, 20/80, respectively, to prepare a 5% solution. This solution wascoated onto a cellulose triacetate film having a thickness of 100 mm and a size of270� 100mmand then driedwith hot air for 2minutes at 100�C.The filmwas rubbedto form an alignment film having a thickness of 0.5 mm.

8B. Formation of Optically Anisotropic Layer

On the alignment film obtained in Step 8A, a coating was evaluated for opticallyanisotropic properties by coating a #4 wire bar with the following components.

Step 7 product, 100 parts

Air interface orientation controlling agent, (II), 0.2 parts (unspecified)

Photopolymerization initiator HJ-1, (III), 2.0 parts by mass

Lucirin TPO-L, 2.0 parts

Methyl ethyl ketone, 300 parts

N

N

N

HN

NHNH

OC12H25

OC12H25C12H25O

C12H25O

OC12H25

OC12H25

HOHN

ON

NN

CCl3

CCl3

(II)

(III)

Preparation of Retardation Film? 311

8C. Formation of Retardation Film

The Step 8B film was coated onto the optically anisotropic layer, placed in athermostatic chamber at 80�C, and heated for 5 minutes 60�. Thereafter the film wascooled at 40�C for 30 seconds in a thermostatic chamber that had an oxygen content of2%and then irradiatedwithultraviolet radiationat 600 nm.The filmwasnextcooled toambient temperature, and the retardation film was isolated having an opticallyanisotropic layer thickness of 1.55 mm. The retardation in the direction perpendicularto the face of the retardation film was 150 nm parallel to the rubbing direction.

NOTES

1. Cinnamic acid liquid crystalline derivatives, (IV), capable of exhibiting abiaxial liquid crystal phase were also prepared by the author [1] and used as acomponent in retardation films.

O

O

OROR

RO

O

O

RO OROR

(IV)

R = CH2(CH2)3-OCO-CH=CH2

2. Phenylacetylene derivatives, (V), were prepared by Tang [2] and converted intothe corresponding polyacetylenes, (VI), as illustrated below, containing a side-chain liquid crystal molecular architecture of backboneþ spacerþ mesogenicgroup. These products were subsequently used in electronic and mechanicalapplications.


O

OO

O

O

OO

O

3

5

3

5

(V) (VI)

i

a

i: Rhodium(nitrobenzofuranzan chloride)dimer, THF, triethylamine

3. Coates [3] prepared liquid crystal films with a homeotropic alignment that wasinduced by an aligning perfluoropolymer substrate after UV irradiation of thethree component phenylacetylenemixture, (VII)–(IX).Other cyano-analogues,(X), were prepared by Radcliffe [4].

OO O

OR

O

O

O O

O

CN

C5H11

Component a

(VII)

(VIII)

(IX)

3

6

6

3

CN(X) 2 or 6

a

R

Notes 313

4. Tanaka [4] prepared 30mm-thick retardation films consisting ofmixed esters ofhydroxypropyl cellulose and acryloyl and n-butyryl chlorides, (XI), having aretardation value of 180 nm at a wavelength of 550 nm after photo polymeri-zation.

OO

O

O

O

OO

O

OO

O

a

(XI)

References

1. H. Nishikawa et al., US Patent 7,153,548 (December 26, 2006)2. B.Z. Tang et al., US Patent 7,070,712 (July 4, 2006)3. D. Coates et al., US Patent 7,170,575 (January 30, 2007)4. M.D. Radcliffe et al., US Patent 7,160,586 (January 9, 2007)5. K. Tanaka et al., US Patent 7,163,723 (January 16, 2007)


Title: Perfluoroallyloxy Compound and Liquid CrystalComposition Containing the Same

Author: H. Shinano et al., US Patent 7,001,647 (September 22, 2006)Assignee: Asahi Denka Co., Ltd. (Tokyo, JP)

SIGNIFICANCE

Perfluoroalloxy liquid crystals were prepared by the Williamson ether synthesisusing perfluoro iodopropene. These materials can bemixedwith nematic liquid crystalmaterials to provide liquid crystal compositions having low viscosity, low refractiveindex anisotropy, high dielectric anisotropy, and broad nematic phase ranges.

REACTION

OH O

F2C

F

F

FiC3H7 C3H7

i: Dimethylimidazolidinone, 3-iodoperfluoropropene, triethylamine

EXPERIMENTAL

Preparation of Pentafluoro-3-(4-[4-(4-n-Propylcyclohexyl)Cyclohexyl]Phenoxy)-Propene

A reactor was charged with 4-[4-(4-n-propylcyclohexyl)cyclohexyl]phenol (4 mmol)dissolved in dimethylimidazolidinone (7 g) and then treated with 3-iodoperfluoro-propene (4 mmol) and triethylamine (4.8 mmol). The mixture was reacted for 2 hours,treated with EtOAc and hydrochloric acid, washed with water until neutral, and driedusing MgSO4. The solvent was then exchange with toluene, treated with silica, andconcentrated. The residuewas purified by repeated kugel-rohr distillations followed by

315

re-crystallization in EtOAc/methanol, 1/18, respectively, and then acetone; the productwas isolated as white crystals in 47% yield.

DERIVATIVES

TABLE 1. Phase transition temperatures for perfluorooalloyloxy compounds andcorresponding optical anisotropy (Dn) and dielectric anisotropy (Dee).

Entry Structure

Phase Transition*1

Temperatures(�C) Dn De

1

O

F2C

FF

FC3H7

Sm¼ 157.3N¼ 174.2! I 0.0926 4.3

14

O

F2C

FF

F

F

F

C5H11

C¼ 67.1Sm¼ 84.9

N¼ 114.1! I 0.126 8.47

18 O

F2C

FF

F

F

F

C3H7Sm¼ 41.2N¼ 166.6! I 0.1006 7.3

19

O

F2C

FF

F

F

C5H11

Sm¼ 44.4N¼ 170.8! I 0.101 6.0

Note: All experimental agents were prepared using the Williamson ether synthesis*1Sm: smectic phaseN: nematic phaseI: isotropic phase

1H-NMR d 7.3 7.0 (m, 4H), 2.6 2.3 (m, 1H), 2.2 0.4 (m, 26H)FTIR (cm�1) 2920, 2850, 1794, 1609, 1508, 1447, 1389, 1319, 1223, 1196

316 Perfluoroallyloxy Compound and Liquid Crystal Composition Containing the Same

NOTES

1. Katoh [1] prepared a liquid crystal composition for use as electronic paperconsisting of one dual-frequency switchable smectic liquid crystal, (I), and atleast one dichroic dye.

C6H13

O

O

Cl

O

O

C5H11

(I)

2. Liquid-crystalline phenol esters, (II), having a nematic phase of �30�C and aclearing point above 90�C were prepared by Reiffenrath [2] and used in thin-film transistors. Naphthyl derivatives, (III), prepared by Takehara [3] were alsoeffective in thin film transistor applications.

C3H7

F

F

O

O F

(II)

C3H7

F

OCHF2

F(III)

3. Perfluoropropenylcyclohexane-containing liquid crystals, (IV), prepared byKato [4] were used as components in liquid crystal display elements.

C3H7

FF

CF3(IV)

References

1. T. Katoh et al., US Patent 7,220,466 (May 22, 2007)2. V. Reiffenrath et al., US Patent 7,179,511 (February 20, 2007)3. S. Takehara et al., US Patent 7,145,047 (December 5, 2006)4. T. Kato et al., US Patent 7,074,464 (July 11, 2006)

Notes 317

Title: Liquid Crystal Polymers

Author: B. Benicewicz et al., US Patent 7,148,311 (December 12, 2006)Assignee: Rensselaer Polytechnic Institute (Troy, NY)

SIGNIFICANCE

Liquid crystal copolyesters were prepared using 4-phenylnaphthalene derivativeswith 4-hydroxybenzoic acid, 6-hydroxy-2-naphthoic acid, or other aromatic diacids.These materials display an improved balance of low melt viscosity, fast cycle time inmolding, high tensile, low thermal expansion coefficient, and thermostability.

REACTION

Br

H3CO H3CO

COOH

O

COOH

i ii

iii

O

O

O O

O

O

a

i: 4-Carboxyoxybenzene boronic acid, 1-propanol, palladium acetate, triphenyl-phosphine, sodium carbonate, acetic acid

ii: Hydrobromic acid, acetic anhydride, sulfuric acidiii: 4-Hydroxybenzoic acid, tin (II) trifluoromethane sulfonate

EXPERIMENTAL

1. Preparation of 2-(40-Carboxyphenyl)-6-Methoxynaphthalene

A mixture consisting of 2-bromo-6-methoxynaphthalene (20 mmol), 4-carboxyox-ybenzene boronic acid (20 mmol), and 40ml of 1-propanol were mixed at ambient

318

temperature and then treatedwith palladium acetate (0.06mmol), triphenylphosphine(0.009 mmol), 18ml of 2M Na2CO3 solution, and 8ml of water. The mixture wasrefluxed for 90 minutes then, with 25ml of water while it was still hot, andrefluxed with 50ml of acetic acid for 45 minutes. It was then cooled to ambienttemperature whereupon crystals formed. The crystals were filtered, washed withwater, and re-crystallized from acetone; the product was isolated 83% yield aswhite crystals.

2. Preparation of 2-(40-Carboxyphenyl)-6-Acetoxynaphthalene

Amixture of the Step 1 pro[duct (10mmol), 80ml of 48% aqueous hydrobromic acid,and 150ml of acetic acid were refluxed overnight and then poured into 400ml water.The residue was mixed with 40ml acetic anhydride with 1 to 2 drops of H2SO4 for2 hours, and a pink solid was isolated. This material was re-crystallized from acetoneor pentanone, and the product was isolated in 66% yield as light yellow crystals.

3. Preparation of Polyesters by Bulk Polymerization

A mixture consisting of the Step 2 product and 4-hydroxybenzoic acid with approxi-mately 500 ppm of potassium acetate or Sn(CF3S03)2 was charged into a polymeriza-tion tube with a side branch and then degassed and purged with nitrogen. While themixturewaspurgedwith nitrogen, the reaction temperaturewas increased to250�Cforabout 1.5 hours, 280�C for 30 minutes, 300�C for 30 minutes, and 320�C for 30minutes. During the temperature gradient, acetic acid was collected in a testtube at theend of the side branch. At the final stage the temperature was kept at 320�C to 330�C,and a vacuum was applied for 60 minutes to remove residual acetic acid.

DERIVATIVES

Monomers

X

Y

MP¼ 254–256�CDSC MP¼ 262�CIR (KBr) (cm�1)[nujol] COO�H (2800 3100, broad, m), 1685 (C¼O, s), 1225 (C�O�C, vs), 1365

(CH3CO, s)1H NMR (500MHz, CDCl3) d 2.34 (s, 3H), 7.3 8.4 (m, 10H), 13.02 (s, 1H)

MP¼ 288–289�CIR (KBr) (cm�1))[nujol] 2500 3000 (COO�H, very broad, m), 1030 (OCH3, s), 1678 (C¼O, s).1H NMR (500MHz, CDCl3) d 3.90 (s, 3H), 7.2 8.3 (m, 10H), 12.99 (s, 1H)

Derivatives 319

Polyesters

O

O

OO

O

b

a

TABLE 2. Thermal properties of copolyesters derived from 6-hydroxy-2-naphthoicacid and 6-(40-acetoxyphenyl)-2-naphthoic acid.

Monomer Ratio(a:b)

5% Weight Loss(�C)

10% Weight Loss(�C)

Crystal Mp(�C)

75:25 378 394 35267.5:32.5 373 385 27060:40 426 440 26050:50 420 436 27640:60 425 438 401

Note: Copolymers had limited solubility in perfluorophenol. Endothermic peaks for all materialscorresponding to Tg’s were weak and ambiguous.

TABLE 1. Transition temperatures for selected 4-phenylnaphthalene monomers ofthe current invention.

Entry X YCrystal Mp

(�C)Neumatic Mp

(�C)Isotropic Mp

(�C)

1 OCH3 OCH3 196 187 1422 OH COOH 296 322 ––3 COOH OCH3 269 339 ––4 OCOCH3 OCOCH3 182 207 ––5 OCOCH3 COOH 263 Polymerizes ––6 COOH COOH >350 –– ––

Note: Evidence for liquid crystal formation for meta- and ortho-phenylnaphthalene monomers was notdetected.

320 Liquid Crystal Polymers

O

O

OO

O

a

b

NOTES

1. Multireactive mesogenic triester derivatives, (I), containing at least two poly-merizable components were prepared by Farrand [1] and used as syntheticresins with anisotropic mechanical properties.

C8H17

OO

O

O

O

O

(I)

2. Mesogen-containing acetylene monomers, (II), were prepared by Tang [2] andpolymerized into polyacetylenes, (III). These monomers had excellent tracta-bility typically associated with polymers having flexible backbones.

TABLE 3. Thermal properties of copolyesters derived from 4-hydroxybenzoic acidand 6-(40-acetoxyphenyl)-2-naphthoic acid.

MonomerRatio (a:b)

5% WeightLoss (�C)

10% WeightLoss (�C) Tg (�C)

CrystalMp (�C)

80:20 405 425 242 43565:35 426 430 189 43055:45 409 424 163 41750:50 450 460 160 42040:60 423 435 –– 408

Note: Although Tg’s provided by the author were reproducible, peaks were weak and ambiguous.

Notes 321

OO

OO

O66

OO

OO

O66

n

i

(II)

(III)

i: Rhodium(2,5-norbornadiene)chloride dimer, THF, triethylamine

3. Liquid crystal polymers prepared by Wellinghoff [3] by UV-curing of meso-genic dimers such as methacrylate carboxylic acid esters, (IV), and diacrylatedimethylsiloxanes, (V), had good fracture toughness, limited shrinkage, me-chanical strength, and four-point bending strength and were used in dentalapplications. Liquid crystal monomers, (VI), with ultra–low cure shrinkagewere prepared by Norling [4] and were used in dental resin composites.

O

O

O

t-C4H9

OO

O

OO O

O

t-C4H9 O

8

(IV)

O

O

O

t-C4H9

OO

SiO

O

t-C4H9O

OSi

OSi

O

(V)

6

O

OO

OO

O

OO O

O

6

(VI)

322 Liquid Crystal Polymers

4. Vaughn-Spickers [5] prepared chiral photoisomerizable mesogenic com-pounds, (VII), that retained their chirality upon photoinitation and were usedin optical and electrooptical devices.

OO

O

O

O

O

O O

O

C5H11

3

(VII)

References

1. L. Farrand et al., US Patent 7,125,500 (October 24, 2006)2. B.Z. Tang et al., US Patent 7,070,712 (July 4, 2006)3. S.T. Wellinghoff et al., US Patent 7,098,359 (August 29, 2006) and US Patent 7,094,360 (August 22,

2006)4. B.K. Norling et al., US Patent 7,135,589 (November 14, 2006)5. J. Vaughn-Spickers et al., US Patent 7,122,227 (October 17, 2006)

Notes 323

XV. NANOPARTICLES

A. Carbon Nanotubes

Title: Method of Coating a Substrate with a PolymerHaving a Combination of Crown Ether and CarbonNanotubes Having Guanidine Groups

Author: H. S. Lee, US Patent 7,261,924 (August 28, 2007)Assignee: Samsung Electro-Mechanics Co., Ltd. (Suwon, KR)

SIGNIFICANCE

A functionalized carbon multi-walled nanotube, MWNT, was prepared in 2 steps byinitially oxidizing the unfunctionalized nanotubewithmixed acids followed by amida-tion with guanidine. When reacted with polystyrene-g-dibenzo-18-crown-6-ether,the polymer, polystyrene-g-dibenzo-18-crown-6-ether-g-(nanotube-g-guanidine),was formed having the nanotube component aligned perpendicular to the polystyrenebackbone.


325

REACTION

c

aa

COOH

CO2H O

O

O

O

OO

O

O

HNO NH2

NH

Nanotube Intermediate

i ii

Intermediateiii iv

O

O

O

O

OO

O

O

HN

O

NHNH

O

a b

i: Sulfuric acid, nitric acidii: Guanidine, CH2Cl2iii: Polystyrene-g-carboxylic acid, hydroxylmethyl dibenzo-18-crown-6-ether, pyr-

idine, wateriv: Ethanol

EXPERIMENTAL

1. Preparation of Multi-walled Carbon Nanotube-g-Carboxylic Acid

MWNTs (40mg) were added to a mixture of 60ml of H2SO4 and 20ml of HNO3 andthen reacted for 24 hours at 50�C with ultra-sonication at about 30 kHz. The stronglyacidic reaction solutionwas dilutedwithwater to a pHof roughly 7, filtered through of0.5 to 1-mm filter paper, dried at 80�C for 6 hours, and the product was isolated.

FTIR (cm�1) 1700, C¼O, 3300, O�H

326 Method of Coating a Substrate with a Polymer Having a Combination of Crown Ether

2. Preparation of Nanotube-g-Guanidine

Amixture consisting of the Step 1 product (10mg), guanidine (20mg), and 5ml of 2Moxalic acid were dissolved in CH2Cl2 and heated for 6 hours at 50

�C. Themixturewasthen filtered, and the product was isolated.

3. Preparation of Polystyrene-g-Dibenzo-18-Crown-6-Ether

Polystyrene-g-carboxylic acid (5 g) and hydroxylmethyl dibenzo-18-crown-6-ether(1g) were dissolved in 500ml of pyridine and reacted at ambient temperature for 5hours. The mixture was then treated with water, and the layers were separated. Theorganic phase was concentrated, and the product was isolated.

4. Preparation of Polystyrene-g-Dibenzo-18-Crown-6-Ether-g-(Nanotube-g-Guanidine)

A 1-mm thick copper substrate was coated with a 200 -mm thick film consisting of theStep 3 product and then dried at 50�C. The film was coated with 200 mm of the Step 2product (10mg) dispersed in 100ml of ethanol. Thereafter the coating was dried at70�C, and the product was isolated having MWNTs aligned perpendicularly to thecopper substrate at regular intervals.

DERIVATIVES


NOTES

1. Hwang [1] prepared polymers, (I), of polyphenylenebisbenzothizaole andSWNT-g-carboxylic acid as a method of improving the solubility of nanotubesin organic solvents.

a

N

X X

N HN

O

(I)Nanotube

X = O,S

Notes 327

2. Chen [2] enhanced the solubility of nanotubes in organic solvents by anoncovalent, nonwrapping approach using p-stacking with rigid-rod conjugat-ed polymers, (II).

a

OC10H21

C10H11O

OC10H21

C10H21O

S

(II)

S

O

3. Nanotube patterned films were prepared by Park [3] using surface-modifiedcarbon nanotubes with polyoxetanes.

References

1. W.-F. Hwang et al., US Patent 7,262,266 (August 28, 2007)2. J. Chen et al., US Patent 7,244,407 (July 17, 2007) and US Patent 7,241,496 (July 10, 2007)3. J.J. Park et al., US Patent 7,229,747 (June 12, 2007)

328 Method of Coating a Substrate with a Polymer Having a Combination of Crown Ether

Title: Process for Derivatizing Carbon Nanotubeswith Diazonium Species

Author: J. M. Tour et al., US Patent 7,250,147 (July 31, 2007)Assignee: William Marsh Rice University (Houston, TX)

SIGNIFICANCE

Single-walled carbon nanotubes, SWNT, having a diameter of 0.7 nm were electro-chemically derivatized on the sides and ends with diazonium tetrafluoroboratederivatives. In this process the estimated degree of functionality was about 1 out ofevery 20 to 30 carbons in the nanotube. These chemically modified nanotubes haveapplications in polymer composite materials, molecular electronic applications, andsensor devices.

REACTION

C14H29 NH2 C14H29 N2BF4

C14H29

C14H29

C14H29

iii

Nanotube

+ _

i: 4-Tetradecylaniline, acetonitrile, CH2Cl2, tetrafluoroborateii: Bucky paper, 1,2-dichlorobenzene, acetonitrile, tetra-n-butylammonium tetra-

fluoroborate

329

EXPERIMENTAL

1. Preparation of 4-Tetradecylbenzenediazonium Tetrafluoroborate

4-Tetradecylaniline (1 eq) was dissolved in a 1:1 mixture of acetonitrile and CH2Cl2and then added to tetrafluoroborate (1.2 eq) at�30�C. Stirring was continued for 30minutes, and the cooling bath was removed. After stirring for an additional 30minutes, the solution was diluted with two times its volume with diethyl etherproduct. The precipitated that formed was filtered and isolated in 69% yield,MP¼ 82�C.

2. General Procedure for Electrochemical Derivatization of SWNT

A three-electrode cell with an Ag/AgNO3 reference electrode and platinum wirecounterelectrode was used in the electrochemical derivatization experiments wherebucky paper (1–2mg) served as the working electrode. The bucky paper wasprepared by filtering a 1,2-dichlorobenzene suspension of the bucky paper overa 0.2-mM Teflon 47mm membrane. After drying under vacuum, the paper waspeeled off the membrane and a piece was excised for use in the derivatizationprocess. The paper was held with an alligator clip previously treated with colloidalsilver paste and immersed in an acetonitrile solution of 0.5mM diazonium salt and0.05M tetra-n-butylammonium tetrafluoroborate. A potential of �1.0 V wasapplied for a period of 30 minutes while nitrogen was bubbled through the solution.Thereafter the portion of the bucky paper that was not immersed in the solution wasexcised while the remainder was soaked in acetonitrile for 24 hours, washed withacetonitrile, chloroform, and ethanol. After drying, this material was sonicated inacetonitrile for 20 minutes, filtered, re-washed with acetonitrile, 2-propanol, andchloroform. The residue was dried under vacuum at ambient temperature, and theproduct was isolated.

DIAZONIUM TETRAFLUOROBORATE DERIVATIVES

R N2BF4

+_

1H NMR (400MHz, CDCl3) d 8.02 (ABq, J¼ 8.8Hz, 2.76 (t, J¼ 7.7Hz, 2H), 1.61 (quin, J¼ 7.8Hz,2H),1.23 (s, 22H), 0.85 (t, J¼ 7.0Hz, 3H)

13C NMR (100MHz, CDCl3) d 159.92, 133.26, 131.94, 110.96, 37.49, 32.34, 30.87, 30.12, 30.10, 30.07,30.04, 29.91, 29.78, 29.75, 29.72, 23.11, 14.55

IR (KBr) (cm�1) 3103.8, 2919.5, 2289.6, 1577.8, 1473.7, 1070.8, 1024.8, 844.5, 813.8, 716.9, 541.0, 510.2

330 Process for Derivatizing Carbon Nanotubes with Diazonium Species

NOTES

1. Stoddart [1] noncovalently wrapped nanotubes with poly{(5-alkoxy-m-phenylenevinylene)-co-[(2,5-dioctyloxy-p-phenylene)vinylene]}, (I), as amethod of increasing the solubility of nanotubes in selected solvents.

OC8H17

C8H17O

OR

a

R = CH2OCH3(CH2)6OH

(I)

2. Khabashesku [2] functionalized carbon nanotubes utilizing peroxides asillustrated below. Niu [3] introduced hydroxycarbonyl functions onto thesurface of single-walled carbon nanotubes using ammonium persulfate andsulfuric acid.

HO OO

O O

O

OH

OH OH

O

HO

O

OH

O2

2

2

22 .

3. Sidewall-functionalized carbon nanotubes were prepared by Wong [4] usingozone with an oxygen carrier then postreacted with sodium hydride or DMS todecompose primary ozonides to form aldehydes and ketones.

TABLE 1. Summaryof diazonium tetrafluoroborate derivatives prepared accordingto the Step 1 procedure.

Entry R Melting Point (�C) Yield (%)

1 Bromo 138 853 Fluoro 160 795 Nitro 142 676 Methoxycarbonyl 113 809 CH3O(CH2CH2O)2CH2CH2O — 52

Notes 331

References

1. J.F. Stoddart et al., US Patent 7,220,818 (May 22, 2007)2. V.N. Khabashesku et al., US Patent 7,125,533 (October 24, 2006)3. C. Niu et al., US Patent 7,045,248 (July 4, 2006)4. S. Wong et al., US Patent Application 2005-0147553 (July 7, 2005) and US Patent 7,122,165 (October

17, 2006)

332 Process for Derivatizing Carbon Nanotubes with Diazonium Species

Title: Carbon Nanotube Adducts and Methodsof Making the Same

Author: S. S. Wong et al., US Patent 7,169,329 (January 30, 2007)Assignee: The Research Foundation of State University of NewYork (Albany, NY)

SIGNIFICANCE

A method for covalently incorporating Wilkinson’s complex onto a multi-walledcarbon nanotube is described. Semiconductor carbon nanotubes derived from thesematerials hadmobilities and transconductanceproperties thatwere superior to thoseofexisting semiconductors.

REACTION

O

OH

Rd P(C6H5)3

P(C6H5)3

Cl

O

OH

Rd P(C6H5)3

P(C6H5)3

Cl

O OHRd

(C6H5)3P

ClP(C6H5)3

HO

ORd

Cl

(C6H5)3PP(C6H5)3

O

HO

OHORdRd

(C6H5)3P

(C6H5)3P Cl

(C6H5)3P P(C6H5)3Cl

CO2H

HO2C

i ii

i: Potassium permanganate, hydrochloric acidii: Wilkenson’s complex, DMSO

333

EXPERIMENTAL

1. Preparation of Nanotube-g-Carboxylic Acid

Raw nanotubes having a mean diameter of 1.41 nm containing about 30 wt% metalcatalysts, such as Ni and Co, were purified by oxidation with acidic KMnO4 solutionand then washed with HCl and water. The purified tubes were dried at 100�C anddispersed in DMSO by mild sonication.

2. Preparation of Nanotube-g-Carboxylic Acid/Wilkenson’s Catalyst

A Schlenk apparatus was charged with the briefly sonicated Step 1 product dispersedin DMSO and treated with the dropwise addition of 10ml of a 10mM solution ofWilkinson’s complex in DMSO. The reaction mixture was stirred at 55�C to 60�C for80 hours and filtered through a 0.2 mm nylon membrane. Dissolved tubes wereprecipitated out by treating the solutionwith saturated brine. The precipitatedmaterialwas purified by filtering over a 0.2 mm nylon membrane and washing in DMSO,ethanol, and water.

ANALYTICAL

1. Both scanning electron microscopy and atomic force microscopy of thefunctionalized multi-walled nanotubes indicated a high density of smallnanotube bundles whose diameters were on the order of 15 to 20 nm.

2. PowderX-ray diffraction indicated that the tubeswere able to coalesce togetherupon solvent removal.

3. 31P-, 13C-, and 1H � NMR spectroscopy confirmed the coordination ofWilkinson’s complex with the nanotubes.

NOTES

1. Massey [1] functionalized graphitic nanotubes including C60-fullerenes, (I),which were then used in electrogenerated chemiluminescence assays.

Gly Lys Phe Gly NH

N

N

N N

N

N

RuTrypsin Chymotrypsin

(I)

C60

334 Carbon Nanotube Adducts and Methods of Making the Same

2. Barraza [2] prepared single-walled nanotube/polystyrene composites by mini-emulsion polymerization, using surfactants, styrene, and nanotubes graftedwith varying degrees of glucosamine, (II).

O

O

O

OH

OHH2N

HO

(II)

a

References

1. R.J. Massey et al., US Patent 7,052,861 4 (May 30, 2006)2. H.J. Barraza et al., US Patent 7,153,903 (December 26,2006)

Notes 335

Title: Modification of Nanotubes by Oxidationwith Peroxygen Compounds

Author: C. Nie et al., US Patent 7,070,753 (July 4, 2006)Assignee: Hyperion Catalysis International, Inc. (Cambridge, MA)

SIGNIFICANCE

Amethodofpreventingaggregationofnanotubes isdescribed.Theprocedure entails theambient temperature introductionofcarboxylicacidsontothenanotubesubstrateusingamixture of ammonium persulfate and sulfuric acid. By this method up to 0.76meq/gcarboxylic acid was introduced onto a nanotube surface after two days.

REACTION

Nanotube

HOOCHOOC COOH

COOH COOH COOH

iNotes 1,2

i: Ammonium persulfate, sulfuric acid

EXPERIMENTAL

Oxidation was carried out by stirring the nanotubes in a mixture consisting of 1M(NH4)2S2O8 and 1M H2SO4 for between one to seven days at ambient temperature.The oxidationmixturewas prepared by dissolving (NH4)2S2O8 in 1MH2SO4 solution.The nanotube concentrations ranged from 3.247 to 15 g in 300ml of the oxidationagent mixture. During the oxidation thick nanotube slurries formed that weresubsequently filtered, washed with water, and dried; the oxidized nanotubes werethen isolated.

336

SCOPING STUDIES

Sample Preparation for Electrochemical Testing

Electrodes with a diameter of 0.5 inch were prepared by sonicating a mixture of 0.3 goxidized nanotubes with 300ml of water and 5 drops Triton X-100 using a 400Wultrasonic processor. A mat was initially prepared by drying the nanotubes at 100�C,the nanotubes were then further heated to 350�C in air for 4 hours. The final weight ofthe mat was 283mgwith a thickness of 0.0049 inch and a density of 0.41g/ml. Testingresults provided in Table 2.

NOTES

1. Nanotube oxidations using ClO2, CO2, NO, NO2, and O3 are described by theauthor [1].

2. In a subsequent investigation by the author [2] functionalized nanotubes of thecurrent invention were amidated with nylon-6 macromolecules so that the

TABLE 2. Results of electrochemical testing of oxidized nanotubes.

Entry

ElectrodeThickness(inch)

Density(g/ml)

EquivalentSeries

Resistance(ohm)

SpecificCapacitance

(F/g)

KneePoint

Frequency(Hz)

PoreResistance(ohm)

1 0.0049 0.41 0.052 46.7 150 0.0052 0.0045 0.42 0.045 49.2 154 0.0063 0.0049 0.43 0.044 44.6 150 0.0054 0.0049 0.43 0.037 45.6 151 0.005

Note: The results indicate that other than specific capacitance, which increased slightly with higher surfaceoxidation, no significant differences were detected. All electrodes had excellent frequency responses.

TABLE 1. Summary of surface oxidation of nanotubes in 300ml 1Mammonium persulfate/sulfuric acid mixture.

Entry Fibrils (g)Oxidation Duration

(days)Surface Groups

(meq/g)

1 15 2 0.732 7.521 2 0.763 7.492 1 0.524 3.247 1 0.52

Note: Oxidized nanotubes had the appearance of weathered rope with many broken andloose ends.

Scoping Studies 337

polymer composite contained between 3 and 10wt% polymer. Dai [3]modifiedamidated nanotubes of the current invention with conjugates containingoxidized-biotin-Strepavidin complexes, (I).

O

NH

HN

O S

NH

HNO

H

H Alexa Fluor Streptavidin

Nanotube (I)

3. Fisher [4] introduced sulfonic acid groups and tubular fullerenes onto graphiticnanotubes, using sulfuric acid in order to induce cyclic compounds to becomeadsorbed onto the surface.

4. Khabashesku [5] used selected peroxides to functionalize single-wall nano-tubes, as indicated below.

References

1. C. Nie et al., US Patent Application 2006-0239891 (October 26, 2006)2. C. Nie et al., US Patent Application 2006-0249711 (November 9, 2006)3. H. Dai et al., US Patent Application 2006-0275371 (December 7, 2006)4. A. Fisher et al., US Patent Application 2006-0193868 (August 31, 2006) and US Patent 6,203,814

(March 20, 2001)5. V.N. Khabashesku et al., US Patent 7,125,533 (October 24, 2006)

ENTRY REAGENT(S)INTRODUCED

FUNCTIONALITY

2 Benzoyl peroxide Phenyl

3 a-Iodoethyl acetatebenzoyl peroxide

a-Ethyl acetate

338 Modification of Nanotubes by Oxidation with Peroxygen Compounds

Title: Arylcarbonylated Vapor-Grown CarbonNanofibers

Author: L.-S. Tan et al., US Patent 7,005,550 (February 28, 2006)Assignee: The United States of America as Represented by the Secretary of the Air

Force (Washington, DC)

SIGNIFICANCE

There is a continuing need for achieving a good dispersion of single-wall carbonnanotubes to ensure high performance of these materials. To address this concern,dispersed carbonyl-functionalized nanoscale tubes have been prepared by reacting 4-(2,4,6-trimethylphenoxy)benzoic acid with vapor-grown carbon nanofibers in thepresence of polyphosphoric acid.

339

REACTION

OHO

CN

O

CO2H

i ii

O

O

O

O

O

O

O

O

iii

Nanoscale tubes

i: Benzonitrile, potassium carbonate, toluene, NMPii: Phosphoric acidiii: Vapor-grown carbon nanofiber, polyphosphoric acid, phosphorous pentoxide

EXPERIMENTAL

1. Preparation of 4-(2,4,6-Trimethylphenoxy)Benzonitrile

A 250-ml round-bottomed flask was charged with 2,4,6-trimethylphenol (44.1mmol), 4-fluoro-benzonitrile (44.1 mmol), potassium carbonate (52.8 mmol), and amixture of 100ml NMP and 60ml of toluene and then heated to 140�C for 8 hours.The mixture was filtered, the filtrate poured into 5% hydrochloric acid, and theorganic and aqueous layers separated. The organic layer was diluted with CH2Cl2and concentrated. After the light brown oily residue was freeze-dried, the productwas isolated in 97% yield.

1H-NMR (CDCl3) d 2.05 (s, 6H, CH.sub.3), 2.30 (s, 3H, CH.sub.3), 6.81 6.84 (d, 2H, Ar), 6.91 (s, 2H, Ar),7.53 7.56 (d, 2H, Ar)

13C-NMR (CDCl3) d 16.10, 20.79, 115.48, 129.07, 129.15, 129.88, 130.48, 134.25, 147.84, 150.03,161.44.

340 Arylcarbonylated Vapor-Grown Carbon Nanofibers

2. Preparation of 4-(2,4,6-Trimethylphenoxy)Benzoic Acid

A reaction flask was charged with the Step 1 product (42.0 mmol) and 100ml ofphosphoric acid and heated to 150�C for 8 hours; themixturewas then poured into 5%hydrochloric acid. The resulting precipitate was collected, dried, and dissolved inwarm heptane. The filtrate was cooled to ambient temperature, and the product wasisolated in 42% yield as a white solid, MP¼ 236–238�C.

3. Functionalization of Vapor-Grown Carbon Nanofiberwith 4-(2,4,6-Trimethylphenoxy)Benzoic Acid

A 250ml resin flask equipped with a high-torque mechanical stirrer was charged withthe Step 2 product (1.95 mmol), vapor-grown carbon nanofibers (0.50 g) havingdiameters and lengths of 100 to 200 nm and 30 to 100 mm, respectively, and 83%polyphosphoric acid. Thereafter the mixture was heated to 130�C for 3 hours, treatedwith phosphorous pentoxide (5.0 g) in one portion, and maintained at 130�C for80 hours. After cooling to ambient temperature, water was added, and the resultingprecipitate was collected and washed with diluted ammonium hydroxide. Theprecipitate was next Soxhlet extracted for three days apiece using water and thenmethanol. After drying over phosphorous pentoxide at 100�C for 72 hours at0.05mmHg, the product was isolated in 85% yield.

DERIVATIVES


NOTES

1. To increase the solubility of single-walled nanotube in selected solventsStoddart [1] noncovalently wrapped tubes with poly(2,6-pyridinyleneviny-lene)-co-[(2,5-dioctyloxy-p-phenylene)vinylene], (I).

1H-NMR (d6 -DMSO) d 2.00 (s, 6H, CH.sub.3), 2.67 (s, 3H, CH.sub.3), 6.74 6.77 (d, 2H, Ar), 6.98 (s, 2H,Ar), 7.82 7.86 (d, 2H, Ar)

13C-NMR (d6 -DMSO) d 15.80, 20.41, 113.80, 127.65, 129.69, 129.81, 130.12, 134.47, 147.95, 159.95,167.06

Elemental analysis Calcd. C, 92.63%; H, 2.36%; 0, 5.00%.Found: C, 90.93%; H, 2.82%; O, 4.89%.Calcd for VGCNF C, 100.00%Found: C, 98.67%; H, 1.10%; O, 0.20% (less than detection limit)

FTIR (KBr cm�1) 1240, 1590, 1646, 2922, 3434

Notes 341

aOC8H17

C8H17O

N

(I)

2. Hwang [2] functionalized nanocapsules with polyaniline as a method fordispersing carbon nanocapsules.

Nanocapsule

O

HN

NHa

O

NH

HN

a

O

HN

NH

a

(II)

3. Dennis [3] used end-capped nonfunctionalized nanotubes, (III), as deliveryagents for human umbilical vein endothelial cells. Carbon nanotubes closed ateither end by caps were used by Glatkowski [4] as sunscreen delivery agents.

SH SH

SH

HS

SH

SH

Nanotube

Encapsulated Tube capendothelial cells

(III)

References

1. J.F. Stoddart et al., US Patent 7,220,818 (May 22, 2007)2. G-L. Hwang et al., US Patent 7,217,748 (May 15, 2007)3. D.M. Dennis et al., US Patent 7,195,780 (March 27, 2007)4. P.J. Glatkowski et al., US Patent 7,195,754 (March 27, 2007)

342 Arylcarbonylated Vapor-Grown Carbon Nanofibers

B. Inorganic Nanotubes

Title: Polymeric and Carbon Compositionswith Metal Nanoparticles

Author: T. M. Keller et al., US Patent 7,198,771 (April 3, 2007)Assignee: The United States of America as Represented by the Secretary of the

Navy (Washington, DC)

SIGNIFICANCE

The use of transition metals containing carbon or ceramic intermediates as a methodfor preparing nanoparticles is virtually unexplored. To address this deficiency, ironthermosets and nanoparticles were prepared by pyrolysis of ferrocene-containingcompounds.

REACTION

Fe Fe

Br

Fe

ThermosetIron nanoparticles

i iiNote 1

i: 1-Bromo-3-iodobenzene, palladium acetate, phosphine, THF, pyridine, diisopro-pylamine, copper (I) iodide

ii: Phenylacetylene, palladium acetate, phosphine, THF, pyridine, diisopropylamine,copper (I) iodide

343

EXPERIMENTAL

1. Preparation of 1-(Ferrocenylethynyl)-3-Bromobenzene

A 50-ml round-bottomed flask was charged with 1-bromo-3-iodobenzene(0.114 mmol) and ethynylferrocene (2.38 mmol) and then treated with Pd(OAc)2(2.27 mmol) and PPh3 (0.341 mmol) in a mixture consisting of 25ml of THF, 5ml ofpyridine, and 5ml of diisopropylamine at 25�C. The solution was stirred at ambienttemperature for 20 minutes, treated with CuI (0.0568 mmol), and cooled to�78�C. Itwas then evacuated and backfilled with argon several times, warmed to ambienttemperature, and stirred for 16 hours at 25�C. The mixture was concentrated, theresidue purified using hexane/CH2Cl2 a 5:1, respectively, and the product isolated in92% as an orange-red solid, MP¼ 130�C.

2. Preparation of 1-(Ferrocenylethynyl)-3-(Phenylethynyl)benzene

A 50-ml round-bottomed flask was charged with the Step 1 product (1.37 mmol) andphenylacetylene (0.0686 mmol) and then treated with Pd(OAc)2 (15.4mg) and PPh3(53.9mg) in 25ml of THF, 5ml of pyridine, and 5ml diisopropylamine at 60�C. It wasstirred at ambient temperature for 20 minutes, treated with CuI (0.0568 mmol), andcooled to�78�C. The mixture was evacuated and backfilled with argon several timesand then warmed to ambient temperature and stirred for 16 hours at 25�C. It wasconcentrated, the residue purified using hexane/CH2Cl2 a 5:1, respectively, and theproduct isolated in 92% as an orange-red solid, MP¼ 181�C.

3. Preparation of Thermoset

The Step 2 product was placed into a TGA boat and polymerized by heatingunder a nitrogen atmosphere at 225�C for 5 minutes, 300�C for 30 minutes, and at350�C for 30 minutes. The solid was then cooled, and a solid black material wasisolated.

4. Carbonization of 1-(Ferrocenylethynyl)-3-(Phenylethynyl)Benzene

The Step 3 product was further heated in a TGA boat from 300�C to 1000�C at10�C/min under a nitrogen atmosphere, which resulted in a char yield of 86%. In the

IR (cm�1, KBr): 3111 (C–H), 3097 (C–H), 2212 (C–C), 1597 (C¼C, benzene), 1570 (C¼C, benzene), 1491(C¼C, benzene), 1411 (C¼C, ferrocene)

1HNMR (CDCl3): d 7.67 (m, 1H), 7.53 (m, 2H), 7.44 (m, 2H), 7.34 (m, 3H), 7.29 (t, J¼ 7.8Hz, 1H), 4.50(t, J¼ 1.8Hz, 2H), 4.24 (m, 7H)

Analysis C26H18Fe) Calcd: C, 80.84%; H, 4.70%. Found: C, 80.31%; H, 4.63%.

IR (cm�1, KBr): 3094 (C–H), 3057 (C–H), 2204 (C.ident.C), 1591 (C¼C, benzene), 1583 (C¼C, benzene),1552 (C¼benzene), 1411 (C¼C, ferrocene)

1HNMR (CDCl3): d 7.63 (t, J¼ 1.7Hz, 1H), 7.41 (m, 2H), 7.17 (t, J¼ 7.8Hz, 1H), 4.50 (t, J¼ 1.9Hz, 2H),4.25 (t, J¼ 1.9Hz, 2H), 4.24 (s, 5H)

Analysis C18H13FeBr Calcd: C, 59.22%; H, 3.59%. Found: C, 59.15%; H, 3.84%

344 Polymeric and Carbon Compositions

heat processing the Step 3 product lost 9%of its weight between 400�Cand 600�Cand5% between 600�C and 1000�C, resulting in carbonization and the formation of ironnanoparticles. The iron nanoparticle carbon compositionwas attracted to a permanentmagnet, indicating ferromagnetic behavior.

DERIVATIVES

Additional Step 2 derivatives, (I)–(III), were prepared and converted into thermosetsand iron nanoparticles as are illustrated below.

FeBr

FeFe

Fe

Fe

(I) (II)(III)

NOTES

1. In a subsequent investigation by the author [1] a pyrolysis of siloxane-ferrocenepolymers, (IV), was used to prepare ceramic materials.

Fe

Si

Si

O Si CB10H10C Si O Si

OSiCH10B10CSiOSi

a

(IV)

2. Titanium oxynitride nanoparticles were prepared by Gole [2] and used insolar cells and as a semiconductor-based photocatalytic component in fuelcells.

3. Nanoparticles containing Fe2O3 were prepared by Li [3] and incorporated intocigarette filters as a method of lowering the amount of carbon monoxide and/ornitric oxide in inhaled tobacco smoke.

4. Peng [4] prepared monodispersed nanoparticles between 1 and 20 nm consist-ing of gold, silver, copper, and platinum, which were used as high efficiencyindustrial catalysts.

5. McCormick [5] prepared thiol-stabilized nanoparticles containing gold, plati-num, palladium, rhodium, ruthenium, osmium, and iridium,whichwere used inoptics, immunodiagnostics, and electronics.

Derivatives 345

References

1. T.M. Keller et al., US Patent Application 2007-0073038 (March 29, 2007) and US Patent Application2007-0073036 (March 29, 2007)

2. J.L. Gole et al., US Patent 7,186,392 (March 6, 2007)3. P. Li et al., US Patent 7,168,431 (January 30, 2007)4. X. Peng et al., US Patent 7,160,525 (January 9, 2007)5. C.L. McCormick III et al., US Patent 7,138,468 (November 21, 2006)

346 Polymeric and Carbon Compositions

Title: Metal Oxide Nanotube and Processfor Production Thereof

Author: T. Shimizu et al., US Patent 7,172,747 (February 6, 2007)Assignee: National Institute of Advanced Industrial Science and Technology

(Tokyo, JP)

SIGNIFICANCE

Spiral shaped hollow nanofibers were formed from the reaction of p-aminophenyl-b-D-glucopyranoside and p-dodecanoylaminophenyl-b-D-glucopyranoside with ex-cess tetraethoxysilane. Thediameter distributions of these tubes ranged from1 to 2 nmand from 3 to 7 nm. Metal oxide nanotubes derived from this process displayedexcellent hydrogen adsorption and storage capacity for potential use in hydrogen-powered vehicles.

REACTION

O

OH

HOOH

OHO NO2

O

OH

HOOH

OHO NH2

i ii O

OH

HOOH

OHO

HN

O10

iii

Silicon oxide nanotube cluster

Notes 1,2

i: Palladium on carbon, THF, methanol, hydrogenii: Lauroyl chloride, triethylamineiii: p-Aminophenyl-b-D-glucopyranoside, water, methanol, tetraethoxysilane,

benzylamine

347

EXPERIMENTAL

1. Preparation of p-Aminophenyl-b-D-Glucopyranoside

p-Nitrophenyl-b-D-glucopyranoside (250mg)was dissolved in 20ml ofmethanol and5ml of THF and 10% palladium on carbon (250mg) added to the solution. Hydrogengas was introduced into the solution at ambient temperature for 3 hours. The mixturewas then filtered and the solvent evaporated. The solid residue was purified by silicagel chromatography using THF/CCl3H, 1:1, and the product was isolated in 80% to90% yield.

2. Preparation of p-Dodecanoylaminophenyl-b-D-Glucopyranoside

The Step 1 product (250mg) was dissolved in 20ml of THF, treated with lauroylchloride (300mg) and triethylamine (1.0 g), and refluxed for 5 hours. The solutionwasfiltered to remove solids, and the filtratewas concentrated under vacuum. The residuewas purified using silica gel chromatography with methanol/CCl3H, 1:1, and theproduct was isolated in 80% yield.

3. Preparation of Metal Oxide Nanotubes

Three milligrams apiece of the Step 1 and Step 2 products were dissolved in 10ml ofwater and 1ml of methanol by heating the solution to 70�C. This mixture was thentreated with tetraethoxysilane (20mg) followed by benzylamine (6mg). A gel thatformed during gradual cooling of the mixture stood uninterrupted at ambienttemperature for sevendays. The samplewas then sintered in a nitrogengas atmospherefirst for two hours at 200�C and then for four hours at 500�C, and metal oxidenanotubes were isolated.

ANALYTICAL

1. Themetal oxide nanotubeswere analyzed by scanning electronmicroscopy andfield emission scanning electron microscopy, which indicated the presence of adouble helix.

2. Hydrogen adsorption–desorption isothermal curves for the double-spiral silicananotubes and cylindrical silica were not provided by the author.

1H-NMR (300MHz,CCl3H): d¼ .¼ 0.9 (t, 3H), 1.5 3.0 (m, 15H), 3.50 4.13 (m, 6H); 4.76 (s, 2H), 5.25 5.31(m, 3H), 5.63 (s, 1H), 6.70 (d, J¼ 9.0Hz, 2H), 6.98 (d, J¼ 9.0Hz, 2H), 7.30 (d, 2H)

FT-IR (KBr, cm�1)¼ 3340, 2912, 1630, 1510, 1364, 1217, 1089, 1005, 1035, 999, 806, 706MS (NBA): m/z: 452.27 [MþH]

1H-NMR (300MHz, DMSO-d6): d¼ 3.44 4.10 (m, 6H), 4.76 (s, 2H), 5.25 5.31 (m, 3H), 5.60 (s, 1H), 6.70(d, J¼ 9.0Hz, 2H), 6.95 (d, J¼ 9.0Hz, 2H), 7.37 7.46 (m, 5H)

FT-IR (KBr, cm�1)¼ 3312, 2909, 1635, 1510, 1364, 1217, 1089, 1005, 1035, 999, 806, 706MS (NBA): m/z: 360 [MþH]

348 Metal Oxide Nanotube and Process for Production Thereof

NOTES

1. When hexylamine was used in place of benzylamine in Step 3, double–spiralsilica nanotubes were also obtained.

2. Kornilovich [1] prepared linear aliphatic-, (I), and dimethylsiloxy-functiona-lized silicon oxide nanowire designed to adsorb and store up to 6.5% hydrogen.

Silicon oxide nanowireAdsorbed hydrogen

Grafted linear aliphatic chain

(I)

3. Kiang [2] prepared single-walled nanotubes consisting of up to 30% metallicbismuth and cobalt, which were thread-like at ambient temperatures andpressures. The synthetic method entailed heating a mixture of 90% graphitepowder and 5% apiece of cobalt catalyst and bismuth co-catalyst in an electricarc.

4. Zhang [3] prepared iridium oxide nanotubes using metal-organic chemicalvapor deposition with (methylcyclopentadienyl)(1,5-cyclooctadiene) iridium,(I), followed by heating from 200�C to 500�C.

5. Bronikowski [4] used poly(styrene-b-methylmethacrylate) to form iron-richand iron-deficient nanowires. In this process poly(styrene-b-methylmethacry-late) and FeCl3 were dissolved in acetone and then spin-coated onto a substrateand heated so that the block copolymer formed pillars of PMMA in a PSmatrix.Under these conditions Fe3þ migrated to the more polar PMMA region. Oncethis composite was heated, single-wall carbon and iron-rich nanotubes wereformed.

6. Olesik [5] prepared high-yield low-dispersity nanospheres using self-polymerizing end-capped 1,8-dihydroxymethyl-1,3,5,7-octatetrayne by heat-ing to 70�C for 24 hours using 0.04 wt% phenyltrimethyl amine chloride as thesurfactant.

7. Methods for monitoring the amount of adsorbed hydrogen on palladiummesowire are described by Monty [6] and Penner [7].

Notes 349

References

1. P. Kornilovich,US Patent 7,135,057 (November 14, 2006)2. C.-H. Kiang US Patent 7,112,315 (September 26, 2006)3. F. Zhang et al., US Patent 7,098,144 (August 29, 2006)4. M.J. Bronikowski et al., US Patent 7,115,305 (October 3, 2006)5. S.V. Olesik et al., US Patent Application 2006-0223947 (October 5, 2006)6. G. Monty et al., US Patent 7,104,111 (September 12, 2006)7. R.M. Penner et al., US Patent Application 2003-0079999 (May 1, 2003)

350 Metal Oxide Nanotube and Process for Production Thereof

C. Nanotube Dispersant

Title: Methods for the Synthesis of Modular Poly(Phenyleneethynlenes) and Fine-Tuning the ElectronicProperties Thereof for the Functionalizationof Nanomaterials

Author: H. Ait-Haddau et al., US Patent Application 2006-0054866 (March 16, 2006)Assignee: Zyvex Corporation (Richardson, TX)

SIGNIFICANCE

Carbon nanotubes have limited solubility in most organic solvents. Phenylene-ethynylene derivatives have been prepared and used to noncovalently functionalizeand solubilize these materials by means of the electron donor/electron acceptorcharacteristics of the polymer backbone.

351

REACTION

aa

OH

OH

OC10H21

OC10H21

OC10H21

C10H21O

I I

OC10H21

C10H21O

(H3C)3Si Si(CH 3)3

OC10H21

C10H21O

i ii iii

iv

Intermediate

Br

Br

CO2H

HO2C

Br

Br

COCl

ClOC

Br

Br

COO-t-C 4H9

t-C4H9-OOCIntermediate

v vi vii

OC10H21 COO-t-C 4H9

C10H21O t-C4H9-OOC

OC10H21 CO2H

C10H21O HO2C

viii

i: 1,4-Hydroquinone, potassium carbonate, acetonitrile, 1-bromodecaneii: Potassium iodate, acetic acid, water, sulfuric acid, sodium thiosulphateiii: Diisopropylamine, copper (I) iodide, dichlorobis(triphenylphosphine)palla-

dium(II), trimethyl-silylacetyleneiv: Methanol, potassium hydroxidev: Oxalyl chloride, DMFvi: THF, t-butanol, pyridine, CH2Cl2vii: Toluene, diisopropylamine, tetrakistriphenylphosphine palladium, copper(I)

iodideviii: Water, potassium hydroxide, toluene, ethanol

EXPERIMENTAL

1. Preparation of 1,4-Didecyloxybenzene

Aflaskwas chargedwith 1,4-hydroquinone (0.4mol),K2CO3 (1.2mol), and 500ml ofacetonitrile and then treated with 1-bromodecane (1.0mol). This solution wasrefluxed for 48 hours and poured while hot into a flask containing 1.5 liter water.The beige precipitate was collected by filtration using a Buchner funnel, washedwith 1.0 liter water, and dried. The solid was dissolved in 250ml of hot hexanes andre-precipitated in 1.5 liter of ethanol. The solid was then washed with cool ethanol,dried, and the product was isolated in 97% yield as a fluffy white solid.

1HNMR (CDCl3) d 6.83 (s, 4H), 3.92 (t, J¼ 6.6Hz, 4H), 1.73 (m, 4H), 1.45 (m, 4H), 1.30 (m, 22H), 0.91(t, J¼ 6.7Hz, 6H).

352 Methods for the Synthesis of Modular Poly(Phenyleneethynlenes)

2. Preparation of 1,4-Didecyloxy-2,5-Diiodobenzene

A reaction vessel was charged with potassium iodate (0.066mol), iodine (0.132mol),700ml of acetic acid, 50ml of water, and 15ml of sulfuric acid and then treated withthe Step 1 product (0.132mol) and refluxed for 8 hours. The purple solution wascooled to ambient temperature and treated with a 100ml saturated solution of sodiumthiosulphate. The beige-brown precipitate was collected by filtration, washed with700ml ofwater and 500ml of ethanol, and dried. This solidwas dissolved in 300ml ofhot hexanes and precipitated in 1.5 liter of ethanol. The precipitate was collected byfiltration, washed with 1.0 liter ethanol, and dried; the product was isolated in 92%yield as a white solid.

3. Preparation of 1,4-Didecyloxy-2,5-bis-(Trimethylsilylethynyl)Benzene

A reaction vessel containing 1.5 liter of diisopropylamine was treated with the Step 2product (0.1557mol), CuI (7.78 mmol), and dichlorobis(triphenylphosphine)palladi-um(II) (7.78 mmol). The mixture was stirred for 10 minutes and then treated with theslow addition of trimethylsilylacetylene (0.342mol) at ambient temperature andrefluxed for 8 hours. After cooling, the mixture was diluted with 500ml of hexanes,filtered through a 4 cm silica gel plug, concentrated, and precipitated in 3.0 liter ofCCl3H/ethyl alcohol, 1:1. The solid was filtered, washed with 250ml apiece of waterand ethanol, and dried; the product was isolated in 91% yield.

4. Preparation of 1,4-Diethynyl-2,5-Didecyloxybenzene

Aflaskcontaining200mlofmethanol and120mlof20%KOHwasadded to theStep3product (137.21mmol) dissolved in 500ml of THF at ambient temperature and stirredovernight. The solution was concentrated, and the residue was diluted with 400ml ofethanolwhereupon a yellow solid formed. The solid was isolated, washedwith 250mlethanol, and dried; the product was isolated in 99.7% yield as a yellow solid.

5. Preparation of 1,4-Dibromo-2,5-Dicarboxylic Acid Chloride Benzene

At ambient temperature oxalyl chloride (1.244mol) was slowly added to a suspensionof the dibromo acid (0.518mol) in CH2Cl2. Thismixturewas then treatedwith several

1HNMR (CDCl3) d 6.96 (s, Ph, 2H), 3.98 (t, J¼ 6.58Hz,OCH2, 4H), 3.34 (s, CCH, 2H), 1.82 (m,CH.sub.2,4H), 1.52 (m, CH2, 4H), 1.31 (m, CH2, 22H), 0.88 (t, J¼ 6.71Hz, CH3, 6H)

13CNMR (CDCl3) d 153.9, 117.7, 113.2, 82.4, 79.7, 69.6, 31.9, 29.5, 29.3, 29.1, 25.9, 22.6, 14.1

1HNMR (CDCl3) d 7.21 (s, Ph, 2H), 3.94 (t, J¼ 6.4Hz, OCH2, 4H), 1.82 (m, CH2, 4H), 1.47 (m, CH.sub.2,4H), 1.29 (m, CH2, 22H), 0.90 (t, J¼ 6.72Hz, CH3, 6H)

13CNMR (CDCl3) d 152.8, 122.7, 86.2, 70.3, 31.9, 29.5, 29.3, 29.2, 29.1, 26.0, 22.6, 14.1.

1HNMR (CDCl3) d 6.85 (s, Ph, 2H), 3.93 (t, J¼ 6.4Hz,OCH2, 4H), 1.78 (m,CH2, 4H), 1.27 (m,CH2, 22H),0.88 (t, J¼ 6.42Hz, CH.sub.3, 6H), 0.26 (s, 18H)

13CNMR (CDCl3) d 154.0, 117.2, 113.9, 101.0, 100.0, 69.4, 31.9, 29.6, 29.5, 29.4, 29.3, 26.0, 22.6, 14.1,0.17.

Experimental 353

drops of dryDMFand refluxed for 12 hours.After themixturewas concentrated to halfits original volume, it was treated with 500ml of hexanes. A pale yellow precipitateformed, which was isolated and washed with 250ml of hexanes, and the product wasisolated in 98.8% yield.

6. Preparation of 1,4-Dibromo-2,5-t-Butoxycarboxybenzene

A solution of the Step 5 product (272.72 mmol) dissolved in 25ml of THF was addedover 45 minutes to a solution of t-butanol (110.9 mmol) and pyridine (110.9 mmol) in100ml of CH2Cl2 at 5

�C. The reaction mixture was gradually warmed to ambienttemperature, stirred overnight, and then concentrated. The residue was diluted with a100ml mixture of water/methanol, 1:1, whereupon a white precipitated formed. Theprecipitatewaswashedwith 100ml 1.8MKOHand 100ml of cooledwater/methanol,1:1, dried, and the product was isolated in 76% yield.

7. Preparation of Poly[1,4-Dibromo-2,5-t-Butoxycarboxybenzene)-co-(1,4-Diethynyl-2,5-Didecyloxybenzene)Phenyleneethynylene]

A flask was charged with 35ml of toluene/diisopropylamine, 3:2, respectively,the Step 4 product (1.964 mmol), the Step 6 product (1.785 mmol), (Ph3P)4Pd(1 mol%), and CuI (2.5 mol%). The mixture was then stirred at ambient temperaturefor 30 minutes, warmed to 70�C for 90 minutes, and then added to a flask containing250ml of the stirring methanol. This mixture was stirred for 2 hours at ambienttemperature and an orange precipitatewas isolated. The solidwaswashedwith 100mlof amethanol/ammoniumhydroxide solution, 1:1, 100ml ofmethanol, and thendried,and 1.25 g product was isolated as an orange solid. The polymer repeat unit wasestimated by 1H � NMR to be approximately 60 with a polydispersity index of about1.4 as determined by GPC.

8. Preparation of Poly[1,4-Dibromo-2,5-Hydroxycarboxybenzene)-co-(1,4-Diethynyl-2,5-Didecyloxybenzene)Phenyleneethynylene]

Potassium hydroxide (1.0 g) was dissolved in a mixture of 30ml of refluxing toluene/ethanol, 1:1, and then treated with the Step 7 product (1.0 g) and refluxed 3 hours. Themixture was next treated with 10ml of water, refluxed an additional 24 hours, cooled,and filtered, and the filtrate was acidified using 3M HCl. An orange precipitate wasisolated, washed with 100ml of water, and dried, and 0.75 g of product was isolated.The product was soluble in diethyl ether, THF, DMF, acetone, methyl ethyl ketone,isopropyl alcohol, methanol, ethanol, and related solvents having pH> 8.

DERIVATIVES

A second donor/acceptor phenyleneethynylene derivative was also prepared.


a

C10H21O

OC10H21

O

OO

O

O

OO

O O O

NOTES

1. Smalley [1] solubilized and separatedmetallic nanotubes by initially dispersingthese materials with polyvinyl pyrrolidone or polyvinyl pyrrolidone copoly-mers and then separating them by electrophoresis.

2. Wise [2] prepared selected polyimides, (I), that formed dispersions of carbonnanotubes exhibiting long-term stability. Nanocomposites produced fromthese dispersions were useful in the fabrication of lightweight aerospacestructures.

O

CN

ON

O

O

O

N

O

O

n

(I)

3. Diner [3] demonstrated that RNA-dispersed carbon nanotubes were morereadily oxidized than those dispersed in Triton� X405, a non-ionic surfactant.

4. Blanchet-Fincher [4] determined that when carbon nanotubeswere dispersed ina conductive polyaniline matrix, fewer nanotubes were needed to increaseelectrical conductivity.

Notes 355

References

1. R.E. Smalley et al., US Patent 7,074,310 (July 11, 2006) and US Patent Application 2006-0231399(October 19, 2006)

2. K.E. Wise et al., US Patent Application 2006-0270777 (November 30, 2006)3. B.A. Diner et al., US Patent Application 2005-0232844 (October 20, 2005)4. G.B. Blanchet-Fincher, US Patent Application 2005-0165155 7,169,535 (July 28, 2005)


XVI. NEW SYNTHETIC METHODS

A. Compounds

a. 18F-Fluorobromomethane

Title: Solid-Phase Preparation of [18F]Fluorohaloalkanes

Author: F. Brady et al., US Patent 7,223,891 (May 29, 2007)Assignee: Hammersmith Imanet, Ltd. (London, GB)

SIGNIFICANCE

An eight-step method for the solid-phase preparation of 18F-fluoro-bromoalkanes isdescribed.


357

REACTION

I

F2C

CF2

F2C

CF2

IClO2S

F2C

CF2

F2C

CF2

SO2ClKO3S

F2C

CF2

F2C

CF2

SO3K

HO3S

F2C

CF2

F2C

CF2

SO3HF2C

O2SO

SO2

CF2

CF2F2C

N

O2S

CF2

F2C

CF2

F2C

SO3Na

N

O2S

CF2

F2C

CF2

F2C

SO2Cl N

O2S

CF2

F2C

CF2

F2C

SO2

O Br

18FCH2Br

i ii

iiiivv

vi vii viii

aa

a

i: Sodium dithionite, sodium hydrogen sulphate, water, acetonitrile, chlorine gasii: Potassium hydroxide, wateriii: Water, Amberlyst 15 resiniv: Phosphorous pentoxidev: Polystyrene resin, di-isopropyethyl aminevi: Phosphorous pentachloride, CH2Cl2vii: Bromomethanol, THFviii: Acetonitrile, kryptofix, potassium carbonate, and [18F]-fluoride

EXPERIMENTAL

1. Preparation of Perfluorobutane-1,4-bis-Sulphonylchloride

A mixture consisting of 1,4 diiodoperfluorobutane (53.2mmol), sodium dithionite(117.2mmol), and sodium hydrogen sulphate (152.4mmol) in 36ml apiece of waterand acetonitrile was stirred 2 hours at ambient temperature and then filtered. Thefiltratewas concentrated, and the residuewas added to 100mlwater. The solutionwasthen treatedwith chlorine gas at 0�Cuntil the color of iodine disappeared. Themixturewas extracted with 100ml of CH2Cl2, and the organic phase was washed with water,dried, and concentrated. After re-crystallization from hexane the product was isolatedas off-white needles.

19 F NMR (CDCl3) d �104.4, �119.1.

358 Solid-Phase Preparation of [18F] Fluorohaloalkanes

2. Preparation of Perfluorobutane-1,4-bis-Sulphonate Dipotassium Salt

A solution of potassium hydroxide (5 eq) in 19ml ofwater was reactedwith the Step 1product (35mmol) at 85�Cto90�Cfor4hours. Itwas cooledovernight and filtered; thesolids were washed with cooled water and dried, and the product was isolated.

3. Preparation of Perfluorobutane-1,4-bis-Sulphonic Acid

The Step 2 product (34.2mmol) was dissolved in 100ml of hot water and added to anion exchange column containing an Amberlyst 15 resin. The column was slowlywashedwith distilledwater and the first 300ml of aqueous solutionwas collected. Thesolution was concentrated, the residue dried, and the product isolated in 88% yield.

4. Preparation of Perfluorobutane-1,4-bis-Sulphonic Acid Anhydride

The Step 3 product (�30mmol) was mixed with P2O5 (10 eq), heated to between140�C and 180�C, and distilled under reduced pressure. The crude product wasisolated by distillation and purified by re-distillation.

5. Preparation of Polystyrene-g-(Benzyl-Ethyl-Sulfonamide)Octafluoro-Butane-1-Sulfonic acid

The polystyrene resin (202mg) previously swollen in 2ml of CH2Cl2 and thensuspended in 2ml of CH2Cl2 was treated with the Step 4 product (5 eq) and 0.174mldi-isopropyethyl amine and stirred overnight at ambient temperature. The solventwasremoved by filtration and the resin was washed with consecutive additions of 5mlapiecewithCH2Cl2,methanol,DMF,water,methanol, andCH2Cl2.The resinwas thentreated twice with 2ml of 1M NaOH in THF and water before washing withconsecutive 5ml portions of methanol, CH2Cl2, and methanol. The product wasisolated after drying under high vacuum.

6. Preparation of Polystyrene-g-(Benzyl-Ethyl-Sulfonamide)Octafluoro-Butane-1-Sulfonyl Chloride

Aportion of the Step 5 productwas swollenwith 2ml ofCH2Cl2, washed consecutivelywith5mlof1MHCl, and10 timeswith 5ml ofTHFandwater togive the free sulphonicacid. The resinwas thenwashed consecutivelywithCH2Cl2,methanol, andTHFbeforedryingunder highvacuum.Thematerialwas then suspended inCH2Cl2 and treatedwithexcess phosphorous pentachloride.Themixturewas suspended for 2 hours, filtered, andwashed with CH2Cl2, and THF, and the product was isolated.

19 F NMR [gel phase] d �121.0, �114.8, �113.4

19 F NMR (CDCl3) d �114.00, �120.111 H NMR (CDCl3) d 8.00

19 F NMR (CDCl3) d �114.7, �121.3.

19 F NMR (CDCl3) d �105.7, �121.8.

Experimental 359

7. Preparation of Polystyrene-g-(Benzyl-Ethyl-Sulfonamide)Octafluoro-Butane-1-Sulfonyl Bromomethane

A solution of bromomethanol dissolved in THF was added to a portion of the Step 6product previously swollen in THF. The mixture was then treated with potassiumt-butoxide dissolved in THF, and the suspension was stirred overnight at ambienttemperature. The mixture was next filtered, the resin washed consecutively withCH2Cl2 and THF, and dried, and the product was isolated.

8. Preparation of 18F-Fluorobromomethane

A cartridge was charged with the Step 7 product dissolved in acetonitrile containingkryptofix, potassium carbonate, and [18F]-fluoride. The mixture was then heated to85�C for 10 minutes and filtered. The solution was passed onto a C18 solid-phaseextraction cartridge and washed with water to remove acetonitrile, kryptofix, andpotassium carbonate. Additional acetonitrile was used to wash the radiofluorinatedagent off the extraction cartridge, and the product was isolated.

NOTES

1. Solid-phase electrophilic fluorination was previously used by Luthra [1] toprepare an 18F-L-dopa analogue, (I), for the in situ release of 18F-L-fluorodopa.

18F OH

OH

HO2CNH2

(I)

2. Sn2 displacement of the corresponding tosylate intermediate with 18F anionwas used by Mertens [2] and Chen [3] to prepared 18F-Alanine, (II), and18F-tyrosine, (III), derivatives, respectively.

CO2H

NH2

18F

(II)

CO2H

NH2

O18F

(III)

360 Solid-Phase Preparation of [18F] Fluorohaloalkanes

References

1. S.K. Luthra et al., US Patent 7,115,249 (October 3, 2006)2. J.J.R. Mertens, US Patent 7,189,383 (March 13, 2007)3. J.T. Chen et al., US Patent 7,138,540 (November 21, 2006)

Notes 361

b. Nitrogen Heterocyclics

Title: Vinyl Sulphone Modified Polymer

Author: D. Gani et al., US Patent 7,183,367 (February 27, 2007)Assignee: N.V. Organon (Oss, NL)

SIGNIFICANCE

Atwo-stepmethod for the combinatorial synthesis ofamines and aminoalcohols usingvinylsulfomethylpolystyrene is described. This solid-phase synthetic route requiresvery few reagents for the permutational synthesis of new heterocyclic aminederivatives.

REACTION

Cl SOH

SO2

OH

SO2

Br

SO2

N

SO2

NN

O

i ii iii

iv

v

+

Merrifield resin

Br_

Notes 1,2

SO2

Not isolated

vi

SO2

NN

OH

SO2

N NN

OH

SO2

++

viii

vii

362

i: 2-Hydroxyethanethiol, potassium carbonate, pyridine, DMFii: 3-Chloroperbenzoic acid, CH2Cl2iii: Phosphorous tribromide, CH2Cl2iv: Tetrahydroquinoline, allyl bromide, DMFv: Potassium carbonatevi: DMF, 4-piperazinoacetophenonevii: Phenylmagnesium bromide, THFviii: Potassium carbonate

EXPERIMENTAL

1. Preparation of 2-Hydroxyethyl-Thiomethyl-Polystyrene

A slurry of the Merrifield resin (2.9mmol) in 20ml of dry DMF was treated with2-hydroxy-ethanethiol (15.25mmol),K2CO3 (14.5mmol), and pyridine (12.9mmol),and the suspensionwas stirred for 4 hours at 95�C. It was then left stirring overnight at20�C. The resinwas filtered andwashed extensivelywithDMF,CH2Cl2, water, water/methanol, 1:1, andmethanol. Thematerialwas dried under vacuumat 50�Cand 3.92 gof product were isolated.

2. Preparation of 2-Hydroxyethyl-Sulfomethyl-Polystyrene

The Step 1 product (0.7mmol) in CH2Cl2 was treated with 3-chloroperbenzoic acid(5.2mmol) and the suspensionwas heated at 35�C for a brief period and then stirred at20�Cfor 2days.After filtration the resinwaswashedwithDMF,CH2Cl2,water,water/methanol, 1:1, and finally methanol. After drying at 50�C under vacuum, 1.51 g ofproduct was isolated.

3. Preparation of 2-Bromoethyl-Sulfomethyl-Polystyrene

The Step 2 product (0.65mmol) suspended in 25ml of dry CH2Cl2 was treated withPBr3 (2.28mmol) at ambient temperature for 12 hours and then filtered, washed with200ml of CH2Cl2, and air dried, and the product was isolated.

FTIR (cm�1) in KBr): 1727 (m), 1600, 1491, 1450 (st, polystyrene), 1320, 1119 (st, SO2)

FTIR (cm�1) in KBr): 3450 (br, OH), 1601, 1493, 1453 (st, polystyrene), 1060 (m), 1027 (m)Sulfur analysis: 2.12% (max 2.24%)

FTIR (cm�1) in KBr): 3511 (br, OH), 1601, 1493, 1453 (st, polystyrene), 1317, 1119 (st, SO.sub.2), 1061(m), 1029 (m).

Sulfur analysis: 2.76% (max 2.19%)

Experimental 363

4. Preparation of Vinylsulfomethylpolystyrene and N-AllylTetrahydroisoquinoline HBr

TheStep3productwasmixedwith20mlofDMF, and tetrahydroquinoline (5.7mmol)wasadded.Themixturewasstirredat ambient temperature for24 hours.After filtering,the material was washed with DMF, methanol, CH2Cl2, and methanol and then dried.Thismaterial (0.5mmol)wasre-suspended in10mlofDMF, treatedwithallylbromide(150mm) and stirred 5 days at ambient temperature. It was then filtered and washedwith 100ml apiece of DMF and CH2Cl2. It was further treated with di-isopropylethylamine (1.00mmol) in 25ml of CH2Cl2 and stirred 2 days at ambient temperature. Thesolid was isolated by filtration and then washed with CH2Cl2 and methanol; 59%analytical pure product was isolated.

5. Preparation of N-Allyl Tetrahydroisoquinoline

The Step 4 product was liberated from its HBr salt by treatment with 10ml of a 2MK2CO3 solution and then extracted using EtOAc. The organic layer was dried usingK2CO3, filtered, and concentrated; the product was isolated in 68% yield.

6. Preparation of Sulfomethyl-2-(40-Piperazinoacetophenone)Ethyl-Polystyrene

The Step 3 product (0.36mmol) slurried in 5ml of DMF was treated with4-piperazino-acetophenone (0.47mmol) and agitated on a tube rotator for 24 hours.The resin was drained, washed with DMF, CH2Cl2, and methanol, and 278mg ofproduct were isolated.

7. Preparation of Sulfomethyl-2-[4-Piperazino-4-(a-Methyl-a-Phenyl-Benzylalcohol-)]Ethylpolystyrene

Aslurry of the Step 6 product (0.36mmol) in 5ml of dryTHFwas treatedwith 0.36mlof 1M phenyl-magnesium bromide in THF at 0�C and then stirred for 2 hours atambient temperature. The mixture was next quenched with 5ml of 50% aqueousNH4Cl, and the material isolated. The resin was washed four times with water, THF,CH2Cl2, and methanol and then dried; the product was isolated in quantitative yield.

FTIR (KBr cm�1): 3450 (vst, OH), 1600 (st, polystyrene), 1310, 1139 (st, SO2)

1H-NMR (d 300MHz, CDCl3): 12 (s, br, 1H, HBr), 7.30 7.08 (m, 4H, aromatics), 6.33 (ddt, 1H, Jcis¼10.0Hz, Jtrans¼ 17.15Hz, J¼7.14Hz, CH2�CH¼CH2), 5.61 5.5 (m, 2H, CH2—CH¼CH2),4.35 (br m, 2H, N�CH2-Ph), 3.76 (d, 2H, 3J¼7.14Hz, CH2�CH¼CH2), 3.42 (br m, 4H,N�CH2�CH2-Ph)

13C-NMR (d 74.76MHz, CDCl3): 130.54, 129.13 (.sup.2C, .sup.7C), 128.78, 127.74, 127.05, 126.44,126.38, 126.25 (remaining aromatics and double bond), 57.53 (N�CH.sub.2-Ph), 51.43(N�CH2�CH.dbd.CH2), 48.33 N�CH2— CH2-Ph), 24.22 (N�CH2�CH2-Ph)

Elemental analysis Found C, 56.57; H. 6.57; N, 5.42%. C12H16BrN requires C, 56.71; H, 6.34; N, 5.51%MS m/z (CI) 174 (M.sup.þ-Br.sup.�, 100%).FTIR (KBr cm�1): 1651 (st, C¼O), 1597, 1491, 1449 (st, polystyrene), 1305, 1114 (st, SO2)

364 Vinyl Sulphone Modified Polymer

8. Preparation of N-Allyl-4-Piperazino-4-(a-Methyl-a-Phenyl-Benzylalcohol)

The Step 7 product was treated with Na2CO3 and the product isolated after beingworked up according to the Step 5 procedure.

DERIVATIVES

The following derivatives utilized hydroxymethyl polystyrene as the polymericsubstrate in preparing N-allyl derivatives.

O SO2

X

Cl

N

N

CO2C2H5

X

NOTES

1. Polymer-benzyl vinyl sulfone could either be trapped in situ or isolated andreacted separately.

2. The preferred dehydrohalogenation reagent was diisopropylethylamine.

3. In an earlier investigation by the author [1] polystyrene-g-acrylamide, (I), wasused in the combinatorial synthesis of heterocyclic amines as illustrated below.

HN

O

HN

O

N

CO2C2H5

HN

O

N

CO2C2H5

NO2

N

CO2C2H5O2N

iii

iii

(I)

Br+ _

i: 4-Piperidinecarboxylic acid, ethyl ester, DMFii: 4-Nitrobenzyl bromide, DMFiii: THF, diethanolamine

Notes 365

4. Vaultier [2] prepared functionalized oxonium salts, (II), as soluble supports forpreparing the higher amino acid intermediate, (III). In an earlier investigationfunctionalized soluble oxonium salts prepared by Vaultier [3] were used inDiels-Adler, trans-esterification, trans-amidation, Heck, and Suzuki reactions.

(H3C)HN OH (H3C)HN O

XO

aa a = 0–3

X X

+

_

+

_= Cl, BF4, PF6

(II) (III)

_

References

1. D. Gani et al., US Patent 6,486,354 (November 26, 2002) and US Patent Application 2003-0138846(July 24, 2003)

2. M. Vaultier et al., US Patent Application 2007-0043234 (February 22, 2007)3. M. Vaultier et al., US Patent Application 2006-0128996 (June 15, 2006)

366 Vinyl Sulphone Modified Polymer

c. Nonsymmetrical Peroxides

Title: Ketone Peroxide Derivatives,Their Preparation and Use

Author: A. G. Van De Bovenkamp-Bouwman et al., US Patent 7,078,553(July 18, 2006)

Assignee: Akzo Nobel N.V. (Arnhem, NL)

SIGNIFICANCE

A two-phasemethod for preparing up to 90%monoperoxy esters or carbonates using a2:1 molar ratio of methyl isobutyl ketone peroxide and acid chloride, respectively, isdescribed. Nonsymmetrical diperoxides were also prepared by reacting the mono-peroxy esters or carbonates with a different second mole of acid chloride.

REACTION

Cl

O

i HOO OO

O O OO

O

O

O

ii

Note 1

i: Methylisobutyl ketone peroxide, diethyl ether, sodium hydroxide, potassiumhydroxide, decane, sodium chloride, water

ii: 2-Ethylhexanoyl chloride, decane, sodium chloride, water, potassium hydroxide,sodium sulfite

EXPERIMENTAL

1. Preparation of 1-Hydroperoxy-1,3-Dimethyl Butyl Peroxy-2-EthylHexanoate

A200-mlbeakerwaschargedof98.5%methylisobutyl ketoneperoxide (50 g) indiethylether,decane(25 g),25%aqueousNaCl(10 g),and20mlofdemineralizedwater.ThepHwas adjusted to 13.5 using 45% aqueous KOH at 8�C to 12�C and then treated with

367

2-ethylhexanoyl chloride (0.107mole) for over 25 minutes. Sufficient amount NaOHwasadded tomaintain thepH>13.5,and themixturestirredfor60minutesat5�Cto8�C.The two-phase systemwas separated, and the organic layerwashedwith 4MNaOHand3% to 6% NaHCO3 and then dried over MgSO4. After evaporation of the solvent theproductwasisolatedin85%yield,havinganactiveoxygencontentof5.02%withamono/di peroxide product ratio of 80:20, respectively.

2. Preparation of 2,2-Bis(2-Ethylhexanoylperoxy)-4-Methyl Pentane

A200-ml beakerwas chargedwith the Step 1 product (50 g) dissolved in n-decane, 25%aqueousNaCl (10 g), and 20ml of demineralizedwater. Themixture pHwas adjusted to13.5 using 45% aqueous KOH at 8�C to 12�C and then treated with 2-ethylhexanoylchloride(9.8 g)forover25minutes.AsufficientamountNaOHwasaddedtomaintainthepH>13.5, and themixturewas stirred for 60minutes at 5�C to 8�C.After thewater layerwas separated, the remaining hydroperoxide was reduced with sodium sulphite. Theorganic layer was washed with 3% to 6% NaHCO3 and dried using MgSO4. Afterevaporation of the solvent the product was isolated in 93% yield having a mono/diperoxide of 1:99, respectively, and an oxygen content of 3.77%.

DERIVATIVES

TABLE 1. Reaction scoping for the preparation of 1-hydroperoxyperesters preparedbycondensingmethylisobutyl ketoneperoxidewith anacid chloride at a 1:1molar ratio.

Entry StructureRatio Acid

Chloride/Peroxide

PeroxyProduct Ratio(mono/di) Yield (%)

2 HOO OO

O1:2 9:1 —

3 HOO OO

O5:1 1:1 —

5 HOO OO

O1.7:1 4:1 59

6 HOO OO

O2:1 6:4 80

368 Ketone Peroxide Derivatives, Their Preparation and Use

NOTES

1. Additional mono- and diperoxide derivatives of the current invention aredisclosed by the author [1] in an earlier investigation.

2. The mixed peroxides, t-butylperoxy 2-ethylhexyl, (I), and isobutanoyl-lauroylperoxide, (II), were prepared by Overkamp [2] and Tammer [3], respectively,using t-butyl peroxide and isobutanoyl chloridewith 30%hydrogen peroxide inthe presence of sodiumhydroxide in a two-phase system.Both agentswere usedin vinyl chloride polymerization.

OO

O(I)

OO C11H23

O

O

(II)

3. 3-Alkyl-3,7,7-trimethyl-1,2,4-trioxacycloheptane derivatives, (III), were usedby Hogt [4] in preparing high-solid acrylic, styrenic, and LDPE-type resins.

TABLE 2. Reaction scoping for the preparation of symmetrical and asymmetricdiperesters prepared by reacting 1-hydroperoxyperester with a second moleof a selected acid chloride.

Entry Structure Yield (%) Application

8a O O O

O

O

O

90 Curing agent forunsaturated polyesters

8b O O O

O

O

O90 Initiator in free radical

polymerization of styrene

9 O O O

O

O

O

96 Used in the emulsionpolymerization ofpolyvinyl chloride

Notes 369

O

OO

R

(III)

R = C2H5, i- and n-C3H7

i-C4H9

References

1. A.G. Van De Bovenkamp-Bouwman et al., US Patent 6,770,774 (August 3, 2004)2. J.W.A. Overkamp et al., US Patent Application 2004-0049070 (March 11, 2004) and US Patent

6,610,880 (August 26, 2003)3. M.C. Tammer et al., US Patent 7,087,693 (August 8, 2006)4. A.H. Hogt et al., US Patent 6,720,398 (April 22, 2004) and US Patent 6,566,391 (May 20, 2003)

370 Ketone Peroxide Derivatives, Their Preparation and Use

B. Polymers

a. Biogradable Polyesters

Title: Simplified Method of Producing BiodegradableAliphatic Polyesters

Author: F. Farachi et al., US Patent 7,253,250 (August 7, 2007)Assignee: Ministero dell ‘Universita’e della Ricerca Scientifica e Technologica(Rome, IT)

SIGNIFICANCE

High molecular weight biodegradable polyalkyl sebacate esters have been preparedusing a 1:1molar reagent ratio of diacid, diol, and monobutylstannoic acid as thereaction catalyst. The initial esterification entails heating the mixture to 190�Cfollowed by deglycolation under vacuum by heating the reaction mixture to 230�C.

REACTION

HO2C CO2H HO O O O

O O O

CO2HO O

O O

88 48 48 4 a b

ab >>Not isolated

i ii

Note 1

i: Monobutylstannoic acid, sebacic acid, butanediol

EXPERIMENTAL

Preparation of Polybutylene Sebacate

A 25-liter steel reactor equipped with a mechanical stirrer, an inlet for a nitrogenstream, a condenser, andaconnection to avacuumpumpwaschargedwith sebacic acid

371

(5050 g), butanediol (2362.5 g), andmonobutylstannoic acid (4 g) as reaction catalyst.The reaction was then gradually heated to 190�C and remained at this temperature for210 minutes while 900ml of water were collected. Thereafter the mixture was heatedto 230�C over a period of 6 hours at 0.5 torr for deglycolation to occur. The reactionmixturewasnext cooled, and6 kgof polymerwas isolatedhaving an inherent viscosityof 0.9 dl/g and a melt index of 40 g/10min.

DERIVATIVES

NOTES

1. Mixed biodegradable polysebacate esters containing hexandiol and neopentyldiol were previously prepared by the author [1] using monobutylstannoic acidas catalyst and the products used in film compositions.

2. Polybutandiol sebacate, polyhexandiol sebacate, polynonandiol sebacate, andpolydecandiol sebacate esters were previously prepared by Bastioli [2] andused as biodegradable water vapor barriers.

3. Gross [3] prepared biodegradable polyoctamethylene sebacate containing23mol% blended glycolide by enzyme catalysis using Novozyme-435.

References

1. F. Farachi et al., US Patent 6,562,939 (May 13, 2003)2. C. Bastioli et al., US Patent 6,727,342 (April 27, 2004)3. R.A. Gross et al., US Patent 6,972,315 (December 6, 2005)

TABLE 1. High molecular weight polyalkyl sebacate esters prepared using a1:1molar reagent ratio of sebacis acidwith a selected diol withmonobutylstannoic acidas the reaction catalyst.

Entry Diol CatalystInherent

Viscosity (dl/g)Melt Index(g/10min)

1b Butanediol Dibutyl tin oxide 0.58 —3 Hexanediol Monobutylstannoic acid 1.13 34 Ethanediol Monobutylstannoic acid 1.24 57 Decanediol Monobutylstannoic acid 1.2 5

372 Simplified Method of Producing Biodegradable Aliphatic Polyesters

b. Hydroaminomethylation Reactions

Title: Hydroaminomethylation of Olefins

Author: J. R. Briggs et al., US Patent 7,220,884 (May 22, 2007)Assignee: Dow Global Technologies, Inc. (Midland, MI)

SIGNIFICANCE

Mono- and dihydroaminomethylation of olefins was performed with dicarbonyl-2,4-pentanedionerhodium containing a monodentate phosphite ligand as the catalystunder moderate pressures. The reaction has high region-specificity with yieldsexceeding 90%.

REACTION

N(CH3)2

a b a b

i

i: NeodeneRTM, THF, dicarbonyl-2,4-pentanedionerhodium, tris(2,4-di-t-butyl-phenyl)phosphite, dimethylamine

EXPERIMENTAL

Aminomethylation Procedure

Aonegallon reactorwas chargedwith the polyolefinNeodeneRTM (319 g) dissolved in750ml of THF. The reactionmixturewas then treatedwith dimethylamine (222 g) anda solution of Rh(CO)2(acac) (3.7 g) and tris(2,4-di-t-butylphenyl)phosphite (46.2 g)dissolved in 400ml of THF so that the final rhodium concentration was 900 ppm byweight. The mixture was heated to 80�C and pressurized to 600 psi with syngas andthen stirred under these conditions for 7 hours. The reactor was cooled, excess

373

dimethylamine removed, and the product isolated in 99% yield as a colorless mobileliquid.

SYNTHETIC REACTIONS AND DERIVATIVES

aa

NHO

HO

i

i: Diethanolamine

aa

N(CH3)2

ii

ii: Dimethylamine

aa(C6H5CH2)Niii

iii: Dibenzylamine

NOTES

1. Riermeier [1] prepared amines in high yields by reductive amination ofcarbonyl-containing compounds using hydrogen and primary or secondaryamines with [Rh(COD)Cl]2 and 2,2

0-bis[[bis(3-sulfophenyl)phosphino]-meth-yl]-4,40,70,70-tetrasulfo-1,10-binaphthyl octasodium as catalysts as illustratedbelow. When the reaction was duplicated using [Ir(COD)Cl]2 alone, only 6%2-butylamine was incorporated.

O NH2 OH+i

7 : 3

i: Hydrogen, ammonia, heptane, with [Rh(COD)Cl]2, 2,20-bis[[bis(3-sulfo-

phenyl)phosphino]-methyl]-4,40,70,70-tetrasulfo-1,10-binaphthyl octasodium

374 Hydroaminomethylation of Olefins

2. Donsbach [2] prepared 3,3-diarylpropylamines by hydroformylation/hydro-carbonylation followed by reductive amination using (acetylacetonate)dicar-bonylrhodium as illustrated below, beginning with 4-hydroxybenzoic acid,ethyl ester.

OH

CO2C2H5

OH

CO2C2H5

O

CO2C2H5

O

CO2C2H5

N

i ii iii

i: Phenylene acetylene, tin tetrachloride, tributylamine, 1,2-dichloroethaneii: Benzyl bromide, potassium carbonate, acetoneiii: Diisopropylamine, (acetylacetonate)dicarbonylrhodium, tributylphosphine,

dioxane

3. Aminoalkylation of polyisoprene as viscosity index improvers for crankcase oilusing (acetylacetonate)-dicarbonylrhodium with carbon monoxide and hydro-gen with aminopropyl morpholine was used by Coolbaugh [3] to prepare oildispersants.

References

1. T. Riermeier et al., US Patent 6,884,887 (April 26, 2005)2. M. Donsbach et al., US Patent 6,809,225 (October 26, 2004)3. T.S. Coolbaugh et al., US Patent 6,228,817 (May 8, 2001) and US Patent 6,103,676 (August 15, 2000)

Notes 375

c. Perdeuterated Polyiimides

Title: Perdeuterated Polyiimides, Their Process ofPreparation, and Their Use as Materials Which AreTransparent within the Region from 2500 to 3500 cm�1

Author: E. Anselmi et al., US Patent 7,211,632 (May 1, 2007)Assignee: Commissariat a L’Energie Atomique (Paris, FR)

SIGNIFICANCE

Deuterated aromatic polyimides having excellent mechanical, thermal, and opticalproperties and exhibiting infrared absorption transparency between 2500 and3500 cm�1 have been prepared. These materials are useful in optical transmissionand optical signal processing because of minimum optical losses associated withabsorption.

REACTION

aO O

O

O

O

OD3 D3

N N

O

O

O

OD3 D3D4

iNote 1

i: d8-4-Phenylenediamine, N-methylpyrrolidone

EXPERIMENTAL

In stoichometric amounts, perdeuterated biphenyldianhydride was added to a reac-tion vessel containing perdeuterated 4-phenylenediamine dissolved in anhydrousN-methylpyrrolidone and stirred at ambient temperature for 24 hours. A film of the

376

poly(amic-acid) solution was deposited on a sheet of glass and heated from 50�C to80�C to dry. The film was then cyclized and annealed by heating between 100�C and300�C at a heating rate of between 1�C and 5�C per minute. The sheet was lastimmersed in a water bath in order to detach the polyimide film from the glass sheet.

DERIVATIVES

TABLE 1. dn-Polyimides prepared from perdeuterated dianhydrides and diaminesand physical properties of the corresponding polymer.

Entry dn-Dianhydride dn-Diamine

YoungModulusE (GPa)

Elongationat Break(%)

C–DAbsorbance(cm�1)

Product 1 O O

O

O

O

OD3 D3

ND2

ND2

D48 20 2247

2 O O

O

O

O

OD3 D3

ND2

D4D2N

8 20 2255

3 O O

O

O

O

OD3 D3

D2N ND2D4 D4

O

4 20 2254

6 O O

O

O

O

O

O

D3 D3

ND2

ND2

D47 10 2251

7 O O

O

O

O

O

O

D3 D3

D2N ND2D4 D4

O

3 60 2256

Note: Percent conversions were not supplied by author.

Derivatives 377

NOTES

1. The perfluoropolyimide analogue, (I), of the current invention was previouslyprepared by Kawamonzen [1] and used as an optical waveguide element.

aN N

O

O

O

OF3 F3F4

(I)

2. To minimize optical propagation caused by light absorption of a harmonicovertone vibration mode, Kim [2] and Ding [3] prepared polyether, (II), andpolysulfone, (III), derivatives, respectively, where the majority of hydrogenatoms were replaced by fluorine.

a

aO

F

F

FF

OF2C

F2C OO

F

FF

F

F

FF

F

4 4

(II)

F3C CF3O

O2S O

F

F FF

FF

F

OFF

FF

F3C CF3O

FF

FF

(III)

3. Perfluoropolyimides (IV) prepared by Ando [4] were useful as optical wave-guide circuits for printed wire-board interconnections.

aN

O

O

FO

FF

OFN

F

F

F

O

O

X

F

F

FF F

F F

X = O, S

(IV)

References

1. Y. Kawamonzen et al., US Patent 7,092,608 (August 15, 2006) and US Patent 7,082,244 (July 25, 2006)2. J.-H. Kim et al., US Patent 7,202,324 (April 10, 2007)3. J. Ding et al., US Patent 7,049,393 (May 23, 2006)4. S. Ando et al., US Patent 5,750,731 (May 12, 1998)

378 Perdeuterated Polyiimides, Their Process of Preparation, and Their Use as Materials

d. Polybutadiene (Meth)acrylates

Title: Polybutadiene (Meth)Acrylate Compositionand Method

Author: J. A. Klang et al., US Patent 7,192,688 (March 20, 2007)Assignee: Sartomer Technology, Inc. (Wilmington, DE)

SIGNIFICANCE

A stable ester consisting of polybutadiene diol having a molecular weight of 2200daltonswith termini cappedwith twomoles of ethyleneoxide and acrylic acid hasbeenprepared. In the absence of ethylene oxide, capping of acrylated polybutadiene diolgelled and produced molecular weights of at least 40,000 daltons. After crosslinkingthe stable polybutadiene-EO-acrylate composition materials were used as a photo-polymer printing plates.

REACTION

OO

a b

i

OOH

OHO

OO

a b OO

OO

O O

i: Heptane, methanesulfonic acid, hydroquinone monomethyl ether, acrylic acid

EXPERIMENTAL

Preparation of Polybutadiene-Ethylene Oxide Diacrylate

A reaction flask containing a Dean-Stark trap was charged with heptane (157 g),acrylic acid (43 g), methanesulfonic acid (3.2 gm), hydroquinone monomethyl ether

379

(1.9 g), and a ethylene glycol terminated polybutadiene resin (424 g) with a Mn of2244 daltons. The mixture was heated to reflux to remove water and continuedrefluxing until water collection stopped. After removal of the strong acid catalyst,solvent, and excess acrylic acid, the product was isolated as a viscous light brownliquid.

DERIVATIVES

NOTES

1. PolyBd diol capped with two moles of ethylene oxide has also been used toprepare stable isocyanate-terminated pre-polymers by Bechara [1] using iso-phorone diisocyanate.

2. Acevedo [2] prepared PolyBd diol pre-polymers terminated with isocyanate,acrylate, methacrylate, or organosilanes that weremoisture or radiation curablefor use in sealant compositions.

3. Bonnet [3] prepared aqueous dispersions of bitumen and asphaltenes using theurethane reaction product of 4,40-diphenylmethane diisocyanate and PolyBddiol.

References

1. I. Bechara et al., US Patent 7,160,944 (January 9, 2007)2. M. Acevedo et al., US Patent 7,189,781 (March 13, 2007)3. E. Bonnet et al., US Patent Application 2005-0124736 (June 9, 2005)

TABLE 1. Physical properties of derivatized polybutadiene diol containing a acrylicacid termini.

EntryPolybutadiene

Sample

Moles EthyleneOxide on PolyBd

TerminiMw

(daltons)

Bookfield Viscosity(mPas � s(cPs)

@25�C) Color

1 Krason LBH 2000 2 3,200 5600 70 APHA2 Krason LBH 2000 2 3,000 11,100 150 APHA3 PolyBD diol 0 247,000 Semi-gelled Very dark4 PolyBD diol 0 40,000 54,000 Very dark

Note: In the absence of ethylene oxide capping unregulated polymerization occurred.

380 Polybutadiene (Meth)Acrylate Composition and Method

e. Poly(Aniline-co-Thiophene)

Title: Soluble Aniline-Thiophene Copolymers

Author: S. S. Xiao et al., US Patent 7,193,021 (March 20, 2007)Assignee: Organic Vision, Inc. (Brossard, CA)

SIGNIFICANCE

Four solvent-soluble poly(aniline-co-thiophene) materials have been prepared bycoupling thiophene derivatives with 4-n-butyl aniline using palladium acetate ascatalyst. Mn’s of up to 17,500 daltons with a PDI of 1.1 were obtained.

REACTION

aS SBr Br SN

n-C4H9

iiiNote 1

i: DMF, N-bromosuccinimideii: Toluene, palladium acetate, tri-t-butylphosphine, sodium t-butoxide, 4-n-

butylaniline

EXPERIMENTAL

1. Preparation of 2,5-Dibromothiophene

A reactor wrapped with aluminum foil to avoid light penetration was charged with300ml ofDMFand thiophene (0.5mol) and then treatedwith the dropwise addition ofN-bromosuccinimide (1.1mol) and stirred 48 hours in the dark. The mixture waspoured into 300ml of ice-water and stirred for 2 hours until a yellow suspensionformed. The suspension was extracted 4 times with 200ml diethyl ether, and the

381

combined ethereal solution was washed twice with 100ml water and dried withMgSO4. The mixture was filtered, concentrated, the residue purified by silica gelchromatography, and the product isolated in 91.3% yield.

2. Preparation of Poly(2,5-Thiophene-co-4-n-Butyl-2,6-Aniline)

Under continuous nitrogen flow, a reaction flask was dried with a propane torch flameand then cooled to ambient temperature. The flaskwas chargedwith 180ml of toluene,palladium acetate (0.5mmol), and tri-t-butylphosphine (2.0mmol) and stirred atambient temperature until a thick light yellow suspension was obtained. This mixturewas then treated with 4-n-butylaniline (10mmol), the Step 1 product (10mmol), andsodium t-butoxide (22mmol) and heated overnight at 80�C. The reactionmixturewaspoured into 1000ml of methanol where a brownish precipitation slowly appeared,whichwas isolated by filtration. The brown solidwas dissolved in 50ml of CCl3H andre-precipitated in 500ml ofmethanol, and the productwas isolated in 45.0% yield as abrown powder having a Mw of 7728 daltons with a PDI of 2.12.

DERIVATIVES

TABLE 1. Physical properties of thiophene and aniline copolymers.

Entry StructurePolymerization

Yield (%)Mw

(daltons) PDI Color

2aSS

N

n-C4H9

73.4 5,860 4.1 Black

3 aSN

n-C4H9

C6H13

64.1 17,500 1.1 Brownish

4 aSN

n-C4H9

OO

36.5 3,500 1.15 Black

Note: Limited analytical information supplied by the author.

382 Soluble Aniline-Thiophene Copolymers

NOTES

1. The rationale for preparing this hybrid copolymer was to combine the desirableproperties of polyaniline with those of polythiophene. For example, polythio-phene has demonstrated thermo- and electrochromism, solvatochromism,luminescence, and photoconductivity while polyaniline has demonstratedreversible protonic dupability, excellent redox re-cyclability, and chemicalstability.

2. Wu [2] coupled thiophene with aromatic diethers, (I), to improve the solubilityof polythiophene in common solvents and to increase its flexibility in coatingapplications.

a

S

OC6H13

C6H13O

S

(I)

3. Angelopoulos [2] prepared a 5wt% water-soluble electrically conductingpolymer by polymerizing aniline with polystyrene sulfonic acid for use inorganic discharge layers in electronic applications. In these materials thenumber of acidic groups exceeded the number of protonatable basic atomsin polyaniline. Water-soluble electrically conducting polymers were alsoprepared by Angelopoulos [3] using both polyvinylsulfonic and polyacrylicacids as the acidic blending component.

References

1. Y. Wu et al., US Patent 7,169,883 (January 30, 2007)2. M.Angelopoulos et al., USPatent 7,166,241 (January 23, 2007) andUSPatent 6,830,708 (December 14,

2004)3. M. Angelopoulos et al., US Patent 5,370,825 (December 23, 1994)

Notes 383

f. Aniline Formaldehyde Oligomers

Title: Process for the Preparation of Di- andPolyamines of the Diphenylmethane Series

Author: H. H. Muller et al., US Patent 7,186,857 (March 6, 2007)Assignee: Bayer MaterialScience AG (Leverkusen, DE)

SIGNIFICANCE

Aniline was converted into its novolak analogue by reacting with formaldehyde andhydrochloric acid in the presence of divalentmetal cations such asCaþ2 and Feþ2. Theratio of aniline/formaldehyde/hydrochloric acid was 7.5:1.0:0.3, respectively, using0.00025wt% metal ions. These oligomeric products are designed to be furthermodified to isocyanates by reacting with phosgene.

REACTION

a

NH2 NH2 NH2 NH2

i

i: Hydrochloric acid, formaldehyde, iron(II) chloride

EXPERIMENTAL

Preparation of Diphenylmethane, Di-, and Polyamines

A reactor charged with aniline (931 g) at 80�Cwas treated with the dropwise additionof 32.1wt% aqueous formaldehyde (389 g) over 20 minutes. After the addition wascompleted, the mixture was stirred for a further 5 minutes, and the organic phase wasisolated. The organic phase was then treated with the dropwise addition of 12Mhydrochloric acid (114 g) over 20minutes at 45�C and 0.00025wt% iron(II) chloride.

384

The mixture was then stirred at 45�C for 30 minutes and an additional 30 minutesat 60�C. The reaction temperature was increased to 104�C for 10 hours andthen neutralized with 33wt% aqueous NaOH (62.3 g) at 90�C. A two-phasemixture formed, which was subsequently stirred at 90�C for 5 minutes, andthe organic phase was obtained. After removal of unreacted aniline by distillation,the product mixture was isolated.

DERIVATIVES

Only the Step 1 product mixture was described.

NOTES

1. Methylenedianiline was previously prepared by Klein [1] using an aniline/formaldehyde ratio of 9:1, respectively, in the absence of a metallic salt at60�C. Scale-up production for methylenedianiline using an aniline/formal-dehyde ratio>2 and hydrochloric acid/aniline ratio of 0.05 is described bySteinbrenner [2].

2. Hagen [3] prepared diphenylmethane and polyamines in the absence ofmetallicions using an aniline/formaldehyde ratio of 4:1, respectively, at 80�C.

3. Polyamines prepared by Koch [4] were converted into the correspondingisocyanate derivatives, (I), using phosgene; methylenebis(phenyl isocyanate)was prepared by Strofer [5].

a

NCO NCO NCO

(I)

References

1. S. Klein et al., US Patent 6,649,798 (November 18, 2003)2. U. Steinbrenner et al., US Patent Application 2007-0010692 (January 11, 2007)3. D. Koch et al., US Patent 7,041,776 (May 9, 2006)4. D. Koch et al., US Patent 7,041,776 (May 9, 2006)5. E. Strofer et al., US Patent 6,831,192 (December 14, 2004)

Notes 385

g. Polymaleimides

Title: Method for Preparing Polymer Maleimides

Author: A. Kozlowski et al., US Patent Application 2007-0049688 (March 1, 2007)Assignee: Nektar Therapeutics (San Carlos, CA)

SIGNIFICANCE

Methoxypolyethylene glycolmaleimide has been prepared at ambient temperature byreacting the corresponding polyethylene oxidewithN-methoxycarbonylmaleimide.Since malimide derivatives are ordinarily prepared at 140�C, this ambient tempera-ture imidization procedure dramatically broadens the scope and utilization of thisreaction.

REACTION

H3COO

ONH2

H3COO

O NH

HN

OCH3

O

O

H3COO

ON

O

O

i ii

450

450450 Note 1

i: N-Methoxycarbonylmaleimide, N,N-diisopropylethylamine, CH2Clii: Acetonitrile, N,N-diisopropylethylamine

EXPERIMENTAL

1. Preparation of Methoxypolyethylene Glycol Maleamic Acid

A solution of methoxypolyethylene glycol (0.0025mol) dissolved in 350ml ofCH2Cl2, and N-methoxycarbonylmaleimide (0.0051mol) was stirred at ambienttemperature for one hour and then treated with 1ml of N,N-diisopropylethylamine.The mixture was stirred overnight at ambient temperature and concentrated by

386

distilling off approximately 200ml ofCH2Cl2. Themixturewasprecipitated in diethylether, and 46.3 g of product were isolated.

2. Preparation of Methoxypolyethylene Glycol Maleimide

The Step 1 product (10.0 g) was dissolved in 100ml of acetonitrile containing 10ml ofN,N-diisopropyl-ethylamine and stirred for 48 hours at ambient temperature. Thesolutionwas concentrated by distilling off 80ml of solvent and8.5 g of product isolatedby precipitating in diethyl ether. The product was 93.5% maleimide-functionalized.

DERIVATIVES


NOTES

1. The succinimidyl analogue, (I), of the current invention was previouslyprepared by Harris [1].

H3COO

OO

450O

O

O

ON

O

O(I)

2. In an earlier investigation by the author [2] the reagent 4-chlorobutyaldehydediethyl acetal, (II), was used to convert methoxypolyethylene glycol into thecorresponding aldehyde, which was then used as a conjugate for lysozyme,(III), as illustrated below.

H3COO

OOH

H3COO

OO

OC2H5

i

ii675

675Cl

OC2H5

OC2H5

+

OC2H5

H3COO

OO

O675

H3COO

OO

NH-Lysozyme675iii

(II)

(III)

1H-NMR (d6-DMSO): d 3.24 (s, PEG–OCH3), 3.51 (s, PEG backbone), 7.01 ppm (s,–CH¼CH–,maleimide)

1H-NMR (d6-DMSO): d 3.24 (s, PEG�OCH3), 3.51 (s, PEG backbone), 3.86 (s,CH3O�NH�), 6.20(m, �CH¼CH�), 8.46 (�NH).

Notes 387

i: Toluene, potassium t-butoxide, t-butanolii: Water, phosphoric acid, sodium chloride, sodium hydroxide,iii: Lysozyme, phosphate buffer (pH¼ 7.6), sodium cyanoborohydride

3. Di(1-denzotriazolyl)carbonate, (IV), was also used by the author [2,3] forpreparing 1-benzotriazolyl carbonate esters of polyethylene glycol, (V), whichwere then used to form urethane conjugates, (VI), with aminoacids as illus-trated below.

H3COO

OOH i

450 +N

NN

O O

O

N

NN

H3COO

OO

450O

O

N

NN

H3COO

OO

450NH-Lysine

O

ii

(IV)

(V)(VI)

i: Pyridine, acetonitrileii: Borate buffer, sodium hydroxide, sodium chloride, phosphoric acid.

4. Bifunctional polyethylene glycols, (VII), were prepared by Bentley [4] andused as bioconjugates.

AO

OO

aB

A BOH NH3

+Cl-

OH NH2

OH CH2CO2HNH3

+Cl- CH2C02HC6H5–CH=CH–CH=CH–CO2 CH(OC2H5)2

(VII)

References

1. J.M. Harris et al., US Patent 7,030,278 (April 18, 2006)2. A. Kozlowski et al., US Patent 7,157,546 (January 2, 2007) and US Patent 6,710,125 (March 23, 2004)3. A. Kozlowski et al., US Patent 7,101,932 (September 5, 2006)4. M.D.Bentley et al., US Patent 6,864,327 (March 8, 2005) andUSPatent 6,495,659 (December 17, 2002)

388 Method for Preparing Polymer Maleimides

h. Poly(9-Fluroenone)

Title: Method for Preparing Polymers ContainingCyclopentanone Structures

Author: T. Umemoto, US Patent 7,182,850 (February 27, 2007)Assignee: IM&T Research, Inc. (Denver, CO)

SIGNIFICANCE

A high-yielding single step method for preparing poly(9-fluroenone) by electrolyti-cally polymerizing fluorene in the presence of propylene carbonate and lithiumhexafluorophosphate is described.

REACTION

O

i

a

i: Propylene carbonate, lithium hexafluorophosphate

EXPERIMENTAL

Preparation of Poly(9-Fluroenone)

In a vessel for electrolysis three parallel nickel plates were installed. The inner nickelplate was the working electrode (anode), and the two outer nickel plates were counterelectrodes (cathode). A 1.2 liter mixture consisting of fluorene (0.01mol) and LiPF6(0.1mol) dissolved in propylene carbonate were then added to the vessel. The threenickel plates were immersed in the mixture to a depth of 90mm. Two lithium metalsheets were used as reference electrodes, with each sheet placed between the anodeand the cathode. The electrolysis was carried out by a potential-sweep method for4 hours under a potential width of 4.5 to 6.7Vwith a sweep time of 50mV/s. The inner

389

electrode (anode) onwhich the polymer haddepositedwaspulled out of the electrolytemixture, and the polymer was isolated. The collected polymer was washed withpropylene carbonate and acetonitrile, dried at 120�C for 5 hours, and 0.31 g of productwere isolated as a dark brown to black solid, MP >400�C.

SCOPING STUDIES

NOTES

1. Poly(9-fluroenone) has also been prepared by the oxidation of polyfluoreneusing acetic acid and sodium dichromate, as described by Rauth-Berthelot [1]and Umemoto [2].

2. Methods for preparing poly(9-fluroenone) containing 35% polyfluorene con-tent are described by the author in a subsequent investigation [3].

3. A negative electrode was prepared by the author [4] that consisted of 70% poly(9-fluroenone) or poly(cyclopent[def]fluorene-4,8-dione), (I), with 25wt%acetylene black and 5wt% tetrafluoroethylene using LiAsF6 as the electrolytein propylene carbonate.

TABLE 1. Experimental conditions for preparing poly(9-fluroenone) using 0.1molfluorene in the presence of varying amounts of propylene carbonate.

Entry 5 8 16

Electrolyte andconcentration (mol)

LiPF6, 0.1 Et4BF4, 0.1 LiPF6, 0.1

Propylene carbonate (mol) 0.1 0.025 0.05Working electrode (anode)(mm�mm)

Pt, 25� 25 Pt, 25� 20 GC, 25� 25

Counter electrode (cathode)(mm�mm)

Pt mesh,40� 35

Pt mesh,35� 30

Cu, 25� 30

Conditions 1.6V, 4 hours 2.4V, 3 hour 50mV/s 0.5 – 2.7V 12.3 hour

Polymer yield (mg) 10.8 3.7 25.2

FTIR (KBr, cm�1): 3051(w), 2916(w), 1714(s)(C¼O), 1606(s), 1454(s), 1405(m), 1263(m), 815(s), 767(s),735(s)

Elemental analysis: Found: C, 85.94%; H, 4.29%; O, 8%; F; 0.31%; P, 0.21%: total 98.75% Calcd forC13H6O; C, 87.63%, H, 3.37%, O, 8.98%

390 Method for Preparing Polymers Containing Cyclopentanone Structures

O

O(I)

4. Uckert [5,6] prepared electroactive poly(fluorene-co-fluroenone), (II), andaliphatic and perfluoroaliphatic derivatives for use in as light-emitting diodes.Light-emitting devices consisting of polyfluorene alkoxy derivatives, (III),were prepared by Mizuno [7].

RR

O

(II)

R2-Ethyl-n-hexanePerfluoron-decane OC7H15C7H15O

(III)

aa

References

1. J. Rauth-Berthelot et al., New J. Chem, 10, Sept 23, 19852. T. Umemoto, US Patent 7,087,681 (August 8, 2006)3. T. Umemoto, US Patent Application 2005-0045492 (March 3, 2005)4. T. Umemoto, US Patent Application 2006-0008703 (January 12, 2006)5. F.P. Uckert et al., US Patent 7,183,366 (February 27, 2007)6. F.P. Uckert et al., US Patent 7,183,365 (February 27, 2007)7. Y. Mizuno et al., US Patent 7,184,191 (February 27, 2007)

Notes 391

i. Polypropylene Succinic Anhydride

Title: Polypropylene Having a High MaleicAnhydride Content

Author: P. K. Hanna et al., US Patent 7,183,359 (February 27, 2007)Assignee: Baker Hughes Incorporated (Houston, TX)

SIGNIFICANCE

Amethod of incorporating between 5% to 45%maleic anhydride into polypropylenewithout chain scission or viscosity increase is described. Themethod entails an initialthermally induced ene reaction followed by the free radical addition of the anhydrideto the polymer backbone.

REACTION

OO O OO OOO O

O

O

O

O

O

O

i+

Note 1

(Ene reaction products)not isolated

i: Maleic anhydride, acetone, di-t-butyl peroxide

392

EXPERIMENTAL

Preparation of Poly(Propylene-g-Maleic Anhydride)

A reactor was chargedwith polypropylene containing an ene terminus (250 g), and thetemperature was increased and maintained at 185�C. This material was then treatedwith maleic anhydride (20 g) dissolved in 24ml of acetone followed by the dropwiseaddition of di-t-butyl peroxide (6 g). The reaction was maintained at this temperaturefor 3 hours and then gradually cooled over 60 minutes. The product was isolatedhaving an 11.3% maleic anhydride content.

DERIVATIVES

NOTES

1. The ene reaction of maleic anhydride with vinylidene-terminated polypropyl-ene that results in a highmolecular weight product, (I), and viscosity increase isillustrated below.

OO O OO OO O

OO

On

i

. .

Intermediate 1 Intermediate 2 (I)

aaaaaa

i: Maleic anhydride

2. In the absence of a solvent and using dilaurylperoxide as the free radicalinitiator, Bortolon [1] grafted roughly 3wt% maleic anhydride onto the

TABLE 1. Selected polypropylene succinic anhydrides prepared usingpolypropylene containing an ene terminus and maleic anhydride.

EntryPolypropylene-ene

CopmponentFinal Maleic Anhydride

Content (wt%)

1 Eastman� AP550 4.212 PP-ene-C 11.313 Entry 12 product 16.114 Entry 13 product 28.715 PP-ene-D 0.916 Entry 15 product 7.517 Entry 16 product 4520 Octadecene-ene 35.321 Entry 20 product 51.0

Note: Percent incorporation of maleic anhydride was determined by 13C-NMR.

Notes 393

polypropylene backbone at 90�C under 3 atm of nitrogen pressure afterallowing the mixture to react for two hours at 110�C.

3. High melt flow polypropylene-g-maleic anhydride has also been prepared byreactive extrusion methods. Flaris [2] reacted a mixture of polypropylene,maleic anhydride, and 2,5-dimethyl-2,5-di-(t-butyl peroxide)hexane in a twin-screw extruder having a barrel temperature profile of 175�C, 190�C, 215�C,215�C, 215�C, 200�C, and 170�C. With this technique the grafted maleicanhydride content was about 2wt%. Pradel [3] grafted 1.5wt% maleic anhy-dride onto syndiotactic poly(polypropylene) while co-extruding polyethyleneusing 2,5-dimethyl-2,5-di-(t-butyl peroxide)hexane in an eight-zone extruder.

4. Harrison [4] prepared poly(isobutylene-g-succinic anhydride) by reacting a1:1mole ratio of polyisobutene/maleic anhydride using di-t-butylperoxide ascatalyst where the ratio of di-t-butylperoxide/polyisobutene was 0.05:1, re-spectively. In this procedure polyisobutylene had aMn of roughly 2300 daltonswhile the product had a SAP number of 26.2mg for the KOH/g sample. Poly(isobutylene-g-succinic anhydride) has also been prepared in the simultaneouschlorination/maleation process described by Barini [5].

References

1. V. Bortolon et al., US Patent 6,437,049 (August 20, 2002)2. V. Flaris et al., US Patent 6,228,948 (May 8, 2001)3. J.-L. Pradel et al., US Patent 7,067,196 (June 27, 2006)4. J.J. Harrison et al., US Patent 6,451,920 (September 27, 2002)5. G. Barini et al., US Patent 6,562,904 (May 13, 2003)

394 Polypropylene Having a High Maleic Anhydride Content

j. Cysteine Graft Copolymers

Title: Polyamide Graft Copolymers

Author: A. B. Brennan et al., US Patent 7,169,853 (January 30, 2007)Assignee: University of Florida Research Foundation, Inc. (Gainesville, FL)

SIGNIFICANCE

Polyamide copolymers containing a macromolecular graft substituent were preparedby condensing 4-amino-benzoic acid or a mixture of 1,4-phenylene diamine andadipic acid with 33%, 66%, and 90% S-poly(n-butylacrylate)cysteine macromono-mer.A secondmacromolecularmonomer,S-poly(methylmethacrylate)-cysteine,wasalso prepared and free radically copolymerized with perfluoromethyl methacrylate.

REACTION

O

On-C4H9

H2N OH

S

O


NH

NH

S

O

O


i ii

a

i: 2,20-Azobisisobutyronitrile, cysteine, THF, hydrochloric acidii: Triphenylphosphite, lithium chloride, pyridine, N-methyl-pyrrolidinone, 4-ami-

nobenzoic acid

EXPERIMENTAL

1. Preparation of S-(Poly-n-Butyl Acrylate)-Cysteine Macromonomer

Thesynthesisofpoly(butylacrylate)wascarriedoutusingTHF,ethylalcohol,andwaterwhere the molar ratio of butyl acrylate monomer/cysteine/azobisisobutyro-nitrile

395

was 1000:30:1, respectively. The mixture was then refluxed for 6 hours at 65�Cwhile under constant stirring. After cooling, the cysteine-modified productconsisted of a white precipitate dispersed within a poly(butyl acrylate) matrix.The precipitatewas isolated from the polymer by dissolving the poly(butyl acrylate)in THF and filtering.

2. Preparation of Poly(4-Amino-Benzoic Acid-co-(Cysteine-g-Poly-n-ButylAcrylate)

The Step 1 product (1.37 g; Mn 26,000 daltons), 4-aminobenzoic acid (2.24mmol),triphenyl-phosphite (5mmol), and LiCl 0.09 g were dissolved in 30ml of N-methyl-pyrrolidinone/pyridine solution, 80:20, respectively, and heated to 100�C for 4 hours.The reaction mixture was then precipitated in an excess of water/methanol, 1:1,filtered, andwashedwithmethanol. Thematerialwasdried overnight under vacuumat40�C, and the product was quantitatively isolated.

DERIVATIVES

NOTES

1. Polylysine-g-polyhistidine derivatives, (I), were prepared by Pack [1] and wereeffective as biocompatible endosomolytic delivery agents.

TABLE 1. Selected comonomer(s) reacted with cysteine-g-macromolecularintermediates and corresponding macromolecular content.

Cysteine-g-MacromolecularComponent Comonomer(s)

MacromoleculeContent In

Copolymer (wt%)

Poly(butyl acrylate) 4-Amino-benzoic acid 33Poly(butyl acrylate) 4-Amino-benzoic acid 66Poly(butyl acrylate) 1,4-Phenylene diamine

and adipic acid66

Poly(butyl acrylate) 1,4-Phenylene diamine/adipic acid 90Poly(methyl methacrylate) Perfluoromethyl methacrylate 65

Note: Polymers derived from 4-amino-benzoic acid were insoluble in all solvents except concentratedsulfuric acid. Elemental analysis for all materials supplied by author.

396 Polyamide Graft Copolymers

HN

NH2

O

HN

O

NH

N

NH

a b

(I)

b = 10–100%

O

c

2. Kaneko [2] prepared compatibilizing agents consisting of methacrylate, (II),and styryl, (III), macromolecules, which were polymerized using titanium-based Ziegler–Natta catalysts.

O

OR R = Polyethylene

Polypropylene Poly(ethylene-co-propylene)

O

R(II)

(III)

References

1. D.W. Pack et al., US Patent Application 2001-0006817 (July 5, 2001)2. H. Kaneko et al., US Patent 7,067,587 (June 27, 2006)

Notes 397

k. Guerbet Polymers

Title: Guerbet Polymers

Author: A. J. O’Lenick Jr., US Patent 7,049,476 (May 23, 2006)Assignee: SurfaTech Corporation (Dacula, GA)

SIGNIFICANCE

Highly branched and saturated oily Guerbet polymers having primary alcohols havebeen prepared by condensing 1,9-, 1,10-, or 1,12-aliphatic diols with behenyl alcoholand zinc oxide. To control the molecular weight, each polymer was capped with a C12

or higher fatty alcohol.

REACTION

HO OH

OH

OH

HO

6

6

6

20

i

19

i: Zinc oxide, behenyl alcohol

EXPERIMENTAL

Preparation of Polymeric Guerbet Alcohol

A reaction vessel was charged with behenyl alcohol (0.652 kg), 1,10-decanediol(101 kg), and zinc oxide (6 g) and then heated to 230�C. The reaction began at about170�C and was monitored by the amount of water generated and hydroxyl number ofsample aliquots. When the reaction was completed, the product was used withoutpurification.

398

DERIVATIVES

NOTES

1. Guerbet alcohols were previously used by the author [1] to prepare controlledmolecular weight polyesters derived from succinic acid and used in skin careformulations.

2. In a subsequent investigation by O’Lenick [2] Guerbet acids were convertedinto the corresponding oligomers by reacting with difunctional acids whileusing benzene sulfonic acid as catalyst. Products were used to prepare lipstick.

3. Guerbet triblock alkoxy sulfonates, (I), were prepared by the author [3] andused as emulsifying agents in skin care formulations.

OO

OO

OSO3 Na

9

7 a b a

(I)

4. Dimer quaternary compounds, (II), prepared by the author [4] were used asbarrier agents in personal care products.

C6H13

C6H13

HN

O

CO2H

N(CH3)3

7

7

(II)

TABLE 1. Selected Guerbet oligomers and polymers prepared using C9, C10, or C12

diols with behenyl alcohol and capping with a fatty alcohol.

Entry Capping Alcohol Diol Repeat Unit

1 Capryl 1,10-Decanediol 13 Lauryl 1,12-Dodecyldiol 205 Palmityl 1,10-Decanediol 507 Aracadinyl 1,9-Nonyldiol 1009 Beheny 1,10-Decanediol 20

Note: The catalyst was 0.1wt% zinc oxide based on capping agent. Very limited analytical data weresupplied by the author.

Notes 399

References

1. A.J. O’Lenick Jr., US Patent 7,038,005 (May 2, 2006)2. A.J. O’Lenick Jr., US Patent 7,259,226 (August 21, 2007)3. A.J. O’Lenick Jr., US Patent 7,119,125 (October 10, 2006)4. A.J. O’Lenick Jr., US Patent 7,193,111 (March 20, 2007)

400 Guerbet Polymers

l. Poly(1,4-Phenylene Vinylene) Derivatives

Title: Polymerization Method

Author: A. B. Holmes et al., US Patent 7,005,484 (February 28, 2006)Assignee: Cambridge Display Technology Limited (Cambridge, GB)

SIGNIFICANCE

Beginning with tetra-N-ethyl-terephthalamide a five-step method for preparing poly[2-(dimethyloctylsilyl)-5-(dimethyldecylsilyl)-1,4-phenylene vinylene] is described.The conjugated polymers are useful in electric, electronic, optical, and optoelectronicdevices such as LEDs.

REACTION

a

O

(C2H5)2N N(C2H5)2

O O

(C2H5)2N N(C2H5)2

O

Si

C8H17

O

(C2H5)2N N(C2H5)2

O

Si

C8H17

Si

C10H21

(C2H5)2N N(C2H5)2

Si

C8H17

Si

C10H21

Cl Cl

Si

C8H17

Si

C10H21

Si

C8H17

Si

C10H21

i ii

iiiiv

v

Note 1

401

i: THF, t-butyllithium, chlorodimethyloctylsilaneii: Tetramethylethylenediamine, THF, sec-butyllithium, chlorodimethyloctylsilaneiii: THF, borane-tetrahydrofuran complex, hydrochloric acidiv: CH2C12, vinyl chloroformatev: THF, potassium t-butoxide

EXPERIMENTAL

1. Preparation of 2-Dimethyloctylsilyl-Tetra-N-Ethyl-Terephthalamide

Tetra-N-ethyl-terephthalamide (0.36mmol) dissolved in 30ml of THF was cooled to-78�C and treated with 253ml of t-butyllithium (0.43mmol), and after 30 minutes wastreated with 102ml of chlorodimethyloctylsilane (0.43mmol). Thereafter the mixturewas left to reach ambient temperature over a three-hour period. Brine was then added,and themixturewas extractedwithCH2Cl2; itwas subsequentlydried and concentrated.The residue was purified using column chromatography with hexane/EtOAc, 60:40,respectively, and the product was isolated in 78% yield as a white solid, MP¼ 46�C.

2. Preparation of 2-Dimethyloctylsilyl-5-Dimethyldecylsilyl-Tetra-N-Ethyl-Terephthalamide

Tetramethylethylenediamine (3.7mmol) dissolved in 15ml of THF at -78�C wastreated with 2.9ml of sec-butyllithium. This mixture was then treated with thedropwise addition of the Step 1 product dissolved in THF, and the mixture wasstirred for 20 minutes. After treating this mixture with 1ml of chlorodimethy-loctylsilane, the reaction was left to react at ambient temperature while beingstirred overnight. Following the Step 1 workup using hexane/EtOAc, 80:20,respectively, the product was isolated in 85% yield as a white solid.

3. Preparation of 2-Dimethyloctylsilyl-5-Dimethyldecylsilyl-Tetra-N-Ethyl-p-Xylylenediamine

The Step 2 product (2.3mmol) dissolved in 30ml of THF was treated with a borane-tetrahydrofuran complex (23mmol) and then refluxed for 18 hours and quenchedwithwater. The mixture was concentrated and treated with 6M hydrochloric acid and

1H-NMR (CDCl3) d 7.33 (s, 2H), 3.54 (q, 4H, J¼ 7.15Hz), 3.12 (q, 4H, J¼ 7.15Hz), 1.30 0.52 (m, 50H),0.21 (s, 12H)

13C-NMR (CDCl3) d 172.4, 142.2, 137.3, 132.2, 43.3, 38.9, 33.7, 31.9, 29.7, 29.4, 24.0, 22.7, 16.0, 14.1,13.8, 12.8, -2.3

FTIR (KBr cm�1) 2955, 2922, 28.2, 1635, 1482, 1455, 1424, 1380, 1276, 1247, 1129, 1086, 868, 839, 813.

1H-NMR (CDCl3) d 7.40 (d, 1H, J¼ 1.57Hz), 7.22 (dd, 1H, J.sub.1¼ 7.75Hz, J.sub.2¼ 1.57Hz), 7.09 (d,1H, J¼ 7.75Hz), 3.45 3.36 (m, 4H), 3.06 2.98 (m, 4H), 1.15 0.90 (m, 25H), 0.74 0.64 (m, 4H),0.12 (s, 6H).

13C-NMR (CDCl3) d 171.6, 171.0, 143.6, 137.4, 136.5, 132.8, 126.3, 125.6, 43.4, 38.9, 33.5, 31.8, 29.2,29.1, 23.8, 22.5, 15.9, 14.0, 13.6, 12.7, -2.3.

FTIR (KBr cm�1) 2972, 2926, 2854, 1623, 1484, 1430, 1383, 1291, 1251, 1220, 1105, 1062, 842.

402 Polymerization Method

refluxed for 4 hours. The solution was then cooled and the pH increased to 9 usingsodium hydroxide. Thereafter the aqueous phase was extracted with CH2Cl2, driedwith MgSO4, and re-concentrated. The residue was purified by column chromatogra-phy using hexane/EtOAc, 96/4, respectively, and the product isolated in 52%yield as awhite solid, MP¼ 26�C.

4. Preparation of 2-Dimethyldecylsilyl-5-Dimethyldecylsilyl-1,4-bis(Chloromethyl)Benzene

The Step 3 product (1.09mmol) dissolved in 20ml of CH2Cl2 was cooled to 0�C and

then treated with vinyl chloroformate (82.7mmol) and stirred for 5 hours at ambienttemperature. The mixture was next quenched with brine, and the aqueous phase wasextracted with CH2Cl2 and combined extracts dried with MgSO4 and concentrated.The residue was purified by chromatography using hexane, and the product wasisolated in 65% yield MP¼ 40�C.

5. Preparation of Poly[2-(Dimethyloctylsilyl)-5-(Dimethyldecylsilyl)-1,4-Phenylene Vinylene]

The Step 4 product (0.2mmol) dissolved in 15ml of THF was added to potassiumt-butoxide (112.5mg) dissolved in 5ml THF over 10 minutes and then stirredovernight. The polymer was precipitated in methanol, purified by re-dissolving inTHF, and last precipitated in acetone. After drying, the product was isolated in 26%yield.

DERIVATIVES


NOTES

1. Beginning with p-benzophenone Kreuder [1] devised a seven step method forpreparing poly(1,4-phenylene vinylene) derivatives as illustrated below.

FTIR (KBr cm�1) 2923, 2854, 1466, 1411, 1377, 1344, 1254, 1192, 1172, 1140, 1108, 837, 792, 7161H-NMR (CDCl3) d 7.57 (s, 2H), 4.70 (s, 4H), 1.36 1.29 (m, 29H), 0.92 0.83 (m, 9H), 0.42 (s, 12H)13C-NMR (CDCl3) d 141.9, 140.2, 137.0, 46.5, 33.6, 32.0, 29.7, 29.6, 29.4, 29.3, 24.0, 22.7, 16.5, 14.1, -1.5.UV (CDCl3) dmax: 438 nmUV (film) dmax 430 nmMn¼ 289,000; Mw¼ 1,065,000; PDI¼ 3.7TGA¼ 350�C(dec); DSC¼ 300�C (dec); no Tg or Mp

FTIR (KBr cm�1) 2963, 2922, 2852, 1466, 1370, 1248, 1203, 1166, 1121, 1057, 8351H-NMR (CDCl3) d 7.71 (s, 2H), 3.63 (s, 4H), 2.51 (q, 5H, J¼ 7.10Hz), 1.30 0.81 (m, 50H), 0.30 (s, 12H)13C-NMR (CDCl3) d 143.2, 137.821, 134.7, 58.6, 46.2, 33.7, 31.9, 29.7, 29.3, 24.2, 22.7, 16.6, 14.1,

11.7, 1.3

Notes 403

a

OO

OH

HO

Br Br

OC5H11

C5H11O

Br Br

OC5H11

C5H11O

(HO)2B B(OH)2

OC5H11

C5H11O

B B

O

O O

O

Intermediate

OC5H11

C5H11O

Br Br

OC5H11

C5H11O

Br CHO Br

OC5H11

C5H11O

OC5H11

C5H11O

Br

OC5H11

C5H11O

Intermediate

i ii iii

iv

v vi

vii

i: Br2/HBrii: C5H11Briii: BuLi, B(OCH3) 3, HCliv: 1,3-Propanediolv: BuLi, DMF, HClvi: TiCl4/Znvii: NaHCO3

2. In an earlier investigation by the author [2] poly(phenylene-co-vinylene)containing 2,5-thienylene vinylene, (I), was prepared and used as semicon-ductors in luminescent devices.

S

H3COS

OCH3

a

b

c

d

(I)

3. Corma Canos [3] prepared electroluminescent materials by encapsulatingpolyphenylene-vinylene derivatives in an CsX zeolite.

404 Polymerization Method

4. Stilbene methacrylate esters prepared by Holmes [4] were useful in photo-luminescent and electroluminescent optical devices.

a

O O

(II)

References

1. W. Kreuder et al., US Patent 6,114,490 (September 5, 2000)2. A.B. Holmes et al., US Patent 5,512,654 (April 30, 1996)3. A. Corma Canos et al., US Patent 7,108,802 (September 19, 2006)4. A.B. Holmes et al., US Patent 7,105,621 (September 12, 2006) and US Patent 6,919,415 (July 19, 2005)

Notes 405

m. Branched Polyesters

Title: Process for Producing PolymerizablePolybranched Polyester

Author: H. Hayakawa et al., US Patent 7,141,642 (November 28, 2006)Assignee: Dainippon Ink and Chemicals, Inc. (Tokyo, JP)

SIGNIFICANCE

A new transesterification stanoxane catalyst, tin (di(chlorodimethylsiloxy)-tin chlor-odimethylsilane), has been used to incorporate ethyl acrylate into the condensationpolymer of 2,2-bis(hydroxymethyl)propionic acid. This catalyst is preferable becauseit allows the reaction to proceed under milder conditions than those using a conden-sation esterification reaction route and makes it likely for product crosslinking sidereactions to occur.

REACTION

O O O O

HO

OHO

HO

OH O

O O

OHO

HO

OHO

HO

O O O O

O

O O

HO

OH O

O O

OO

HO

OHO

O

O

O

O

O

i

a

b

a

bNote 1

i: Tin (di(chlorodimethylsiloxy)-tin chlorodimethylsilane), hydroquinone, ethylacrylate

406

EXPERIMENTAL

Preparation of Hyperbranched Polyacrylate Polyol

A reaction vessel equipped with a Dean–Stark decanter was charged with 10 parts ofthe condensation polymer of 2,2-bis(hydroxymethyl)propionic acid having a Mn of2920 daltons, a Mw of 4280 daltons, and a PDI of 1.47. This mixture was then treatedwith tin(di(chloro-dimethylsiloxy)-tin chlorodimethylsilane) (0.25 parts), ethyl ac-rylate (100 parts), and hydroquinone (0.05 parts). The mixture was then heated tobetween 92�C and 95�C so that the amount of distillate to the decanter was 15 to20 parts per hour. Fresh ethyl acrylatewas added to the reactionvessel as neededwhilethe reaction continued for 20 hours.

Following completion of the reaction, excess ethyl acrylate was removed bydistillation and the residue dissolved in 70 parts of EtOAc. The solution waswashed three times with 30 parts of hot water at 50�C to extract the catalyst. Thesolution was further washed four times with 20 parts of 5% aqueous NaOH toremove hydroquinone, followed by a single washing with 20 parts of 1% aqueousH2SO4 and twice with 20 parts of water. The mixture was last treated with 0.0045parts of methoquinone and distilled; 13 parts of product were isolated having a Mnof 3880 daltons, Mw of 7730 daltons, which is equivalent to 25.5 vinyl groups/molecule.

DERIVATIVES

No other derivatives were prepared.

NOTES

1. The formula for the stanoxane catalyst is (ClSi(CH3)2O)2Sn-Sn(CH3)2Cl.

2. Hyperbranched polycarbonates, (I), with only marginal crosslinking sidereactions were prepared by Bruchmann [1] by transesterification, using diethylcarbonate and trihydroxy methylmethane catalyzed by potassium carbonate.

O O O

O

HO

(I)a

3. Amethod for the mild catalysis for ester/transester reactions was developed bySiddiqui [2], using the polymeric titanium glycolate catalyst, (II).

Notes 407

O

O

O

Ti

OO

Ti

O a

(II)

4. Gross [3] incorporated pendant polyalcohols onto polyacrylic acid, (III), andpoly L-glutamic acid, (IV), without crosslinking side reactions, by catalyzingwith the enzyme Novozyme-435.

OO

CHOH

HOHC

CH2OH

n

(III)

n = 0–3

HN

O

CO2H

HN

O

OO

HOHC

CH2OH(IV)

a ba

References

1. B. Bruchmann et al., US Patent Application 2007-0037957 (February 15, 2007)2. J. Siddiqui et al., US Patent Application 2006-0205917 (September 14, 2006)3. R.A. Gross et al., US Patent 6,924,129 (April 2, 2005)

408 Process for Producing Polymerizable Polybranched Polyester

n. Poly(N-Vinylformamide) Derivatives

Title: N-Vinylformamide Derivatives, PolymersFormed Therefrom and Synthesis Thereof

Author: E. J. Beckman et al., US Patent 7,135,598 (November 14, 2006)Assignee: University of Pittsburgh (Pittsburgh, PA)

SIGNIFICANCE

N-Vinylformamide was converted into N-alkyl-N-vinylformamide derivatives byreacting it with an alkyl bromide in the presence of base. When N-vinylformamideintermediates were reacted with 2,20-azobisisobutyronitrile, the polymer wasobtained. Hydrolysis of poly(N-vinylformamide) generated an N-alkyl polyvinyla-mine, a versatile synthetic intermediate.

REACTION

NH

CHO

N

CHO

C6H13

NOHC C6H13

ai iiNote 1 HN

C6H13

aiii

i: THF, potassium t-butoxide, 1-bromohexaneii: 2,20-Azobisisobutyronitrile

EXPERIMENTAL

1. Preparation of N-Hexyl-N-Vinylformamide

A reactor was charged with N-vinylformamide (0.164mol) and 200ml of anhydrousTHF and then cooled to 15�C using an ice bath. The solution was next treated withpotassium t-butoxide (0.167mol) in three portions over 45 minutes followed by thedropwise addition of 1-bromo-hexane (0.179mol) over 30 minutes. The reaction wasslowly warmed to ambient temperature and stirred overnight. Themixturewas filteredto removeKBr and then concentrated, and the residuewas dilutedwith 200ml ofwater.

409

The organic layer was extracted three times with diethyl ether, and the combinedextractionswerewashed twicewithwater and dried usingMgSO4. Themixturewas re-concentrated and then purified by chromatography on silica using diethyl ether/petroleumether,3:7, respectively; theproductwas isolated in63%yield.Otheraliphaticderivatives were prepared according to this procedure and are provided in Table 1.

2. Preparation of Poly(N-Hexyl-N-Vinylformamide)

The Step 1 product (1.0 g) and 2,20-azobisisobutyronitrile (18mg) were added to anampoule and degassed before sealing. The polymerization was carried out in an oilbath at 65�C for 15 hours. The polymer was purified by Soxhlet extraction usingpetroleum ether for 8 hours and dried under reduced pressure at 60�C for 12 hours.Polymer properties of derivatives are provided in Table 2.

3. Preparation of N-Hexyl Polyvinyl Amine

Poly(N-n-hexyl-N-vinylformamide) (0.25 g), 10ml of 2Mhydrochloric acid, and 2mlof dioxanewere stirred under reflux at 80�Cunder a nitrogen atmosphere for 24 hours.The hydrolyzed polymer was recovered by filtering the suspension and washing3 times with 50ml of deionizedwater. The resulting polymer was dried under reducedpressure at 60�C for 12 hours and then isolated.

DERIVATIVES

N

CHO

R

IR (KBr, cm-1): 2957(�CH3); 1671 (�C¼O)1H-NMR (CDCl3, d, ppm): 8.03(b, �C(¼O)H); 4.23, 3.1(b, �H2C�CHN� and �N�CH2CH2�); 2.0,

1.53 (b, �H2C�CHN– and �N�CH2CH2�); 1.31(s, � (CH2)3CH3); 0.91(s, �CH2CH3)

TABLE 1. Selected N-alkyl-N-vinylformamide derivatives prepared by reactionof the corresponding alkyl bromide with N-vinylformamide in the presenceof potassium t-butoxide.

Entry R Yield (%)

1a n-Butyl 561c n-Decyl 891d n-Dodecyl 751e 2-Ethyl-phthalimide —

IR (NaCl, v: cm�1): 1698 (�NHC¼O)H); 1630 (C¼C)1H-NMR (CDCl3, d, ppm): 8.31, 8.14 (2s, 1H,�C(¼O)H); 7.25 7.16, 6.61 6.52 (m, 1H, H2C¼CH�); 4.65

4.54 (m, 1H, HaHbCd¼CH�); 4.45 4.42 (s, 1H, HaHbC¼CH�); 3.60 3.44 (t, 2H,�NCH2CH2�); 1.65 1.56 (m, 2H, � CH2CH2CH2�); 1.31 (m, 6H, �CH2(CH2)3CH3);0.90 0.88 (t, 3H, �NCH2CH2(CH2)3CH3)

410 N-Vinylformamide Derivatives, Polymers Formed Therefrom and Synthesis Thereof

POLYMER DERIVATIVES

NOHC R

a

NOTES

1. Vinylformamidewas previously prepared by the author [1] and illustrated below

H2N

O

O

HNO

O

OOH

HNOi

OH

HNO ii

i: Acetaldehyde, triethyl amine, isooctaneii: Succinic anhydride, ethyl acetate, Amberlyst 15 acid catalyst.

2. The utility of N-alkyl-poly(N-vinylformamide) was illustrated in the currentinvention by the author in the preparation of N-hexyl-N-dihydroperfluorooctylpolyvinylamine (I).

NH

CHO NHai

NCHO

ii

N

O

O

OH N

O

O

O

n-C7F15

O

iii

iv

Intermediate

Na

C7F15

O N

a

C7F15

vIntermediate

C6H13

C6H13 C6H13

C6H13N

a

C6H13 CHO

vi

(I)

TABLE 2. Results of bulk polymerization of N-alkylvinylformamide at 65�C using2,20-azobisisobutyronitrile as the free radical initiator.

Entry RReactionTime (h)

Mn 1� 103

(daltons)Mw 1� 103

(daltons) PDIConversion

(%)

2a n-Butyl 10 13.2 27.3 2.05 862b n-Hexyl 15 8.3 18.9 2.27 822c n-Decyl 15 10.0 20.4 2.05 592d n-Dodecyl 15 10.2 21.3 2.09 59

Notes 411

i: THF, potassium t-butoxide, 1-bromohexaneii: Azobisisobutyronitrileiii: NaOH, dioxaneiv: Perfluorooctanoic acid, methanolv: Polyvinylamine, methanolvi: Borane, THF

3. Copolymers of vinylformamidewith acrylamide,methacrylic acid, (II), metha-crylates, acrylonitrile, and acrylamide were prepared by Hund [2] and used asflocculants and coagulants in waste water treatment. Sommese [3] preparedpoly(vinylamine-co-N-vinylformamide), (III), having molecular weights be-tween 0.8� 106 and 2.0� 106 daltons, which were used as coagulants inwastewater treatment.

NH2 HNCHO

a b a : b1: 1 3: 7

(III)

H2NCHO

b

(II)OO

a

_

+

4. Lindsay [4] used poly(vinylamine-co-N-vinylformamide), (II), containingroughly 70% amine content as a component in textile materials and paper toimprove wet strength properties.

References

1. E.J. Beckman et al., US Patent 7,026,511 (April 11, 2006)2. R. Hund et al., US Patent 6,797,785 (September 28, 2004)3. A.G. Sommese et al., US Patent 6,610,209 (August 26, 2003)4. J. Lindsay et al., US Patent 6,824,650 (November 30, 2004)

412 N-Vinylformamide Derivatives, Polymers Formed Therefrom and Synthesis Thereof

o. Oligonucleotide Preparation

Title: Polymers

Author: E. A. H. Hall et al., US Patent 7,022,808 (April 4, 2006)Assignee: The Secretary of State for Defence DSTL (Salisbury, GB)

SIGNIFICANCE

Peptide nucleic acid derivatives containing s-triazine have been prepared that can actas DNA mimics and as supports for use in oligonucleotide preparation. Theiranticipated use is in the preparation of naturally and unnaturally occurringoligonucleotides.

413

REACTION

H2NNH2

H2NNH2

H2N

HN

H2N

HN Boc

NH

HN Boc

NN

N

Cl

Cl

Intermediate 1

Intermediate 2

i

iiiii

NH

NH

O

O NH

N

O

O

N

N

O

O

NH

HN Boc

NN

NCl

vvi

viN

N

O

O

NH

HN Boc

NN

N

Intermediate 2

Intermediate 1

NH

HN

N

N

O

O

NH

HNBoc

NN

N NH

HN

N

N

O

O

NH

HN Boc

NN

N

vii

i: Benzylchloride, CH2Cl2

ii: CH2Cl2, t-butoxy carbonyl ester anhydrideiii: Cyanuric chloride, acetone, sodium bicarbonateiv: Thymine, acetonitrile, pyridine, benzoyl chloridev: Acetone, sodium bicarbonatevi: THFvii: CH2C12, trifluoroacetic acid, THF, triethylamine

EXPERIMENTAL

1. Preparation of N-Benzyl-Ethylenediamine

Ethylene diamine (10 g) dissolved in 60ml of CH2Cl2 wasmixedwith benzylchloride(21.01 g) in CH2Cl2 and then stirred at ambient temperature for several hours andconcentrated. The residue was dissolved in 100ml of EtOAc, washed twice with100ml apiece of 1MKHCO3 and 5% of NaHSO4, oncewith 100ml of brine, and then

414 Polymers

dried over MgSO4. The solution was concentrated, and the product was isolated in92% yield as a colorless oil.

2. Preparation N-t-Butoxy Carbonyl Ethylenediamine

Ethylene diamine (10 g) dissolved in 60ml of CH2Cl2 was added to a solution oft-butoxycarbonyl ester anhydride (4.90 g) in 60ml ofCH2Cl2 over a 2-hour period andthen stirred for 22 hours at ambient temperature and concentrated. The residue wastreatedwith 100ml of water, and the insoluble product was removed by filtration. Theaqueous solution was extracted three times with 100ml of CH2Cl2, and the combinedorganic layers were re-concentrated. The product was isolated in 83% yield as acolorless oil.

3. Preparation of 1,3-Dichloro-5-[2-(1-N-t-Butoxy CarbonylEthylenediamine)]-s-Triazine

The Step 2 product was added to a slurry of cyanuric chloride (75mg) in 12ml ofacetone and then poured into icewater. NaHCO3 (262mg) was added and stirred for 2hours at 0�C; then awhite solid was filtered off. This solid was washed with water anddried in vacuo over P2O5. After re-crystallization from pyridine the product wasisolated in 93% yield as a white solid.

4. Preparation of N-Benzyl-Thymine

Thymine (2.62 g) was dissolved in 33ml of acetonitrile and 13.5ml of pyridine. Themixture was then treated with benzoyl chloride (11.68 g), stirred at ambient tempera-ture for 24 hours, and concentrated. The residuewas extracted into 62ml of a dioxane/water mixture, 1:1, and treated with K2CO3 (4.86 g); the suspension was stirred atambient temperatureovernight. 1MofHydrochloric acidwas thenadded to the solutionto reduce the pH to 3, whereupon a precipitate was collected and re-crystallized fromethanol. After drying, 2.5 g of product was isolated as pale yellow needles.

5. Preparation of 1-N-Benzyl Thymine-3-[2-(1-N-t-Butoxy CarbonylEthylenediamine)]-5-Chloro-s-Triazine

A reactor was charged with the Step 4 product (0.4 g), Na2CO3 (0.2 g), and the Step 3product (0.5 g) dissolved in 20ml of acetone and 10ml of water; this mixture wasstirred at ambient temperature for 5hours.Theproductwas isolated after filtration, and0.41 g of product was isolated as a yellow solid.

6. Preparation of 1-N-Benzyl Thymine-3-N-Benzyl-Ethylenediamine-5-[2-(1-N-t-Butoxy Carbonyl Ethylenediamine)]-s-Triazine

The Step 5 product (0.1 g) suspended in 5ml of THF was treated with the Step 1product (0.034 g) and then refluxed overnight. The off-white solid that resulted wasfiltered and washed with THF and then re-crystallized from pyridine and the productisolated in 63% yield.

Experimental 415

7. Preparation of Dimer and Higher Analogues

The Step 6 product (0.50mg) was suspended in 300ml of CH2Cl2, treated with 0.5mlof trifluoro-acetic acid, stirred for 1 hour, and then concentrated. The residue wasdissolved in 5ml of THF, then treated with 24.52ml of triethylamine and the Step 5product (34mg). This mixture was stirred for 2 hours at 40�C and treated withtriethylamine until the mixture was basic. The solution was then concentrated and theresidue dissolved in EtOAc. The solutionwaswashed twicewith 5ml ofKHSO4, oncewith 5ml of water, twicewith 5ml ofNaHCO3 and brine, and then dried overMgSO4.Themixturewas re-concentrated, and the product was isolated in 93% yield as an off-white solid.

The Step 7 process could be repeated with the same or different monomers until anoptimum chain length was obtained.

DERIVATIVES


NOTES

1. Nucleic acid mimics were developed by Nielson [1] and Turney [2] that willstrand-invade DNA at purine rich sites to form triplex structures.

2. Peptide nucleic acids, (I), that are not polynucleotides will form complemen-tary DNA and RNA strands stronger than the corresponding DNA, as reportedby Nielson [3].

N

NH

O

O

NOH

O

H2N

(I)

References

1. P.E. Nielson et al., Science, 254: 1497–1506, 19912. D.Y. Turney et al., Proc. Natl. Acad. Sci. USA, 1993, 90, 1667–16703. P. Nielson et al., US Patent 5,977,296 (November 2, 1999)

416 Polymers

p. Multistar Polystyrene

Title: Star-Shaped Polymer, Multiple Star Polymer,and Their Preparation Methods

Author: H.-J. Lee et al., US Patent Application 2005-0209408 (September 22, 2005)Assignee: Korea Advanced Institute of Science and Technology (Daejeon, KR)

SIGNIFICANCE

A method for preparing star-shaped polystyrene by either the incremental or singleaddition of divinyl benzene to a living polystyryl anion is described. Star-shapedpolymers containingup to34armswerepreparedwithpolydispersities of less than1.1.

REACTION

i

Lia b

d e

c

i: Divinylbenzene

EXPERIMENTAL

Preparation of Star Polystyrenes: Generic Procedure

A living polystyryl anion having aMn of 12,000 daltons was prepared by the additionof n-butyllithium dissolved in cyclohexane to styrene. This mixture was then treatedincrementally with divinylbenzene (0.81eq). The material was precipitated in metha-nol and the product isolated with a linking efficiency of more than 95%.

417

STAR FORMATION LINKING PROFILE

NOTES

1. Hyperbranched water-soluble polyesters containing polyethylene glycol andadipic acid were prepared by Stumbe [1] and used as additives in paints.

2. An 8-pedal flower-like nanoparticle and nanostrings consisting of styrene andbutadiene were prepared byWang [2,3], respectively, and used as a componentin tires.

3. Dendritic-based macromolecules containing polystyrene were prepared byFrechet [4] and used in specialty medical applications. Star-shaped conjugateddentrimers containing styrene were prepared by Burn [5] and used as compo-nents in light-emitting diodes.

References

1. J-F. Stumbe et al., US Patent 7,148,293 (December 12, 2006)2. X. Wang et al., US Patent 7,205,370 (April 17, 2007)3. X. Wang, US Patent 7,179,864 (February 20, 2007)4. J.M.J. Frechet et al., US Patent 7,101,937 (September 5 2006)5. P.L. Burn et al., US Patent 7,083,862 (August 1, 2006)

TABLE 1. Physical properties of star polystyrenes prepared by the incrementaladdition of divinylbenzene to a polystyrene anion having a Mn of roughly 26,000daltons.

Entry

Increments of0.74ml of

Divinyl Benzene

Star PolystyreneMn� 104

(daltons)Linking

Efficiency (%) PDINumberof Arms

1 2 31.2 93 1.05 132 5 67.3 98 1.07 263 7 88.8 99 1.09 34

TABLE 2. Physical properties of star polystyrenes prepared by the single additionof divinylbenzene to polystyrene anion having a Mn of roughly 26,000 daltons.

Entry

Single Additionof Divinyl

Benzene (ml)Star PolystyreneMn� 104 (daltons)

LinkingEfficiency (%) PDI

Numberof Arms

1 1.7 42.3 68 1.05 162 3.4 54.1 75 1.05 213 5.1 69.5 79 1.08 27

418 Star-Shaped Polymer, Multiple Star Polymer, and Their Preparation Methods

XVII. OPTICAL MATERIALS

Second-Order Nonlinear Optical Materials

Title: Polymers Having Pendant Nonlinear OpticalChromophores and Electrooptic Devices Therefrom

Author: D. Huang et al., US Patent 7,019,453 (March 28, 2006)Assignee: Lumera Corporation (Bothell, WA)

SIGNIFICANCE

A polymer containing the nonlinear optical chromophore trans-2,20-formyl-3,30,-4,40-tetrabutoxyvinylthiophenewas prepared and proved is effective as a waveguide.


419

REACTION

N

OH

N

OAc

N

OAc

CHO

N

OH

CHO

N

O

CHO

Si(CH3)2t-C4H9

N

OSi(CH3)2t-C4H9

OH

N

OSi(CH3)2t-C4H9

P(C6H5)3Br

N

OSi(CH3)2t-C4H9

SS

C4H9O OC4H9

C4H9O OC4H9

CHO

N

OSi(CH3)2t-C4H9

SS

C4H9O OC4H9

C4H9O OC4H9

O

NC

NC

CN

OH

i ii iii iv

vvivii

viii

ix

420 Polymers Having Pendant Nonlinear Optical Chromophores and Electrooptic Devices Therefrom

N

OSi(CH3)2t-C4H9

SS

C4H9O OC4H9

C4H9O OC4H9

O

NC

NC

CN

O

O

O

F

FF

N

OH

SS

C4H9O OC4H9

C4H9O OC4H9

O

NC

NC

CN

O

O

O

F

FF

N

O

SS

C4H9O OC4H9

C4H9O OC4H9

O

NC

NC

CN

O

O

O

F

FF

O

CO2H

x

xi

xii

Reaction 421

N

O

S

S

C4H9O

C4H9O

OC4H9

OC4H9

O

NC

NC

CN O

O

OF

F

F

O

CO2H

O

O O O

O

FF

F

a b

i: Acetic anhydrideii: DMF, phosphorous oxychlorideiii: Ethanol, potassium carbonateiv: t-Butyldimethylsilyl chloride, imidazole, DMFv: Methanol, sodium borohydride, sodium hydroxidevi: Triphenylphosphine.hydrogen bromide, CHCl3


vii: Butyllithium, trans-2,20-formyl-3,30,4,40-tetrabutoxy-vinylthiophene, THFviii: 3-Cyano-4,5,5-trimethyl-2-(2,2-dicyanovinylidene)-2,5-hydrofuran, piperidine,

CHCl3ix: Pyridine, CH2Cl2, 4-(trifluorovinyloxy) benzoyl chloridex: THF, hydrochloric acidxi: N,N-Dimethylaminopyridine, triethylamine, CH2Cl2, phthalic anhydridexii: Poly(4-vinylphenol), 4-(dimethylamino)-pyridinium 4-toluenesulfonate (0.786

mmol), THF, CH2Cl2, 4-(trifluorovinyloxy) benzoyl chloride, di-isopropylethyl-amine, 1,2-dicyclohexyl-carbodiimide

EXPERIMENTAL

1. Preparation N-Ethyl-N-(6-Hexylacetate)Aniline

N-Ethyl-N-(6-hydroxyhexyl)aniline (0.5mol) and acetic anhydride (0.75mol) weremixed and heated to 65�C for 20 hours. The reaction mixture was then poured intowater and extracted with CH2Cl2. The crude oil was purified by flash columnchromatography with hexane/EtOAc, 3:1, respectively, and the product was isolatedin 84% yield.

2. Preparation N-Ethyl-N-(6-Hexylacetate)-4-Formylaniline

DMF (0.624mol) was placed in a reaction vessel and cooled to 0�C and then treatedwith the dropwise addition of POCl3 (0.499mol). The Step 1 product (0.416mol)was added and stirred 30 minutes at ambient temperature and 3 hours at 100�C. Thereaction mixture was next poured into water and neutralized with NaHCO3. Afterextraction with CH2Cl2 the mixture was purified by flash column chromatographywith hexane/EtOAc, 5:2, respectively, and the product was isolated in 80% yield.

3. Preparation N-Ethyl-N-(6-Hydroxyhexyl)-4-Formylaniline

The Step 2 product (0.33mol) was dissolved in 600ml of ethanol and treated withK2CO3 (0.36mol); the mixture was then stirred 4 hours at ambient temperature. Themixture was extracted with CH2Cl2 and dried with MgSO4. After the mixture wasfiltrated and concentrated, the residue was purified by flash column chromatographywith EtOAc/CH2Cl2, 3:2, respectively, and the product was isolated in 66% yield.

4. Preparation N-Ethyl-N-(6-t-Butyldimethylsilylhexyl)-4-Formylaniline

The Step 3 product (0.217mol), t-butyldimethylsilyl chloride (0.282mol), imidazole(0.563mol), and 140ml of DMF were mixed and heated for 10 hours at 50�C. Themixture was then poured into water and extracted with CH2Cl2. It was dried andconcentrated, and the residue was purified by flash column chromatography withhexane/EtOAc, 3:1, respectively, and the product was isolated in 87% yield.

Experimental 423

5. Preparation N-Ethyl-N-(6-t-Butyldimethylsilylhexyl)-4-Hydroxylmethylaniline

TheStep 4 product (0.187mol)was dissolved in 200ml ofmethanol and treated at 0�Cwith the dropwise addition of NaBH4 mixed with 4ml of 7% NaOH solution dilutedwith 30ml ofwater.After themixturewas stirred at ambient temperature for 3 hours, itwas poured into water and extracted with CH2Cl2. The product was purified by flashcolumn chromatography with hexane/EtOAc, 2:1, respectively, and isolated in 84%yield.

6. Preparation N-Ethyl-N-(6-t-Butyldimethylsilylhexyl)-4-(Triphenylphosphine Bromide) Methylaniline

The Step 5 product (0.157mol), PPh3�HBr (0.142mol), and 400ml of CHCl3 weremixed and refluxed for 3 hours in a reactor containing a Dean–Stark apparatus. Themixture was then concentrated by removing most of the solvent and precipitating indiethyl ether; the product was isolated in 84% yield.

7. Intermediate 7

The Step 6 product (0.103mol) was dissolved in 2000ml of THFand cooled to�40�Cand then treated with the dropwise addition of butyllithium (0.113mol). It wasstirred at ambient temperature for 30 minutes and then treated with the dropwiseaddition of trans-2,20-formyl-3,30,4,40-tetrabutoxy-vinylthiophene (0.09mol) dis-solved in 1400ml of THF. The reaction mixture was stirred for 10 hours andconcentrated, and the residue was purified by flash column chromatography withCH2Cl2/hexane/EtOAc, 4:4:0.2, respectively; the product was isolated in 75% yield.

8. Intermediate 8

A mixture consisting of the Step 7 product (34.5 mmol), 3-cyano-4,5,5-trimethyl-2-(2,2-dicyanovinylidene)-2,5-hydrofuran (41.5 mmol), piperidene (catalytic amount),and 15ml of CHCl3 were refluxed for 5 hours. The mixture was then purified by flashcolumn chromatography with hexane/EtOAc/CH2Cl2, 4:1.2:4, respectively, and theproduct was isolated in 45% yield.

9. Intermediate 9

The Step 8 product (6.52 mmol) and 1.32ml pyridine were dissolved in 80ml ofCH2Cl2 and then treated with the dropwise addition of 4-(trifluorovinyloxy) benzoylchloride (13.04mmol) dissolved in 10ml of CH2Cl2 at 0

�C. Themixturewas stirred atambient temperature for 12 hours and poured intowater. It was extracted with CH2Cl2and purified by flash column chromatography with hexane/CH2Cl2/EtOAc, 4:4:0.4,respectively, and the product was isolated in 91% yield.


10. Intermediate 10

TheStep 9 product (5.875mmol) dissolved in 150ml ofTHFwas treatedwith 50ml of1M HCl and then stirred at ambient temperature for 12 hours and neutralized withNaHCO3 solution. After being extracted with CH2Cl2, it was purified by flashchromatography using hexane/CH2Cl2/EtOAc, 1:2:1, respectively, and the productwas isolated in 82% yield.

11. Intermediate 11

The Step 10 product (0.848 mmol), N,N-dimethylaminopyridine (0.017 mmol), andtriethylamine (1.7 mmol) were dissolved in 30ml of CH2Cl2 and then treated withphthalic anhydride (1.06 mmol). Themixturewas next stirred at ambient temperaturefor 12 hours. The solution was washed with 1M of HCl solution, extracted withCH2Cl2, and washed with NaHCO3 solution and water. The mixture was purified byflash chromatography using CH2Cl2/acetone, 2.5:1, respectively, and the product wasisolated in 73% yield.

12. Preparation of Polymer

Vacuum dried poly(4-vinylphenol) (0.9436 g), 4-(dimethylamino)pyridinium 4-to-luenesulfonate (0.786 mmol), and the Step 11 product (1.044 g) were dissolved into30ml of THF and 10ml of CH2Cl2. After the addition of 1,2-dicyclohexylcarbodii-mide (1.965 mmol) the solution was stirred at ambient temperature for 40 hours.Thereafter 4-(trifluorovinyloxy) benzoyl chloride (17.12 mmol), 1,2-dicyclohexyl-carbodiimide, and di-isopropylethylamine (14 mmol) were added, and the mixturestirred an additional 24 hours. The solution was then concentrated to about 10ml andprecipitated in methanol. The solid was isolated, re-dissolved in CH2Cl2, and re-precipitated in methanol, the process being repeated 10 times. The product was driedand 2.43 g were isolated as a dark blue powder.

DERIVATIVES

Only the Step 12 derivative was prepared

TESTING

A electrooptic polymer crosslinked film was formed by spin-coating a 25 wt% of theStep 12 product in cyclopentanone onto an ITO covered glass slide. The solution wasfiltered through a 0.2 mm nylon filter, spin-coated at 500 rpm for 6 seconds and1000 rpm for 30 seconds, and then soft baked at 50�C overnight under vacuum togivea3.2 mmthick film.The filmwascoronapoledwith aneedle at 20 kVandheated to220�Cfor 5minutes for crosslinking. The filmwas then cooled to ambient temperatureunder the applied field to give an electro-optic film with an r33 of 36 pm/Vat 1.31 mm.

Testing 425

NOTES

1. Additional Step 12 polymeric nonlinear optical chromophores and electro-optic devices were prepared by the author [1] in earlier investigations.

2. Compositions comprising a crosslinkable perfluoro poly(aryl ether), (I), and anonlinear optical chromophore were prepared by the author [2] and Chen [3].

OCF3

CF3

O O O

O

O

O

F

F

F

(I)

F4F4 F4F4

a

3. Nonlinear optical phenyldiazo chromophores, (II), and (III), were prepared byGharavi [4] and Lindsey [5], respectively, and used as multifunctional opticalswitches.

NN N

N OH

O2N

(II)

N

N

H3CO OCH3

N

N

O2N

OH OH

NO2

(III)

References

1. D. Huang et al., US Patent 6,750,603 (June 15, 2004) and US Patent 6,716,995 (April 6, 2004)2. D. Huang et al., US Patent Application 2007-0032628 (February 8, 2007)3. B. Chen et al., US Patent 7,196,155 (March 27, 2007)4. A. Gharavi et al., US Patent 7,205,347 (April 17, 2007)5. G.A. Lindsay et al., US Patent 7,071,268 (July 4, 2006)


XVIII. PHOTOACTIVE POLYMERS

A. Photoluminscence

Title: Polymeric Compound and OrganicLuminescence Device

Author: J. Kamatani et al., US Patent 7,238,435 (July 3, 2007)Assignee: Canon Kabushiki Kaisha (Tokyo, JP)

SIGNIFICANCE

Iridium-containing copolymers have been prepared by postreacting fluorene-orbiphenyl copolymers with a cyclic bidentate ligand iridium derivatives. These blockcopolymers demonstrate exceptionally high luminescent efficiency.

REACTION

C8H17 C8H17B B

O

O O

O C8H17 C8H17

N

C8H17 C8H17

N

C8H17 C8H17

N

N

N

Ir

i iia

ba c


427

i: 2,5-Dibromopyridine, THF, potassium carbonate, tetrakistriphenylphosphinepalladium

ii: Iridium acetylacetone complex, glycerol, hydrochloric acid

EXPERIMENTAL

1. Preparation of Poly[2,7-(9,9-di-n-octyl-fluorene)-co-2,5-Pyridine]

A 20-ml flask was charged with a fluorene-borate complex (2.0mmol),2,5-dibromopyridine (2.0mmol), and a mixture of 8ml of THF and 6ml of aqueous2MK2CO3. Once the mixture was dissolved, the solution was treated with Pd(PPh3)4(0.0015mmol) and refluxed for 48 hours. Thereafter methanol was added to thesolution, causing a precipitate to form. The solid was washed with water and thenSoxhletwas extractedwith acetone for 24 hours; the productwas isolated in 85%yieldhaving a Mn of 11,000 daltons.

2. Preparation of Poly[2,7-(9,9-di-n-Octyl-Fluorene)-co-2,5-Pyridine]

A 100-ml round bottomed flask containing 50ml of glycerol was treated with theStep 1 product (1.0 mmol) and the iridium acetylacetone complex (0.2mmol).The mixture was heated for 18 hours and then cooled to ambient temperatureand poured into 300ml of 1M HCl. The resulting precipitate was isolated,washed with water, and dissolved in chloroform and filtered. The material wassubjected to Soxhlet extraction with acetone for 24 hours, and 0.50 g of a yellowpowder was isolated. The product had a Mn of 13,000 daltons with a polydis-persity of 2.1.

LUMINESCENT TESTING

A selected experimental agent was dissolved in chloroform and a 0.1 mm thicksample spin-coated onto a quartz substrate. Thereafter the sample was exposed topulsative nitrogen laser light at an excitation wavelength of 337 nm at ambienttemperature using a luminescence life meter. After completion of the excitationpulses, the decay time of luminescence intensity was measured. Testing results areprovided in Table 1.

428 Polymeric Compound and Organic Luminescence Device

TABLE 1. Selected iridium-containing polymers and corresponding luminescenthalftimes after excitation at 337 nm.

Entry Structure Luminscent Halftime (h)

1a

C8H17 C8H17

N

C8H17 C8H17

N ba c350

1b

C8H17 C8H17

N

C8H17 C8H17

N

N

N

Ir

ba c337

4

C8H17 C8H17

N

C8H17 C8H17

Ob

a

c

OIr OO

(Acac)2

700

5

Ob

a

c

O Ir OO

(Acac)2

C6H13C6H13

C6H13 C6H13600

NOTES

1. Polymerizable iridium-containing compounds, (I), were prepared by Takeuchi[1] and used in light-emitting devices.

N

R

N

Ir

O

O

O

O

R = H, Cl, NO2

(I)

Notes 429

2. Fryd [2] prepared rhenium, (II), and iridium copolymers that exhibitedphotoluminescent and electroluminescent properties.

O

O

SO2

O

Re

COOC CO

N N

(II)

a b

3. Macromolecular quinoxaline, (III), and pyran derivatives, (IV), were preparedby Shitagaki [3] and Yamagata [4], respectively, and used in light-emittingelements.

N

NN

N

N

N

N

N

(III)

430 Polymeric Compound and Organic Luminescence Device

O

NC CN

NN

(IV)

4. A polymeric fluorescent material exhibiting fluorescent properties was pre-pared by Noguchi [5] having an excellent fluorescence quantum yield and lightemitting efficiency when used a light-emitting device.

C8H17 C8H17

Na

(IV)

References

1. M. Takeuchi et al., US Patent Application 20040247934 (December 9, 2004)2. M. Fryd et al., US Patent 7,060,372 (June 13, 2006)3. S. Shitagaki et al., US Patent 7,245,073 (July 17, 2007)4. S. Yamagata et al., US Patent 7,217,465 (May 15, 2007)5. T. Noguchi et al., US Patent 7,258,932 (August 21, 2007)

Notes 431

Title: Electroactive Fluorene Copolymers and DevicesMade with Such Polymers

Author: F. P. Uckert et al., US Patent 7,211,643 (May 1, 2007)Assignee: E. I. du Pont de Nemours and Company (Wilmington, DE)

SIGNIFICANCE

There is a continuing need for preparing photoactive compounds having bothimproved efficiency and processes associated with their production. To address thisneed, electroluminescent conjugated copolymers containing 2,7-fluorenyl units havebeen prepared in a single synthetic step that require limited processing efforts and thatare suitable for emission in the blue and blue-green spectral region.

REACTION

I I

C2H5C2H5 C2H5C2H5

N

C6H13

ia

432

EXPERIMENTAL

Preparation of Electroluminescing Copolymer

A 50-ml Schlenck tube equipped with a stirring bar containing bis(1,5-cyclooc-tadiene)-nickel(0) (4.48mmol), 2,20-bipyridyl (4.48mmol), and 1,5-cycloocta-diene (4.48mmol) was treated with 5ml of DMF and the ensuing deep blue/purple solution stirred at 60�C for 30 minutes. The mixture was then treatedwith 2,7-diiodo-9,9-bis(2-ethylhexyl)fluorene (1.68mmol) and 2,5-bis(p-bromo-phenyl)-N-(p-hexylphenyl)pyrrole (0.56mmol) in 20ml of toluene by syringeand then stirred for 5 days at 75�C. The solution was cooled to ambienttemperature and precipitated into a mixture of 100ml apiece of methanol andacetone and 5ml concentrated hydrochloric acid. After of the mixture wasstirred for 2 hours, it was filtered; the solid residue was dissolved in chloroformand re-precipitated in methanol and acetone solution, and re-filtered. The residuewas successively washed with methanol, water and methanol, and dried; theproduct was isolated having a Mn of 47,200 daltons.

DERIVATIVES

TABLE 1. Monomers used in preparing fluorene copolymers.

Entry Monomer 1 Monomer 2 Mn (daltons)

1

I I

C2H5C2H5 Br N

C6H13

Br 47,200

2

Br Br

C2H5C2H5

CO2CH3

BrBr

68,700

3

Br Br

C2H5C2H5

CO2CH3

BrBr98,488

(continued)

Derivatives 433

TESTING

Fluorene copolymers were tested as light-emitters in a light-emitting diode. Theanode used was indium tin oxide supported by a glass substrate where the holeinjection/transport layer was spin-coated onto the indium tin oxide. The holeinjection/transport layer was poly(3,4-ethylenedioxy-thiophene) at a thickness ofabout 2000A

�or a bilayer of poly(3,4-ethylene-dioxythiophene) and polyvinyl-

carbazole at the same thickness. The experimental copolymer was dissolved intoluene to form a 2.0% solutionthen filtered through a 0.22 m filter and spin-coated over the hole injection/transport layer. The target thickness of thecopolymer layer was 800A

�, with actual thicknesses typically in the range of

500 to 1000A�. Light-emitting test results are provided in Table 2.

Entry Monomer 1 Monomer 2 Mn (daltons)

4

Br Br

C2H5C2H5

NN

OBr Br

67,300

5

Br Br

C2H5C2H5

Br Br60,900

Note: Entry 1 was stirred for 5 days at 75�C and then cooled, while Entries 2 to 5 were capped withbromobenzene after 4 days of heating.

TABLE 2. Light-emitting testing for fluorene copolymers in a light-emitting diodeusing different hole injection/transport layers.

EntryHole Injection/

TransportVoltage at100 Cd/m2

Cd/A*1 at25mA

Cd/A(at mA)

Cd/m2

(at V)QE%(at V)

1 PEDOT*2 — — — 849 (12V) 0.18 (12V)2 PVK*3 6.6 0.06 0.068 (55mA) — —3 PVK 6.9 0.2 0.22 (20mA) — —4 PEDOT/PVK >10 0.68 0.87 (3mA) — —5 PEDOT/PVK >10 1.14 3.74 (0.04mA) — —

*1Candela*2 Poly(3,4-ethylene-dioxythiophene)*3 Polyvinylcarbazole


434 Electroactive Fluorene Copolymers and Devices Made with Such Polymers

NOTES

1. Aluminium-pyrazol-5-one derivatives, (I), prepared by Kathirgamanathan [1]were effective as white light emitters and used in organic electroluminescentdevices. Bis(2-phenylimidazo[1,2-a]pyridinato-N,C)iridium derivatives, (II),prepared by Lussier [2] were effective as phosphorescent emission agents.

AlO

O

NN

(I)

3N

NIr

O

O

2

(II)

2. Fluorene copolymers, (III), were prepared by Sohn [3] that offered improvedemission efficiency and blue light color purity and were used in organo-electroluminescent devices.

N

N

C8H17

C8H17 C8H17 C8H17

0.1

0.9

(III)

3. Regiogegular fluorcene, (IV), and carbazole polymers, (V), prepared byHeeney[4] and Leclerc [5], respectively, were useful as electroluminescent devicesbecause of their solubility in organic solvents and ease of processability.

S S

C12H25C12H25

(IV)

n

N

S

(V)

OC8H17

C6H13

n

Notes 435

4. Light-emitting fluorene polymers, (VI), displaying blue electroluminescencewere prepared by Mullen [6] and used in electronic devices.

C8H17 C8H17

C8H17 C8H17

C8H17 C8H17

C8H17 C8H17

(VI)

n

References

1. P. Kathirgamanathan et al., US Patent 7,211,334 (May 1, 2007)2. B.B. Lussier et al., US Patent 7,147,937 (December 12, 2006)3. B.h. Sohn et al., US Patent 7,172,823 (February 6, 2007)4. M. Heeney et al., US Patent 7,126,013 (October 24, 2006)5. M. Leclerc,US Patent Application 2007-0069197 (March 29, 2007)6. K. Mullen et al., US Patent 7,119,360 (October 10, 2006)

436 Electroactive Fluorene Copolymers and Devices Made with Such Polymers

Title: Light-Emitting Polymers

Author: M. O’Neill et al., US Patent 7,199,167 (April 3, 2007)Assignee: University of Hull (North Humberside, GB)

SIGNIFICANCE

Conventional displays comprise twisted nematic liquid crystals that require intensebacklighting, causing a heavy battery power drain. A process for preparing a new classof light-emitting polymers that require lower power consumption and have higherbrightness is described. The combination of these new light-emitting polymers withexistingLCD technologyoffers theprospect of low-cost, bright, portabledisplayswiththe benefits of simple manufacturing.

437

REACTION

S

S

C3H7 C3H7

S

S

C3H7 C3H7

Br

Br

S

S

C3H7 C3H7

OH

OH S

S

C3H7 C3H7

OCH3

OCH3

S

S

C3H7 C3H7

O

O

O

O

O

O

iii

iiiiv

Note 1

Note 2

i: N-Bromosuccinimide, hydrochloric acid, CH2Cl2, CCl3Hii: 4-(Methoxyphenyl)boronic acid, tetrakis(triphenylphosphine)palladium, ethy-

lene glycol dimethylether, sodium carbonate, hydrochloric acidiii: Boron tribromide, CCl3Hiv: 1,6-Heptadienyl-6-bromohexanoate, potassium carbonate, acetonitrile

EXPERIMENTAL

1. Preparation of 2,7-bis(5-Bromothien-2-yl)-9,9-Dipropylfluorene

A mixture consisting of 2,7-bis(thien-2-yl)-9,9-dipropylfluorene (5.55mmol) dis-solved in 25ml ofCCl3Hwas slowly treatedwithN-bromosuccinimide (12mmol) andthen refluxed for 1 hour. Thereafter the solution was diluted with 100ml of CH2Cl2,washed with 100ml of water, 150ml of 20% hydrochloric acid, 50ml of saturatedaqueous sodium bisulphite solution, and dried with MgSO4. The mixture wasconcentrated thenpurifiedby re-crystallization using ethanol/CH2Cl2, and theproductwas isolated in 86% yield as yellow-green crystals, MP¼ 160–165�C.

438 Light-Emitting Polymers

2. Preparation of 2,7-bis[5-(4-Methoxyphenyl)Thien-2-yl]-9,9-Dipropylfluorene

A mixture of the Step 1 product (4.7mmol), 4-(methoxyphenyl)boronic acid(14mmol), tetrakis(triphenylphosphine)palladium(0) (0.3mmol),Na2CO3 (29mmol),and 20ml of water in 100ml of ethylene glycol dimethylether was refluxed for 24hours.Once themixture cooled, additional 4-(methoxyphenyl)boronic acid (6.5mmol)was added and the mixture was again refluxed for 24 hours. Thereafter 20ml of DMFwas added to the solution, and it was further heated to 110�C for 24 hours, cooled, andtreated with 100ml 20%hydrochloric acid. The cooled reactionmixturewas extractedwith 250ml of diethyl ether, and the combined ethereal extracts were washed with100ml of water, dried with MgSO4, and concentrated onto silica gel. The mixture waspurified by chromatography using CH2Cl2/hexane, 1:1, re-crystallized from CH2Cl2/hexane, and the product was isolated in 63% yield as a green crystalline solid.

3. Preparation of 2,7-bis[5-(4-Hydroxyphenyl)Thien-2-yl]-9,9-Dipropylfluorene)

The Step 2 product (2.1mmol) was treated with the dropwise addition of 9ml of1M solution boron tribromide in CCl3H at 0�C and then stirred at ambienttemperature and quenched by adding it to 200ml of ice-water. The product wasextracted using 200ml of diethyl ether and washed with 150ml of 2M aqueoussodium carbonate and dried using MgSO4. The mixture was purified by columnchromatography with silica gel using CH2Cl2/diethyl ether/ethanol, 40:4:1, re-spectively, and the product was isolated as a green solid in 96% yield.

4. Preparation of 2,7-bis(5-{4-[5-(1-allylbut-3-enyloxycarbonyl)pentyloxy]phenyl}thien-2-yl)-9,9-dipropylfluorene

A mixture of the Step 3 product (1.0mmol), 1,6-heptadienyl-6-bromohexanoate(2.7mmol), and potassium carbonate (3.6mmol) dissolved in 25ml of acetonitrilewas refluxed for 20 hours, filtered, and the precipitate isolated and rinsed with230ml of CH2Cl2. The solution was concentrated onto silica gel and purified bycolumn chromatography using CH2Cl2/hexane, 1:1. The solid was re-crystallized

1HNMR (CDCl3): d 7.66 (2H, d), 7.49 (2H, dd), 7.46 (2H, d), 7.12 (2H, d), 7.05 (2H, d), 1.98 (4H, t), 0.69(10H, m)

IR (KBr cm�1): 3481 (w), 2956 (s), 1468 (s), 1444 (m), 1206 (w), 1011 (w), 963 (w), 822 (m), 791 (s), 474 (w)MS (m/z): 572 (Mþ), 529, 500, 487, 448, 433, 420, 407, 375, 250, 126

1HNMR (CD2Cl2): d 7.71 (2H, dd), 7.61 (8H,m), 7.37 (2H, d), 7.24 (2H, d), 6.95 (4H, d), 3.84 (6H, s), 2.06(4H, m), 0.71 (10H, m)

IR (KBr pellet cm�1): 2961 (w), 1610 (m), 1561 (m), 1511 (s), 1474 (s), 1441 (m), 1281 (m), 1242 (s), 1170(s), 1103 (m), 829 (m), 790 (s)

MS (m/z): 584 (Mþ -C3H7), 569, 555, 539, 525, 511, 468, 313, 277Elemental analysis Calculated: wt % C 78.56%, H 6.11%, S 10.23%. Found: C 78.64%, H 6.14%,

S 10.25%

Experimental 439

using CH2Cl2/ethanol mixture, and the product was isolated as a green-yellowsolid in 21%yield.

DERIVATIVES

S

S

C3H7 C3H7

O

OR

RO

O

O

O

A

A

1HNMR (CDCl3) d 7.68 (2H, d), 7.60 (2H, dd), 7.58 (2H, d), 7.57 (2H, d), 7.33 (2H, d), 7.20 (2H, d), 6.91(2H, d), 5.75 (4H,m), 5.08 (8H, m), 5.00 (2H, quint), 4.00 (4H, t), 2.33 (12H,m), 2.02 (4H, t), 1.82(4H, quint), 1.71 (4H, quint), 1.53 (4H, m), 0.72 (10H, m)

IR (KBr pellet cm�1): 3443 (s), 2955 (s), 1734 (s), 1643 (w), 1609 (m), 1512 (m), 1473 (s), 1249 (s), 1178(s), 996 (m), 918 (m), 829 (m), 799 (s)

APCI-MS (m/z): 1015 (Mþ, M100), 921Elemental analysis Calculated: wt % C¼ 76.89, wt% H¼ 7.35, wt% S¼ 6.32%. Found: wt% C¼ 76.96,

wt% H¼ 7.42, wt% S¼ 6.23

TABLE 1. Selected light-emitting pre-polymers prepared according to the currentinvention.

Entry R A

2 CH2(CH2)3CH2 CH2

3 CH2(CH2)2CH2 CH2

5 CH2(CH2)6CH2 N CH2

1HNMR (d-acetone): d 8.56 (2H, s), 7.83 (2H, dd), 7.79 (2H, d), 7.68 (2H, dd), 7.57 (4H, dd), 7.50 (2H, dd),7.31 (2H, dd), 6.91 (4H, dd), 2.15 (4H, m), 0.69 (10H, m)

IR (KBr pellet cm�1): 3443 (s, broad), 2961 (m), 1610 (m), 1512 (m), 1474 (m), 1243 (m), 1174 (m), 1110(w), 831 (m), 799 (s)

MS (m/z): 598 (Mþ), 526, 419 (M100), 337


NOTES

1. The preparation of the Step 1 reagent, 2,7-bis(thien-2-yl)-9,9-dipropylfluorene,(I), was provided by the author [1] as illustrated below.

S

S

C3H7 C3H7

Br Br

C3H7 C3H7

C3H7 C3H7C3H7

i ii iii

iv

i: Butyl lithium, THF, propyl bromideii: Butyl lithium, THF, propyl bromideiii: Bromine, CCl3Hiv: 2-(Tributylstannyl)thiophene, tetrakis(triphenylphosphine)-palladium,DMF

2. Photopolymerization of pre-polymers was conducted by the author using a300 nm lamp having a constant intensity of 100MWcm�2. Polymer repeat unitsare illustrated in the two equations below.

aO O

R

O O

R

O

O

R

O

R

O O

R

a

Notes 441

3. Additional light-emitting pre-polymer derivatives, (I), were prepared by theauthor [1] in an earlier investigation and are discussed.

NS

N

O O

O

O O

O(I)

4. Ise [2] prepared a light-emitting element consisting of a light-emitting layer,(II), placed between a pair of electrodes containing a perfluoroaromatics-triazine derivative, (III), layer.

N

N N N

N

N

F4

F5 F5

F5

(II) (III)

5. Fujii [3] prepared a five-component, (IV) – (VIII), organic light-emitting devicethat emitted a spectral component in the wavelength range of blue or shorter.

N

N N N N

N

N N

Ir 3

N

O t-C4H9

CNNC

(V) (VI)

(VII) (VIII)

(IV)


6. Swagger [4] prepared solid films of a new luminescent and conductive polymercomposition, (IX), containing chromophores that exhibited increased lumines-cent lifetimes, higher quantum yields, and amplified emissions.

ON

ON

C8H17

C8H17

C8H17

C8H17

(IX)

7. Organic light-emitting compounds, (X) and (XI), prepared by Lee [5] and Kim[6], respectively, had excellent electrical characteristics, thermal stability, andphotochemical stability while providing a low turn-on voltage and color puritycharacteristics when used in organic light-emitting devices.

X

t-C4H9

X = CH, N(CH3), O, S

(X)

N

N

t-C4H9

t-C4H9

(XI)

References

1. M. O’Neill et al., US Patent 7,166,239 (January 23, 2007) and US Patent Application 2005-0004252(January 6, 2005)

2. T. Ise et al., US Patent 7,189,989 (March 13, 2007)3. H. Fujii,US Patent 7,201,975 (April 10, 2007)4. T.M. Swagger et al., US Patent Application 2007-0081921 (April 12, 2007)5. D.H. Lee et al., US Patent Application 2007-0069203 (March 29, 2007)6. M.S. Kim et al., US Patent Application 2007-0072002 (March 29, 2007)

Notes 443

Title: Modified Suzuki-Method for Polymerizationof Aromatic Monomers

Author: C. Towns et al., US Patent 7,173,103 (February 6, 2007)Assignee: General Electric Company (Schenectady, NY)

SIGNIFICANCE

A modified Suzuki coupling catalyst has been used for preparing high molecularweight aromatic copolymers derived from fluorene and triphenylamine or benzothia-diazole. The coupling reagent consists of a palladium (II) catalyst containing ortho-substituted phosphines and can be used to generate polymers with molecular weightsexceeding 500,000 daltons. The polymeric materials are useful in electronic andoptoelectronic applications.

REACTION

aBr N Br N

C8H17 C8H17

i

i: 9,9-Di-n-octylfluorene-2,7-di(ethyleneborate), dichlorobis(tri-o-tolylphosphine)-palladium(ll), toluene, tetraethylammonium hydroxide, bromobenzene, phenyl-boronic acid

444

EXPERIMENTAL

Preparation of Poly(N,N-bis(Phenyl)-4-sec-Butylphenylamine-4,04-di-yl)-co-(9,9-di-n-Octylfluorene-2,7-di-yl) [Poly(TFB-co-F8)]

A reaction vessel was charged with 285ml of toluene, 9,9-di-n-octylfluorene-2,7-di(ethyleneborate) diester, [F8], (15.17 g), and N,N-bis(4-bromophenyl)-4-sec-butylphenylamine, [TFB], (13.12 g), the mixture was degassed by sparging withnitrogen at 25�C to 35�C for 60 minutes. The mixture was then treated withdichlorobis(tri-o-tolylphosphine)palladium(ll) (66.8 mg) and stirred for 15 min-utes and further treated with 96ml of 20% aqueous tetraethylammonium hydrox-ide. The mixture was then refluxed for 18 to 20 hours at 115�C. The product wasend-capped by adding 3ml of bromo-benzene and refluxing for 60 minutes at115�C. It was further treated with phenylboronic acid (3 g) and refluxed for anadditional hour. The reaction mixture was last cooled to ambient temperature andprecipitated by pouring into 4 liter of methanol. The product was isolated and had aMn of roughly 220,000 daltons.

DERIVATIVES

NOTES

1. In an earlier investigation by the author [1] an emulsion polymerization wasused to prepare the products of the current invention using dichlorobis(triphe-nylphosphine) palladium(II) as the Suzuki catalyst.

2. Suzuki polymerization of 9,9-di-n-octylfluorene-2,7-di(ethyleneborate) dies-ter, (I), with a biphenyl, (II), or triphenylamine derivative, (III), was used by

TABLE 1. Effect on polymer formation using a modified Suzuki reaction with apalladium catalyst containing an ortho phosphine substitutent.

EntryF8*1 DiesterComonomer

Pd CatalystPrecursor

o-TolylphosphineReagent

Mn

Polymer

2 TFB*2 Pd(BuCN)2Cl2 P(o-tol)3 169,0003 TFB Pd2(dba) 2 P(o-tol)3 241,0004 TFB Pd(BuCN)2Cl2 None No polymer8 BT*3 Pd(BuCN)2Cl2 P(o-tol)3 148,00010 BT Pd2(dba)2 P(o-tol) 3 523,00011 BT Pd(BuCN)2Cl2 PPH3 54,000

*19,9-di-n-Octylfluorene-2,7-di(ethyleneborate) diester*2N,N-bis(4-bromophenyl)-4-sec-butylphenylamine*32,7-dibromobenzothiadiazole

Experimental 445

O’Dell [2,3] to prepare polyaromatic polymers, (IV) and (V), respectively,which were used in optoelectronic applications.

a

B

C8H17 C8H17

B

C8H17 C8H17

C7H15

C7H15

O

O O

OBr

C7H15

C7H15

Br

(I) (II) (III)

N

Br

Br

C8H17 C8H17

N

(IV) (V)

a

3. Polyaromatic phosphine oxide, (VI), and diamines, (VII), were prepared byTowns [4] and coupled with fluorene derivatives, (VIII), to produce thecorresponding polyaromatic polymers.

B

C8H17 C8H17

B

O

O O

O

(VIII)

C8H17 C8H17

PO

Br Br

(VI)

n-C4H9

N

N

Br

Br

n-C4H9

(VII)

4. Hexaalkylated phenyl monomer derivatives and pentaaromatic diamines wereused by O’Dell [5] to prepared conjugated polymers, (IX), which were used inelectroluminescent devices. In a separate investigation by O’Dell [6], terpo-lymers, (X), were also prepared.

446 Modified Suzuki-Method for Polymerization of Aromatic Monomers

a

n-C4H9

N

N

n-C4H9

C8H17

C8H17 C8H17 C8H17

C8H17C8H17

(IX)

C8H17 C8H17

n-C4H9

N

N

n-C4H9

C5H11O

C5H11O

OC5H11

OC5H11

(X)

a

b

References

1. C. Towns et al., US Patent 7,074,884 (July 11, 2006)2. R. O’Dell et al., US Patent 7,125,952 (October 24, 2006)3. R. O’Dell et al., US Patent 6,998,181 (February 14, 2006)4. C. Towns et al., US Patent Application 2007-0031698 (February 8, 2007)5. R. O’Dell et al., US Patent Application 2007-0034832 (February 15, 2007)6. R. O’Dell et al., US Patent Application 2006-0149016 (July 6, 2006)

Notes 447

Title: Block Copolymer and Polymeric LuminescentElement

Author: T. Noguchi et al., US Patent 7,125,930 (October 24, 2006)Assignee: Sumitomo Chemical Company, Ltd. (Osaka, JP)

SIGNIFICANCE

Block copolymers consisting of twoormoreblocks bonded through a conjugatedbondhave been prepared that fluoresce in the solid state. The molecular weight of at leastone block is between 1.0� 104 and 2.7� 105 daltons. Unlike low molecular weightlight-emitting materials, however, these light-emitting agents are soluble in a varietyof organic solvents and are easily spin-coated as thin films onto selected surfaces foruse in polymer light-emitting devices.

REACTION

a

b

C8H17 C8H17

OHC CHO

O

O

O

O

i ii

C8H17 C8H17O

O

O

O

O

OCH3

C5H5

a

448

i: 9,9-Dioctyl-2,7-dibromofluorene, 4-bromo-2,5-(3,7-dimethyloctyloxy)benzalde-hyde, 2,20-bipyridyl, THF, bis(1,5-cyclooctadiene)nickel (0)

ii: 2-Methoxy-5-(2-ethylhexyloxy)-p-xylylene dichloride, triethyl phosphite, THF,potassium t-butoxide

EXPERIMENTAL

1. Preparation of 3,7-Dimethyloctyloxy)Benzaldehyde-TerminatedPoly[9,9-Dioctyl)2,7-Fluorine]

A mixture consisting of 9,9-dioctyl-2,7-dibromofluorene (2.7 g), 4-bromo-2,5-(3,7-dimethyloctyloxy)-benzaldehyde (2.3 g), 2,20-bipyridyl (2.7 g), and 150ml of THFwas charged into a reaction container under argon. It was then treated with bis(1,5-cyclooctadiene)nickel(0) (5.0 g), stirred for 10 minutes at ambient temperature, andreacted at 60�C for 7 hours. Themixturewas cooled and precipitated into a solution of25%NH4OH (aq)/methanol/water, 50ml:100ml:100ml, respectively, and then stirredfor 1 hour and isolated. The residuewas dried, dissolved in chloroform, filtered, and re-precipitated in methanol. The solid was dried under reduced pressure, and 1.4 g ofproduct was isolated.

2. Preparation of Block Copolymer

2-Methoxy-5-(2-ethylhexyloxy)-p-xylylene dichloride and triethyl phosphate wereinitially reacted to generate the corresponding phosphonate. Thereafter a mixture ofthe phosphonate (0.016 g), the Sep 1 product (0.5 g), and 50ml of THF was chargedinto a reactor and treated dropwise at ambient temperature with potassiumt-butoxide (0.07 g) dissolved in 5ml of THF over a 10 minute period. The mixturereacted for 2.5 hours at ambient temperature and was then neutralized with aceticacid. The polymer was precipitated by pouring into methanol and dried, and theproduct was isolated.

DERIVATIVES

Three fluorescent polymeric derivatives, (I)–(III), are provided below.

ba

C8H17 C8H17O

OCH3

C5H5

OCH3OCH3

(I)

Derivatives 449

ba

C8H17 C8H17O

O

O

O

N N1

(II)

C8H17 C8H17O

O

O

O

N N0.7

(III)

t-C4H9t-C4H9

0.3 b

NOTES

1. Bazan [1] prepared cationic conjugated flexible block copolymer derivatives,(IV), containing alkyl substituents along the main chain that disrupted extend-ed-rod structure formation. These were then used in optoelectronic devices andbiosensors.

TABLE 1. Physical properties of experimental polymers prepared accordingto the current invention.

Entry Mn (daltons) Mw (daltons) Peak Fluorescence (nm)

Step 2 product 3.7� 104 9.6� 104 504I 1.1� 104 2.7� 105 456II 1.0� 104 2.5� 104 470III 2.1� 104 6.3� 104 474

450 Block Copolymer and Polymeric Luminescent Element

cab

(H3C)3N N(CH3)32Br(IV)

2. Jen [2] prepared thermally reversibly electrooptic polymers, (V), via a Diels–Alder reaction, as illustrated below, that were used in second-order nonlinearoptical devices.

OO

O

O

N

O

O

O

OO

O

O

N

O

O

aa

(V)

Retro Diels–Adler

Diels–Adler

3. Grushin [3] prepared electroluminescent iridium compounds containing fluo-rinated phenyl-pyridines, (VI), phenylpyrimidines, and phenylquinolines foruse in organic electronic devices such as a light-emitting layer.

IrO

IrO

N

N

F CF3

CF3 F

H

H

22

(VI)

Notes 451

References

1. G.C. Bazan et al., US Patent 7,138,483 (December 5, 2006)2. K.-Y. Jen et al., US Patent 7,144,960 (December 5, 2006)3. V. Grushin et al., US Patent 7,132,681 (November 7, 2006)

452 Block Copolymer and Polymeric Luminescent Element

Title: Soluble Poly(Aryl-Oxadiazole) ConjugatedPolymers

Author: H. Wang et al., US Patent 7,105,633 (September 12, 2006)Assignee: E.I. Du Pont de Nemours and Company (Wilmington, DE)

SIGNIFICANCE

A single-step preparation of a new class of soluble co- and terpoly(arylene-oxadia-zole) polymers containing at least 20 repeat units have been prepared by thecondensation of aromatic dicarboxylic acids with hydrazine hydro-chloride. Photo-luminescence efficiencies of 50% were reported. Targeted applications includeelectroluminescent devices, photovoltaics, and diodes.

REACTION

C2H5 C2H5C2H5 C2H5 NN

Oi

aHO2C CO2H

i: Phosphorus pentoxide, methylsulfuric acid, 9,9-di-(2-ethylhexyl)-fluorene-2,7-dicarboxylic acid, hydrazine hydrochloride

EXPERIMENTAL

Preparation of Poly(9,9-di-(2-Ethylhexyl)-Fluorene-Oxadiazole)

Phosphorus pentoxide (3.0 g) was dissolved in 50ml of methylsulfuric acid at 110�Cand then treated with a mixture of 9,9-di-(2-ethylhexyl)-fluorene-2,7-dicarboxylicacid (2.0 g) and hydrazine hydrochloride (286mg). After the suspension was stirred

453

over 5 hours, a homogeneous viscous solution formed and was cooled to ambienttemperature and poured into 500ml of water. The polymer was precipitated as awhitefiber that was isolated by filtration and washed with aqueous Na2CO3, water, andmethanol. The crude polymer was dried under vacuum at ambient temperatureand then dissolved in 25ml of THF. The solution was filtered through a 5 mm filterand re-precipitated inwater. The polymerwas re-isolated, re-washed inwater and thenmethanol, and vacuum dried at ambient temperature. After repeating this purificationprocess three times, the polymer was isolated in 78% yield.

DERIVATIVES AND TESTING RESULTS

TABLE 1. Photoluminescence efficiencies for selected experimental agents activatedusing a UV lamp at 365 nm.

Photoluminesence Efficiency

Entry Polymer Structure l(nm) Zsolution(%) Zfilm(%)

Step 1Product

— 432 49 13

10NN

O O

NN

a b

430 36 8

11

a b

C2H5 C2H5 NN

O O

NN430 47 15

14

a b

C2H5 C2H5 NN

OS

O

NN500 61 30

(continued)

1H-NMR (500MHz,THF-d8) d8.42 (s, 2H, fluorene ring), 8.26 (d, 2H, fluorene ring), 8.13 (d, J¼ 8Hz, 2H,fluorene ring), 2.2 2.5 (br, 4H, H-alkyl), 0.8 1.1 (br, 16H, H-alkyl), 0.59 0.65 (br, 14H, H-alkyl).

454 Soluble Poly(Aryl-Oxadiazole) Conjugated Polymers

NOTES

1. In a subsequent investigation by the author [2] additional poly(aromatic-oxadiazole) agents were prepared using [1,2-d:4,5-d’]bisoxazole, (I), andderivatives.

C2H5 C2H5

N

O

O

N

(I)

C2H5 C2H5

X X X = Br, Cl

2. Poly(aryl-oxadiazole) conjugated polymers having tunable energy levels, (II),were prepared by the author [2] by adjusting HOMO and LUMO energy levelsof precursors and used in light-emitting electronic devices.

Photoluminesence Efficiency

Entry Polymer Structure l(nm) Zsolution(%) Zfilm(%)

17a

O

O

O

NN454 10 —


Notes 455

N N

O

a

(II)3. Kambe [3] prepared electroluminescent devices containing two or more

stacked organic layers, one of which consisted of an electron injectingan organic layer of conjugated poly(aryl-oxadiazole) derivatives, (III) and (IV).

N N

OF3C

F3Ca

(III)

Mw = 20,000

N N

O

O OO

O a a = 12

(IV)

4. Thin films containing electron injecting layers of low crystalline oxadiazolederivatives, (V) and (VI), were prepared by Saitoh [4] and used in electrolu-minescence device.

ON

N

ON

NNN

O

ON

NNN

O

t-C4H9 t-C4H9(V) (VI)

456 Soluble Poly(Aryl-Oxadiazole) Conjugated Polymers

5. Arylamine polythiophene derivatives, (VII), were prepared by Okada [5] andused as thin film transitors.

NS

C8H17 C8H17

S

a

(VII)

References

1. H. Wang et al., US Patent 7,138,483 (November 21, 2006)2. H. Wang et al., US Patent 7,132,174 (November 7, 2006)3. E. Kambe et al., US Patent 7,018,724 (March 28, 2006)4. A. Saitoh et al., US Patent 7,129,386 (October 31, 2006)5. T. Okada et al., US Patent Application 2002-0048637 (March 1, 2007)

Notes 457

B. Photorefraction

Title: Fullerene-Containing Polymer, ProducingMethod Thereof, and Photorefractive Composition

Author: M. Yamamoto, US Patent 7,186,781 (March 6, 2007)Assignee: Nitto Denko Corporation (Osaka, JP)

SIGNIFICANCE

A composition comprising a C60 fullerene-terminated poly(N-[(propylphenyl]-N,N0,N0-triphenyl-(1,10- biphenyl)-4,40-diamine)methacrylate has been prepared by livingradical polymerization.When blendedwith a plasticizer and a nonlinear chromophore,photorefractive efficiencieswere improved by up to 9%at a biased voltage of 60V/mm.

REACTION

OO

O

N

N

OO

O

N

N

OO

O

N

N

OO

O

N

N

iii

a a

i: Bis(2-bromo-2-methylpropionate), toluene, copper (I) bromide, bipyridine

ii: Bipyridine (0.256mmol), chlorobenzene, THF, C60 fullerene

EXPERIMENTAL

1. Preparation of Poly(N-[(Propylphenyl]-N,N0, N0-Triphenyl-(1,10-Biphenyl)-4,40-Diamine)Methacrylate

Thechargetransportagent,N-[(meth)acroyloxypropylphenyl]-N,N0,N0-triphenyl-(1,10-biphenyl)-4,40-diamine (2.6mmol), bipyridine (0.525mmol), ethylene bis(2-bromo-2-

458

methylpropionate) (0.105mmol), and toluene (2.1 g)were charged into a flask and thenpurged with argon gas. The mixture was treated with Cu(I)Br (0.209 mmol), heated to90�C and polymerized for 18 hours. 1H � NMR indicated that the reaction extent was71%. The mixture was then diluted with toluene and filtered to remove insolubleimpurities. The polymer was precipitated from the solution by adding methanol,filtering, and washing with diethyl ether and methanol to remove unreacted acrylatemonomer. The product was dried, and the product isolated had a Mw of 8317 daltons.

2. Preparation of Poly{(N-[(Propylphenyl]-N,N0, N0-Triphenyl-(1,10-Biphenyl)-4,40-Diamine)Methacrylate}-C60 Fullerene

The Step 1 product (680mg), bipyridine (0.256mmol), and 4ml of chlorobenzenewere charged into a flask and then purged with argon gas for 1 hour. This mixture wasnext treated with Cu(I)Br (0.100mmol) and C60 fullerene (0.111mmol) and heated to90�Cfor 18hours and the residue dissolved inTHF.The solutionwas filtered through a0.2 mm pore size teflon filter to remove unreacted C60 fullerene. The polymer wasprecipitated from the solution by adding methanol; it was re-filtered and washed withmethanol; the product was isolated as a black solid having a Mw of 10,413 daltons.

DERIVATIVES

An additional nonlinear optical copolymer derivative, (I), plasticizer, (II), andnonlinear optical chromophore, (III), were also prepared.

OO

O

N

N

OO

O

N

N

O O

N

CHO

OO

O

N

N

O O

N

CHO

(I) (II)Nonlinear optical copolymer Plasticizer

N

CN

OH

(III)

Nonlinear optical chromophore

a

Derivatives 459

Photorefractive Efficiency Testing

Photorefractive evaluation of experimental agents was done by initially dissolvingsamples in toluene, evaporating off the solvent, and then heating to 150�C to make200 to 300 mm thick films. Samples were sandwiched between indium tin oxideand separated by a 105 mm spacer. The diffraction efficiency was measured at633 nm using four-wave mixing experiments. Steady-state and transient four-wavemixing experiments were done using two writing beams making an angle of 20.5�

in air; the bisector of the writing beams make a 60�-degree angle relative to thesample normal. The four-wave mixing experiments consisted of two s-polarizedwriting beams with equal intensity of 0.2W/cm2 in the sample with a spot diameterof 600 mm. Testing results are provided in Table 1.

NOTES

1. In earlier investigations by the author [1,2] an additional nonlinear opticalchromophore, (IV), and charge transport agent, (V), respectively, were pre-pared and used in photorefractive applications.

N

O

O

(V)

N

CN

CN

(IV)

TABLE 1. Photo diffraction efficiency testing results for sample blends at a biasedvoltage of 60V/lm.

Sample Blend Diffraction Efficiency (%)

Step 1 product, 30% 8Step 2 product, 30%Nonlinear optical copolymer, 25%Plasticizer, 15%Step 1 product, 45% 9Step 2 product, 15%Nonlinear optical copolymer, 25%Plasticizer, 15%

460 Fullerene-Containing Polymer, Producing Method Thereof, and Photorefractive Composition

2. Photorefractive carbazolyl-functionalized cyclic oligosiloxanes, (VI), wereprepared by Xu [3] and used in organic light-emitting diodes.

OSi

O SiOSi

OSi

N

N

N

N

(VI)

3. Hyperbranched polyester crosslinked photorefractive polymers were preparedby Nishikata [4] consisting of Dispersant Red-19, (VII), and trimesic acid ortrimesic acid containing isophthalic acid. Perfluorobenzoate Dispersant Red-19 derivatives, (VIII), were also prepared by the author [5].

N

HO OH

NO2

(VII)

N

O

NO2

O

FC

CF2

(VIII)

References

1. M. Yamamoto et al., US Patent Application 2006-0235163 (October 9, 2006)2. M. Yamamoto et al., US Patent 6,653,421 (November 25, 2003)3. S. Xu,US Patent Application 2006-0232201 (October 19, 2006)4. Y. Nishikata et al., US Patent Application 2006-0214140 (September 28, 2006)5. M. Yamamoto,US Patent Application 2006-0094845 (May 4, 2006)

Notes 461

XIX. POLYMERIZATION METHODS

A. Anionic

Title: Method for Anionic Polymerization of Oxiranes

Author: P. Desbois et al., US Patent Application 2007-0100097 (May 22, 2007)Assignee: BASF Aktiengellschaft

SIGNIFICANCE

A method for preparing homopolymers or copolymers of oxiranes by anionicpolymerization using s-butyl lithium and triisobutylaluminum but without crownethers or cryptands during the polymerization process is described.

REACTION

OOLi

OH

a bai ii

i: Cyclohexane, s-butyl lithiumii: Triisobutylaluminum, oxirane

EXPERIMENTAL

1. Preparation of Polystyryllithium

A reaction vessel was charged with 3.5ml of styrene diluted with 14ml of cyclo-hexane and then treated with 1.25ml of 1M s-butyl lithium and polymerized at 0�Cfor 2 hours. The polystyryl lithium block obtained had a polydispersity index of 1.1and a Mn of 1700 daltons.


463

2. Preparation of Poly(Oxirane-b-Styrene)

A second vessel was charged with 1.75ml of triisobutylaluminum and 4ml of theStep 1 product and then treated with 6ml of oxirane where the aluminum/lithiummolar ratio was 5:1, respectively. The mixture was polymerized at 0�Cfor 60 minutes and 20�C for 15 hours and then terminated. The results for thePS-PPO block copolymerization was an 98% conversion, a polydispersity indexof 1.7, and a Mn of 7700 daltons.

NOTES

1. Knoll [1] anionically prepared styrene-butadiene block copolymer mixturesusing sec-butyllithium followed by hydrogenation, and the material was thenused as transparent films.

2. The author [2] prepared poly(a-methylstyrene-b-styrene) copolymers usings-butyl lithium and triisobutylaluminum.

References

1. K. Knoll et al., US Patent 7,064,164 (June 20, 2006)2. P. Desbois et al., US Patent 7,101,941 (September 5, 2006)

464 Method for Anionic Polymerization of Oxiranes

Title: Amido-Organoborate Initiator Systems

Author: S. Feng et al., US Patent Application 2007-0083051 (April 12, 2007)Assignee: The Dow Chemical Company (Midland, MI)

SIGNIFICANCE

A new free radical class of polymerization agents consisting of amido-boratecompounds have been prepared by reacting an organoborate with a hydrocarbylamine. These reagents are particularly useful as hardeners in polymer formulations.

REACTION

NN

(C2H5)3B

NaB(C2H5)3

NN

Li i

Notes 1,2

i: THF, triethylborane

EXPERIMENTAL

Preparation lithium dimethylamidotriethylborate

A slurry of sodium imidazole (50mmol) in 30ml of THF was treated with the slowaddition of triethylborane (100mmol) and then stirred for 5 hours at ambienttemperature. The mixture was next concentrated and a brown oil isolated. The crudeproduct was isolated in 98% yield and used without additional purification.

465

DERIVATIVES

NN

(C2H5)3B

Li

NN

(C2H5)3B

P((CH2)2CH3)4

B(C2H5)3

N B(C2H5)3

Li

NOTES

1. The amido-organoborates were used as hardeners in formulations as illustratedbelow:

A mixture of 633 parts of methyl methacrylate, 180 parts of poly(methylmetha-crylate), and 45 parts of styrene butadiene styrene block copolymerwere placed ina half gallon paint can and rolled on a roller mill overnight. Once the polymerswere dissolved, 85.8 parts were placed into an 8 oz plastic container and treatedwith 2 parts fumed silica and 2 parts of glass beads then mixed by hand using atongue depressor. Finally 10 parts of amido-borate hardener were added to thecontainer and mixed and the resulting cement packaged in an 8 oz plastic cup.

2. Comprehensive hardening formulations using amido-organoborates are de-scribed by the author [1] in an earlier investigation.

3. Organboranes such as sodium tetraethyl borate, lithium phenyl triethyl borate,and tetramethylammonium phenyl triethyl borate were prepared by Kneafsey[2] and Maandi [3], respectively, and used as initiators and adhesive agents forlow surface energy substrates.

4. An initiator system consisting of triethylborane and hexamethylenediaminewas prepared by Deviny [4] and used in adhesives.

References

1. S. Feng et al., US Patent Application 2007-0079931 (April 12, 2007)2. B.J. Kneafsey et al., US Patent 7,189,463 (March 13, 2007)3. E. Maandi et al., US Patent 7,098,279 (August 26, 2006)4. E.J. Deviny et al., US Patent 7,189,303 (March 13, 2007)

466 Amido-Organoborate Initiator Systems

Title: Process for Manufacturing Vinyl-richPolybutadiene Rubber

Author: L. Jiang et al., US Patent 7,186,785 (March 6, 2007)Assignee: Changchun Institute of Applied Chemistry Chinese Academy of Science

(Changchun, CN)

SIGNIFICANCE

A method for converting 1,3-butadiene into polybutadiene having at least an 88.4%vinyl content using iron isooctanoate, triisobutylaluminum, and ethyl phosphite isdescribed. The optimum weight ratio of reagents of aluminum/iron was 5:100 with aphosphite/iron ratio of 1:20, respectively.

REACTION

i

Notes 1, 2, 3 a

i: Hexane, iron isooctanoate, triisobutylaluminum, ethyl phosphite

EXPERIMENTAL

1. Preparation of Polybutadiene Having an 88.4% Vinyl Content

A reactor was charged with 84ml of hexane and butadiene (10 g) and then treatedsequentially with iron isooctanoate (0.0124mmol), triisobutylaluminum(0.19mmol), and ethyl phosphite (0.0295mmol). The mixture was placed into a50�Cwater bath and polymerized for 4 hours. Thereafter an aqueous alcohol solutioncontaining 2,6-di(t-butyl)-4-cresol was added to precipitate the rubber sample. Thematerial was dried, and the product was isolated.

467

SCOPING REACTIONS

NOTES

1. In a subsequent investigation by the author [1], high cis-content polybutadienehaving a controlled molecular distribution was prepared using neodymiumneodecanoate, AlH(i-C4H9)2, methylaluminoxane, and Al(i-C4H9)2Cl.

2. Luo [2] prepared syndiotactic polybutadiene having a high vinyl content usingiron(III) 2-ethylhexanoate, bis(2-ethylhexyl) hydrogen phosphate, and tri-n-butylaluminum.

3. Using diisobutylaluminum hydride and triisobutylaluminum, 20:80, respec-tively, with neodymium [III] neodecanoate, Luo [3] also prepared poly(buta-diene) having a 98.7% 1,4-linkage. By using only diisobutylaluminum hydridewith neodymium (III) versatate, Luo [4] also prepared high cis-contentpolybutadiene having an 98.4% 1,4-linkage.

References

1. L. Jiang et al., US Patent Application 2005-0113544 (May 26, 2005)2. S. Luo, US Patent 6,720,397 (April 13, 2004) and US Patent 6,620,760 (September 16, 2003)3. S. Luo et al., US Patent 7,094,849 (August 22, 2006)4. S. Luo et al., US Patent 7,008,899 (March 7, 2006) and US Patent 6,699,813 (March 2, 2004)

TABLE 1. Conversion of 1,3-butadiene into poly(butadiene) having a high vinylcontent using iron isooctanoate, triisobutylaluminum, and ethyl phosphite.

Entry

Reagent AdditionIron Isooctanoate (A)

Triisobutylaluminum (B)Ethyl Phosphate (C)

Conversion(%)

[Z](dL/g)

GelFormation

(%)

VinylContent

(%) Tg (�C)

1 A, B, C 95 6.54 1.4 88.4 ––2 A, C, B 98 –– –– 86.4 �383 A, B, C 95 8.0 5.0 83.8 ––4 A, B, C 99 –– –– –– �23

Note: The sequential reagent addition marginally impacted the overall vinyl incorporation levels.

468 Process for Manufacturing Vinyl-rich Polybutadiene Rubber

Title: Catalyst for Synthesizing High Transpolymers

Author: A. F. Halasa et al., US Patent 7,189,792 (March 13, 2007)Assignee: The Goodyear Tire and Rubber Company (Akron, OH)

SIGNIFICANCE

A catalyst combination consisting of the barium salt of tri(ethyleneglycol)ethyl ether,Ba(OCH2CH2OCH2CH2OCH2CH3)2, with tri-n-octyl aluminum and n-butyl lithiumhas been used to prepare random poly(styrene-co-butadiene) containing a highbutadiene transcontent. These polymers were designed to be co-cured with naturalrubber and used as components in automotive tires.

REACTION

a

b c

d

a > bc > di

Notes 1, 2, 3, 4

i: bis[2-(2-Ethoxyethoxy)-ethanolato-O,O0,O00] barium, ethyl benzene, tri-n-octylaluminum, n-butyl lithium, butadiene

EXPERIMENTAL

1. Preparation of Catalyst

The catalyst was prepared by treating a 37.33% solution of bis[2-(2-ethoxyethoxy)-ethanolato-O,O0,O00] barium dissolved in ethyl benzene with 50% tri-n-octyl alumi-num in hexane so that the aluminum/barium ratio was 4:1, respectively. This mixturewas then treated with sufficient 15% n-butyl lithium so that the lithium/barium ratiowas 3:1, respectively. The catalyst was used immediately.

469

2. Preparation of Poly(Styrene-co-Butadiene)

A 500-gall reactor was charged with a 40:60 pre-mix of styrene/butadiene, respec-tively, at a total weight of 862 kg. Themixturewas then treatedwith the Step 1 catalyst(0.325mmol of barium per 100mmol of butadiene) at 66�C. The polymerizationoccurred immediately and had a peak exotherm of 118�C within 45 minutes with amaximum pressure of 541 Pas within 38 minutes. After two hours the reactor wascooled, and the polymer cement was de-solventized to recover the product.

OPTIMIZATION STUDIES

NOTES

1. Poly(styrene-co-butadiene) was previously prepared byWeydert [1] containinga high butadiene trans content using tri-n-butylaluminum and the bariumsalt of tri(ethyleneglycol)ethyl ether, Ba(OCH2CH2OCH2CH2OCH2CH3)2,4:1 respectively.

2. High trans poly(styrene-co-butadiene) was also prepared by the author [2] in asubsequent investigation using a catalyst derived from the barium salt of (a)di(ethylene glycol) ethyl ether and di(N,N-dimethyl/amino ethylene glycol)ethyl ether or di(ethylene glycol) hexyl ether and triisobutyl aluminum.Materials prepared using this catalyst mixture were used as componentsautomotive tires.

3. Standstrom [3] improved the elongation at break properties of tires by blending70% cis-poly(1,4-isoprene) with 30% poly(butadiene) containing a high transcontent. The latter was prepared using barium di(ethylene glycol) ethyl ether,tri-octyl aluminum, and n-butyllithium as the reaction catalyst mixture.

4. High trans content copolymers of styrene and butadiene were also obtained byHalasa [4] using the calcium salt of tetrahydrofurfuryl alcohol and n-butyllithium.

TABLE 1. Physical properties of copolymers prepared by bulk polymerization usingbis[2-(2-ethoxyethoxy)-ethanolato-O,O0,O0 0] barium, ethyl benzene, and tri-n-octylaluminum as the high trans catalyst mixture.

Entry

RatioStyrene/butadiene

RatioBarium/Butadiene Tg (�C)

StyreneIncorporation

(%)Cis(%)

Trans(%)

Vinyl(%)

11 33/67 0.325 �73.1 27.4 12.7 55.5 4.413 28/72 0.325 �71.1 21.3 18.8 62.0 3.914 22/78 0.325 �74.6 18.5 13.8 63.6 4.119 37/63 0.400 �68.8 32.9 11.0 51.7 4.3

Note: All percentages were determined by 1H-NMR; molecular weights were not supplied by author.

470 Catalyst for Synthesizing High Transpolymers

5. Poly(styrene-b-butadiene) was anionically prepared by the author [5] usingn-butylithium and tetramethylethylenediamine. The product was used as acomponent in automotive tires.

6. Dendrimeric rubbery copolymers having a molecular weight of roughly250,000 daltons and containing siloxane linkages were prepared by the author[6] by copolymerizing 12% styrene and 88% butadiene in combinationwith of 2-butyl lithium, hexachlorodisiloxane, and N,N,N0,N0-tetramethyl-1,2-ethanediamine.

References

1. M. Weydert et al., US Patent 6,889,737 (May 10, 2005)2. A.F. Halasa et al., US Patent Application 2006-0149010 (July 6, 2006)3. P.H. Sandstrom et al., US Patent Application 2005-0245688 (November 3, 2005) and US Patent

Application 2005-0272852 (December 8, 2005)4. A.F. Halasa et al., US Patent 7,087,549 (August 8, 2006)5. A.F. Halasa et al., US Patent 7,064,171 (June 20, 2006)6. A.F. Halasa et al., US Patent Application 2007-0010629 (January 11, 2007) and US Patent Application

2006-0247360 (November 2, 2006)

Notes 471

Title: Method for the Preparationof Poly(a)-Methylstyrene

Author: A. Balland-Longeau, US Patent 7,179,870 (February 20, 2007)Assignee: Commissariat A L’Energie Atomique (Paris, FR)

SIGNIFICANCE

Poly(a-methylstyrene) having a Mn> 300,000 daltons with of PDI < 1.06 was pre-pared using sec-butyl lithium. The process entails initially treating the monomer withsec-butyl lithium to dry and to neutralize impurities while monitoring this process byUV. The monomer was then re-treated with butyl lithium, THF, and toluene andpolymerized 24 hours. The material is intended for inertial confinement chambers infusion experiments.

REACTION

a

i

Note 1

i: s-Butyl lithium, toluene, THF

EXPERIMENTAL

A 100-ml reactor connected to a cryostat equipped with a UV cell was charged with55ml of toluene and a-methylstyrene (22 g). While monitoring by UV, the monomerwas dried by the dropwise addition of s-butyl lithiumat ambient temperature, resultingin a slightly yellow coloring of the monomer. The mixturewas then cooled to�25�C,treatedwith s-butyl lithium (0.073mmol), stirred for 4 hours after which 10ml ofTHF

472

and toluenewere added. Themixture became a vivid red andwas stirred an additional24 hours at�25�C, until the solution became viscous. The reaction was quenched byadding 1ml of ethanol and gradually warmed to ambient temperature. The mixturewas precipitated in methanol, and the product was isolated by filtration in 91% yieldhaving a Mn of 312,000 daltons with a polydispersity index of 1.06.

NOTES

1. Moore [1] prepared polystyrene having a Mn of 130,000 daltons with aPDI of 1.05 by initially drying the monomer and neutralizing impuritieswith n-butyllithium prior to polymerization. n-Butyl-lithium was also usedwith potassium t-amyloxide by Malanga [2] in preparing ultra-pure poly(a-methylstyrene).

2. Andrekanic [3] prepared poly(a-methylstyrene) using tin(IV) chloride asinitiator in toluene with unpurified plant grade a-methylstyrene.

3. Poly(butadiene-b-a-methylstyrene-b-styrene) was prepared by Tung [4] usingsec-butyl-lithium and 1,3-di(1-phenylethenyl)benzene.

4. Poly(a-methylstyrene-co-styrene) was previously prepared by Desbois [5]using s-butyl lithium and triisobutylaluminum.

References

1. E.R. Moore et al., US Patent 4,883,846 (November 28, 1989)2. M.T. Malanga et al., US Patent 7,045,248 (May 31, 1988)3. R.A. Andrekanic et al., US Patent 6,649,716 (November 18, 2003)4. L.U. Tung et al., US Patent 4,431,777 (February 14, 1984)5. P. Desbois et al., US Patent 7,101,941 (September 5, 2006)

Notes 473

Title: Use of Sulfur Containing Initiators for AnionicPolymerization of Monomers

Author: T. E. Hogen et al., US Patent 7,153,919 (December 26, 2006)Assignee: Bridgestone Corporation (Tokyo, JP)

SIGNIFICANCE

Sulfur-vulcanizable elastomers have been prepared that are designed to reducehysteresis in tires by reducing the number of polymer free ends. The method forthis preparation entails anionically preparing poly(styrene-co-butadiene) using alithium thioacetal initiator followed by incorporation of a vulcanization agent intothe elastomer terminus.

REACTION

SS

SS Li

SSH

+_i ii

Notes 1, 2

a b c d e fVulcanize

i: THF, butyllithiumii: Styrene,butadiene, hexane, cyclicoligomericoxolanyl alkane (Note1) isopropanol

EXPERIMENTAL

1. Preparation of 2-Lithio-2-Methyl-1,3-Dithiane

Areactorwas chargedwith 350mlofTHFand2-methyl-1,3-dithiane (83.5mmol) andthen cooled to�78�Cand treatedwith 55.83ml of 1.51Mbutyllithium (84.3mmol) in

474

hexane. The mixture was stirred at�78�C for 3 hours and stored at�25�C overnight.Titration of the resulting solution indicated that the solution contained 0.234Mactive lithium.

2. Preparation of Poly(Styrene-co-Butadiene) with 2-Lithio-2-Methyl-1,3-Dithiane

A 1.75 liter reactor was charged with 1.12 kg of hexane, 0.48 kg of 33wt% styrene inhexane, and 2.89 kg of 22.0 wt% butadiene in hexane. The reactor was then heated to24�C and treated with 0.5ml of 1.6M of a selected cyclic oligomeric oxolanyl alkanemodifier (Note 1) in hexane and 22.63ml of the Step 1 dissolved in THF. The mixturewas heated to 54�C for 15 minutes, and an exotherm peaking at 76.5�Cwas observed.After an additional 25 minutes the mixture was removed from the reactor andcoagulated in isopropanol containing butylated hydroxy toluene. After drying, theproduct was isolated, and it consisted of 21.7% styrene, 1.3% block styrene, 32.1%vinyl, and 46.2% 1,4 butadiene having a Mn of 15,300 daltons, Mw of 16,700 daltons,and a Tg¼�44.4�C.

DERIVATIVES

TABLE 1. Effect of lithium thioacetal anionic initiators on poly(styrene-co-butadiene) properties.

Poly(styrene-co-butadiene) Properties

Initiator Mn (kg/mol) Mw (kg/mol) Tg (�C)

SS Li 208.0 240.0 �43.8

SS Li

135.8 137.2 �69.0

SS Li

N(CH3)2

123.0 135.0 �34.3

BuLi (Reference) 110.6 114.8 �29.9

Derivatives 475

NOTES

1. Cyclic oligomeric oxolanyl alkanes were used when diene polymerizationutilized a lithium-based initiator. Cyclic oligomeric oxolanyl alkanes aredescribed by Lin [1] and include 2-20-di(tetrahydrofuryl) propane, dipiperidylethane, hexamethyl phosphoramide, N-N0-dimethyl piperazine, anddiazabicyclooctane.

2. Halasa [2] reduced hysteresis in tires by anionically copolymerizing functio-nalized butadiene, (I), and styrene, (II), to enhance elastomer compatibilitywith carbon black and silica fillers.

N

N

(I) (II)

TABLE 2. Physical properties of styrene-butadiene elastomers initiatedwith selected thioacetals and terminated with vulcanization agents.

Poly(styrene-co-butadiene) Properties

Initiator TerminatorMn

(kg/mol)Mw

(kg/mol)Tg(�C)

Styrene(Block)(%)

Vinyl(%)

Budiene(%)

SS Li Si(OC2H5)4 219 285 �31.5 20.6

(2.0)31.8 45.6

SS Li

Sn(C2H5)3Cl 106 113 �31.3 21.0(2.0)

31.4 45.6

SS Li

N(CH3)2

N

NO 108.5 117.6 �29.7 — — —

SS Li

SS 111 126 �30.9 20.7

(1.9)31.8 45.6

476 Use of Sulfur Containing Initiators for Anionic Polymerization of Monomers

3. Tires having reduced hysteresiswere prepared byKerns [3] by vulcanizing highvinyl content poly(styrene-co-butadiene) using butadienyllithium or styryl-lithium as the catalyst.

4. Tire tread rubber formulations were prepared by Parker [4] and consisted ofpoly(styrene-co-butadiene) rubber terminated with N-isopropylphenylnitrone,(III), to promote interaction between the polymer end-groups and carbon blackand silica fillers to reduce hysteresis.

(III)

NO

5. Obrecht [5] prepared rubber vulcanizates consisting of poly(styrene-co-buta-diene) containing 2-t-butylamino-ethylmethacrylate, (IV), which were used inautomotive tire applications.

O

O

NH

t-C4H9

(IV)

References

1. C.J. Lin et al., US Patent 7,119,150 (October 10, 2006)2. A.F. Halasa et al., US Patent 7,041,761 (May 9, 2006) and US. Patent 6,995,224 (February 7, 2006)3. M.L. Kerns et al., US Patent 7,153,920 (December 26, 2006)4. D.K. Parker, US Patent 7,125,934 (October 24, 2006)5. W. Obrecht et al., US Patent 7,134,466 (November 14, 2006)

Notes 477

Title: Production Method of Polyisocyanateby End-Capping with Acyl Chloride

Author: Jae-Suk Lee et al., US Patent 7,135,536 (November 14, 2006)Assignee: Gwangju Institute of Science and Technology (Gwangju, KR)

SIGNIFICANCE

Anionic polymerization of hexylisocyanate has been used to prepare polyamidateshaving controlled molecular weights and polydispersites. The method entailed usingsodium N-phenyl benzyl amine as the anionic catalyst acyl chloride derivatives asend-capping agents. End-capping efficiencies ofmore than 90%of the living polymerwere observed.

REACTION

a aO C N

C6H13N N

O

N

O

C6H13 C6H13i ii

O

N N

O

N

O

C6H13 C6H13

_

Note 1 Note 2

Not isolated

i: Sodium N-phenyl benzyl amine, THFii: Pyridine, methacryloyl chloride

EXPERIMENTAL

Anion Polymerization of Poly(n-Hexylisocyanate) End-Cappedwith Methacryloyl Chloride

n-Hexylisocyante was polymerized for 50 minutes at 1� 10�6 torr at�98�C in THFusing sodiumN-phenyl benzyl amine as catalyst and end-capping for 10minutes withpyridine and methacryloyl chloride. Specific stoichometries and polymer character-istics are provided in Table 1.

478

SCOPING REACTIONS

NOTES

1. Living poly(n-hexylisocyanate)was previously prepared by titanium-catalyzedcoordination polymerization as described by Pattan [1].

2. Other encapping agents were used to functionalize poly(n-hexylisocyanate) inthe current investigation. (s)-(�)Acetopropionyl chloride was used to preparean optically active terminus, (I), while suberoyl chloridewas used to prepare thecorresponding acid chloride terminus, (II).

aaN N

O

N

O

C6H13 C6H13

O

O

(I)

N N

O

N

O

C6H13 C6H13

O

(II)

Cl

O

6

3. Optically active polyhexylisocyanates were prepared by Gu [2] by copolymer-izing 1- and 2-deuterium-hexylisocyanatewith with hexylisocyanate, (III) and(IV), respectively.

bbaN

O

N

O

H

DN

O

N

O

D

H

(IV)(III)

a

TABLE 1. Polymer properties from four 50minute anionic polymerization reactionsusing n-hexyl isocyante in THF with sodium N-phenyl benzyl amine as initiator andthen quenching for 10 minutes using methacryloyl chloride dissolved in pyridine.

EntryCatalyst(mmol)

Monomer(mmol)

End-CappingAgent (mmol)

Pyridine(mmol)

CalculatedMn (daltons)

MeasuredMn (daltons) PDI

1 0.10 4.04 0.81 1.75 5,000 5,600 1.072 0.11 6.60 0.62 1.60 7,000 6,900 1.133 0.07 6.76 0.65 1.44 12,500 12,800 1.144 0.05 6.71 0.53 1.58 15,500 15,700 1.17

Notes 479

4. Azo-functionalized polyhexylisocyanate, (V), was prepared by Se [3] byendcapping with 4-(phenylazo)benzoyl chloride.

N

O

C 6H13

O

N

N

(V)

a

References

1. T.F. Pattan et al., J. Am. Chem. Soc. 113: 5065, 1991, and Macromolecules 26: 436, 19932. H. Gu et al., Marcomolecules, 1998, 31, 63623. K. Se et al., Marcomolecules, 2003, 36, 5878

480 Production Method of Polyisocyanate by End-Capping with Acyl Chloride

B. Catalytic Agents

a. Acyclic Diene Metathesis Catalyst

Title: Methods for Making Functionalized Polymers

Author: K. B. Wagener et al., US Patent 7,172,755 (February 6, 2007)Assignee: University of Florida Research Foundation, Inc. (Gainesville, FL)

SIGNIFICANCE

A new acyclic diene metathesis polymerization method has been developed using1,3-dimesityl-4,5-dihydroimidazol-2-ylidene)benzylidene ruthenium(II) dichlorideas catalyst. This reaction catalyst was used for preparing oligomers and polymerscontaining amino acids or polypeptides.

REACTION

OHN

O

OCH3

OHN

O

OCH3

i

a

Note 1

i: 1,3-Dimesityl-4,5-dihydroimidazol-2-ylidene)benzylidene tricyclopentylpho-sphine ruthenium(II) dichloride, CH2Cl2

EXPERIMENTAL

1. Polymerization of Methyl N-[2-(3-Butenyl)-6-Heptenoyl]-L-Leucinate

Polymerization reactions were conducted under a protective argon atmosphere. AvesselwaschargedwithmethylN-[2-(3-butenyl)-6-heptenoyl]-L-leucinate(1.62mmol)

481

and 1,3-dimesityl-4,5-dihydroimidazol-2-ylidene)benzylidene ruthenium(II) dichlo-ride (0.016mmol) and then placed in a Shlink flask with a stirring bar and a condenser.Argon was next flowed through the system and then vented through a bubbler. Themixturewas heated to 60�Cwith rapid stirring for 5 days;when the solution became tooviscoustostir,additionalCH2Cl2wasadded.Theproductwasisolatedfollowingvacuumremoval of the reaction solvent.

DERIVATIVES

HN

O

O R

O

aa b

HN

O

i-C4H9

O

H3CO

a b c

TABLE 1. Selected acyclic diene metathesis polymers preparedusing optically active monomers.

Entry a R

2 2 i-Propyl3 2 i-Butyl4 3 i-Butyl5 8 i-Propyl6 8 i-Butyl

TABLE 2. Selected acyclic diene metathesis polymers preparedusing optically active monomers.

Entry a b

7 2 38 3 3

Tm¼ 114�CMn¼ 31,000 daltons1H NMR d 0.75 0.90(dm, 6H, C.sub.C,D–H), 1.20 1.70(m, 9H, C.sub.A,B,4,6,7–H), 1.85 2.10(m, 4H, C5,

8–H), 2.15 2.30(m, 1H, C5–H), 3.60(s, 3H, OCH3), 4.25 4.35(m, 1H, C.sub.A–H), 5.30 5.50(m,2H, C.sub.1,2–H), 8.20(m, 1H, NH).

C,H,N Analysis: Theoretical C68.5H9.7N4.9; Found C66.21H9.01N4.67

482 Methods for Making Functionalized Polymers

NOTES

1. In an earlier investigation by the author [1] an additional acyclic dienemetathesis ruthenium polymerization catalyst, (I), was identified and used inthe metathesis of alkenyl alcohols.

N N

RuCl

Cl

P

(I)

3

2. Angeletakis [2] prepared metathesis-curable dental compositions using 1,3-bis-(2,4,6-trimethylphenyl)-2-(imidazolidinylidene) dichloro(o-isopropoxy-phenylmethylene) ruthenium, (II), with norbornene-terminated siloxanemacromolecules, (III).

N N

Ru

O

Si OSi

OSi

OSi

Sia b

(III)(II)

a = 30–1500b = 1 – 100

TABLE 3. Physical properties of acyclic diene metathesis polymers illustratedin Tables 1 and 2.

Entry [a] Monomer (�) [a] Polymer (�) Mn (daltons) PDI Tm (�C)

2 �32 –– 900 1.49 ––3 �32 –– 900 1.13 ––4 �32 �32 4,700 1.73 ––5 �34 �20 27,000 1.77 296 –– �40 33,000 1.64 ––7 �13 �64 31,000 202 1148 �13 �7 26, 000 210 135

Note: Mn values were calculated by GPC using polystyrene standards.

Notes 483

3. Grubbs [3] prepared high activity metathesis ruthenium metal carbene com-plexes, (IV), that were effective as depolymerization catalysts of unsaturatedpolymers and synthetic agents in preparing telechelic and alkene polymers.Other high activity metathesis ruthenium carbene metal complexes, (V), wereprepared by Fogg [4].

RuCl

PR3

PR3

Cl

X

R = C6H5

C 5H9

X = H

N(CH 3)2

OCH3

CH 3

F

Cl

NO2

(IV)

RuOC6X 5

NX

X

(V)

X = F, Cl, Br

4. Piccinelli [5] used (tricyclopentylphosphine)dichloro(3-methyl-butenylidene),(VI), or related cyclic derivatives, (VII), to prepared anti-fog agents, (VIII), bycoupling 2-norbornene and allyl-terminated oligomeric ethylene oxide usingring opening metathesis polymerization as illustrated in (VIII) below.

P

t-C4H9 t-C4H9

t-C4H9t-C4H9

RuCl

Cl

OO O

OO O

6

6

a a a =5–10

(VI)(VII)

+i

Ru(C5H9)3P

Cl

Cl

(VIII)

i: Toluene, VI or VII

484 Methods for Making Functionalized Polymers

5. An azo-free method for preparing the ruthenium metathesis catalysts wasdeveloped by Nolan [6].

RuCl2P(C6H5)3 Ru

P(C6H5)3

P(C6H5)3

Cl

ClRu

PCy3

PCy3

Cl

Cli ii

i: 3,3-Diphenylpropargyl alcoholii: Triscyclopentadienyl phosphine

References

1. K. Wagener et al., US Patent 6,605,748 (August 12, 2003)2. C. Angeletakis, US Patent 7,173,097 (February 6, 2007) and US Patent 7,060,770 (July 13, 2006)3. R.H. Grubbs et al., US Patent 7,102,047 (September 5, 2006)4. D.E. Fogg et al., US Patent 7,094,898 (August 22, 2006)5. P. Piccinelli et al., US Patent 7,160,969 (January 9, 2007)6. S.P. Nolan, US Patent 7,205,424 (April 17, 2007)

Notes 485

C. Cationic

Title: Polymerization of i-Butene in HydrocarbonMedia Using bis(Borane) Co-Initiators

Author: S. Collins, US Patent 7,196,149 (March 27, 2007)Assignee: BASF Aktiengesellschaft (Ludwigshafen, DE)

SIGNIFICANCE

A polymerization method for cationically polymerizing liquefied isobutyleneusing the initiator pair 1,2-bis(9-bora-1,2,3,4,5,6,7,8-octafluoro-fluorenyl)-3,4,5,6-tetrafluorobenzene and tri-n-octylaluminum is described. The method is particularlyunique in that the polymerization occurs in a nonchlorinated solvent. Isobutylenecatalyzed using these co-reagents had molecular weights upto 258,000 daltons.

REACTION

ai

Note1

i: Tri-n-octylaluminum, 1,2-bis(9-bora-1,2,3,4,5,6,7,8-octafluorofluorenyl)-3,4,5,6-tetrafluorobenzene, toluene

486

EXPERIMENTAL

Preparation of Polyisobutylene

Isobutene was condensed at �78�C into a graduated cylinder under nitrogen, and12ml were transferred into a reaction vessel containing 1 g of tri-n-octylaluminum.The mixture was stirred for 30 minutes at �78�C and then transferred to a secondreaction vessel. It was then treated with 48 mml of 0.05M 1,2-bis(9-bora-1,2,3,4,5,6,7,8-octafluorofluorenyl)-3,4,5,6-tetrafluorobenzene dissolved in toluene,which resulted in an uncontrolled, exothermic polymerization accompanied by rapidgelation of the solution. The mixture was quenched with 1ml of 0.2M NaOCH3 inmethanol. The volatiles were removed and the residue washed with methanol thendissolved in hexane. The solution was filtered, concentrated, and the product isolated.Reaction scoping results are provided in Table 1.

REACTION SCOPING

NOTES

1. The co-catalyst, 1,2-bis(9-bora-1,2,3,4,5,6,7,8-octafluorofluorenyl)-3,4,5,6-tetrafluorobenzene, (I), was prepared according to the method of Williams [1].

2. In a subsequent investigation by Kennedy [2], the co-catalyst, 1,2-bis(9-bora-1,2,3,4,5,6,7,8-octafluorofluorenyl)-3,4,5,6-tetrafluorobenzene, was also usedto polymerize 1-butene.

3. Wang [3] polymerized ethylene using boron containing activators tris(penta-fluorophenyl)-borane, (II), and lithium tetrakis(pentafluorophenyl)borate,(III). Using tris(pentafluorophenyl)-borane, (II), with alumoxane, Arriola[4] prepared poly(ethylene-co-propylene) and polypropylene.

TABLE 1. Isobutylene polymerization scoping reactions using tri-n-octylaluminumand 1,2-bis(9-bora-1,2,3,4,5,6,7,8-octafluorofluorenyl)-3,4,5,6-tetra fluorobenzene asthe catalyst pair.

EntryCo-catalyst(mmol)

Isobutylene(mol)

Mw 1� 103

(daltons) PDI

1 0.20 14.6 69.0 3.163 0.64 0.56 97.8 2.224 2.00 3.3 195 3.185 2.00 3.3 258 2.28

Note: In all cases the conversion was 100%.

Notes 487

B

FF

F

FF

FF

F

F

F

FF

FF

F

B

FF

F

FF

FF

F

F

F

FF

F

F

F

F

F

FF

F

Li

(II) (III)

4. Using 2-chloro-2,4,4,-trimethylpentane as the initiator and ethylaluminumdichloride as the Lewis acid, McDonald [5] and Shaffer [6] prepared highmolecular weight polyisobutylene with perfluorinated alkanes as polymeriza-tion solvents.

5. Goodall [7] polymerized norbornene using the cationic chromium-palladium/boron pair complex, (IV) to aMwof roughly 1,200,000 daltonswith a PDI indexof 1.2.

CrO (NCCH3 )2

Cl

Pd(C6H5)3P

B

FF

F

FF

FF

F

F

F

FF

F

F

F

F

F

FF

F

(IV)

References

1. W. Williams et al., J. Am. Chem. Soc. 1991, 121, 3244–32452. J.P. Kennedy et al., US Patent 7,202,317 (April 7, 2007)3. S. Wang et al., US Patent 7,196,147 (March 27, 2007)4. D.J. Arriola et al., US Patent 7,193,024 (March 20, 2007)5. M.F. McDonald et al., US Patent Application 2006-0111522 (May 25, 2006) and US Patent Application

20060089467 (April 27, 2006)6. T.D. Shaffer et al., US Patent Application 2006-0100398 (May 11, 2006)7. B.L. Goodall et al., US Patent 7,172,986 (February 6, 2007)

488 Polymerization of i-Butene in Hydrocarbon Media Using bis(Borane) Co-Initiators

Title: Copolymers of Tetrahydrofuran, EthyleneOxide,and an Additional Cyclic Ether

Author: G. Pruckmayr et al., US Patent 6,989,432 (January 24, 2006)Assignee: Invista North America S.a.r.l. (Wilmington, DE)

SIGNIFICANCE

Terepolymers having Mn’s less than 3200 daltons have been prepared consisting ofTHF, 3-ethyl-tetrahydrofuran, and ethylene oxide, which were catalyzed by the acidresin NAFION� NR-50. Terpolymer hydrophobic/hydrophilic properties were con-trolled by the ethylene oxide content.

REACTION

OO

OO

a b c

i

d

i: 3-Ethyl-tetrahydrofuran, 1,4-butanediol, NAFION� NR-50

EXPERIMENTAL

A reactor was charged with THF (2.22mol), 3-ethyl-tetrahydrofuran (0.4mol), 1,4-butanediol (0.01mol), andNAFION� NR-50 (10 g) cryoground to less than 80mesh.The mixture was heated to 50�C and treated with ethylene oxide (0.19 mols) over a 4hour period. Heating was continued for an additional 15 minutes and then cooled to30�C and filtered. The polymer solution was concentrated, and the product wasisolated in 24% yield as a viscous liquid having a Mn of 3,100 daltons with a THFcontent of 72mol%, ethylene oxide content of 25mol%, and a3-ethyl-tetrahydrofurancontent of 3 mol%.

489

REACTION SCOPING

NOTES

1. PolyTHF was prepared by Meier [1] using a catalyst mixture consisting ofSiO2 containing 21wt% NiO, 7.3wt% CuO, and 2wt% Mn3O4 and thenpolymerized using Montmorillonite Catalyst K 306. Calcined TiO2 VKR 611containing ammonium paratungstate and oxalic acid dihydrate were used bySteinbrenner [2] to polymerize the THF.

2. THF was copolymerized with 3-methyl-THF in the presence of 1,4-butanediolby Pinkos [3] using the catalyst dodecatungstophosphoric acid.

3. Schlitter [4] demonstrated that catalysts of themontmorillonite/saponite group,the kaolin/serpentine group, and the palygorskite/sepiolite groupwere effectiveas the THF polymerization agents.

TABLE 1. Summary of terepolymers produced when catalyzed by the solidperfluorosulfonic acid resin NAFIONR NR-50.

Reaction Charge Polymer Properties

EntryTHF(g)

EthyleneOxide (g)

Co-component(g)

PolymerMn

(daltons)

THFContent(%)

Co-component(%)

EthyleneOxideContent(%)

2 26 6.5 3-Ethyl-THF(13)

1075 49 20 31

3 10 9 Oxepane (10) 2430 45 20 354 800 55 3-Ethyl-THF

(100)2700 68.1 3.9 28

TABLE 2. Summary of terepolymers produced when catalyzed by the compoundfluorosulfonic acid.

Reaction Charge Polymer Properties

EntryTHF(g)

3-EthylTHF (g)

EthyleneOxide(g)

PolymerMn

(daltons)

THFContent(%)

3-EthylTHF

Content(%)

EthyleneOxide

Content (%)

5 663 176 37.1 1,804 85.7 9.5 4.89 1,448 385 81 1,778 85.7 9.6 4.713 2,768 792 204 1,497 80.1 8.1 11.8

490 Copolymers of Tetrahydrofuran, Ethylene Oxide, and an Additional Cyclic Ether

References

1. A. Meier et al., US Patent 7,148,318 (December 12, 2006)2. U. Steinbrenner et al., US Patent 7,074,944 (July 11, 2006)3. R. Pinkos et al., US Patent 7,098,349 (August 29, 2006)4. S. Schlitter et al., US Patent 7,041,752 (May 9, 2006)

Notes 491

D. Chain Transfer Agents

Title: Dithiocarbamic Esters

Author: D. Achten et al., US Patent 7,169,937 (January 30, 2007)Assignee: Bayer Aktiengesellschaft (Leverkusen, DE)

SIGNIFICANCE

A method for the controlled emulsion polymerization of chloroprene using dithio-carbamic esters as sulfur-based chain transfer agents is described. Themethod providesindustrially relevant molar masses with Mn’s > 50,000 daltons with good yields inacceptable times. It was further determined that when pKa values for the dithiocar-bamic acid precursors were less than 12, the thioester was ineffective as a regulator.

REACTION

HN N

SS

N

SS ClNa

Not isolated Polymerization regulator

i ii

Cl

Cl

Cl

Cl

1,2-addition 3,4-addition 1,4-addition

iii

Regulator a b c............ ...... ......

...... ......++

i: THF, potassium, carbon disulfide, 1,3-dichloro-2-buteneii: Dresinate 731, water, naphthalenesulphonic acid, sodium hydroxide

EXPERIMENTAL

1. Preparation of 3-Chloro-2-Butenyl-1H-Pyrrole-1-CarbodithioateRegulator

A1-liter reactionvesselwas chargedwith 500ml of THF and potassium (1mol) undernitrogen at ambient temperature and then treatedwith 1H-pyrrole (1mol) dissolved in

492

150ml of THF over 30 minutes. This mixture was treated with carbon disulphide(1mol) dissolved in 240ml of THF and stirred for 1 hour. It was then posttreated with1,3-dichloro-2-butene (1.5mol) with the reaction extent monitored using GC. Thereaction solution was concentrated in vacuo, the residue slurried with 500ml ofpentane, and the product isolated by filtration.

2. Preparation of Polychloroprene by Emulsion Polymerization

A 3-liter glass reactor was charged with 125 parts of deionized water (1250 g), 2.80parts of Dresinate 731 in the form of 70% strength solution (40 g), 0.3 part ofcondensed naphthalenesulphonic acid in the form of 30% strength solution (10 g),and 0.65 part ofNaOH (6.5 g). This aqueousmixturewas then treatedwith 100 parts ofchloroprene and the Step 1 product (15mmol). The polymerization was conducted at45�C using a 2.5% strength solution of formamidinesulphinic acid as the initiator andcontinued for 90 minutes until a 60% product conversion was obtained.

DERIVATIVES

TABLE 1. Effect on the polymerization of chloroprene using selecteddithiocarbamic esters as sulfur-based chain transfer agents.

Entry Regulator

PolychloropreneSolution

Viscosity (mPas)PolychloropreneMn (daltons)

1 N

SS Cl14 50,000

2

N

N

SS Cl35 101,000

3 N S

S

Gelled —

5N S

SOCH3

O

Gelled —

(continued)

Derivatives 493


Entry Regulator

PolychloropreneSolution

Viscosity (mPas)PolychloropreneMn (daltons)

6 N S

S Cl

Gelled —

7 S S

SO

S O

O

O

O O

67 168,000

9 O S

SOCH3

O

Gelled —

Note: Very limited characterization data were provided by the author.

TABLE 2. Acidity constants for selected dithiocarbamic acids.

Entry R pKa

1N

17.0

2N

N14.5

3,5,6N

5.1

Note: An aliphatic dithiocarbamic ester acid precursor having a pKa value less than 12 was ineffective as asulfur-based chain transfer agents.

494 Dithiocarbamic Esters

NOTES

1. Chiefari [1] prepared sulfur-containing chain transfer agents, (I) and (II), tocontrol the polydispersity and multimodal molecular weight distribution ofmethyl methacrylate during free radical polymerization. The synthesis of apolymeric chain transfer agent analogue, (III), was also proposes by the author.

S S

(I)

SS

S

(II)

S

SR

(III)

R > C 1

a

2. Dithiocarbonylated ethyl xanthates, (IV), dithiophosphorylates, (V), and azoderivatives, (VI), prepared by Wilczewska [2], Destarac [3], and Charmot [4],respectively, and were effective as chain transfer agents in free radicalpolymerization reactions.

O

S SC2H5

(IV)

H3CO

O

S O

S PO OC2H5

OC2H5

(V)

C2H5O

OS S

NN

(VI)

3. Charmot [5] developed amethod for removing the thiocarbonylthio or thiopho-sphorylthio end group of polymers and re-functionalizing it with N-methyl-malimide.

S N

OO

OO

........

S

OO

OO

........

NO O

CNi

a

i: Methyl ethyl ketone, N-methyl-malimide, 2,20-azobisisobutyronitrile

Notes 495

References

1. J. Chiefari et al., US Patent Application 2004-0024132 (February 5, 2004)2. Z.A. Wilczewska et al., US Patent 7,109,276 (September 19, 2006)3. M. Destarac et al., US Patent Application 2003-0045661 (March 6, 2003)4. D. Charmot et al., US Patent 7,012,119 (March 14, 2006)5. D. Charmot et al., US Patent 6,919,409 (July 19, 2005)

496 Dithiocarbamic Esters

E. Emulsifing Agents

a. Polymeric

Title: Amphiphilic Copolymers Useful Especiallyas Emulsifiers

Author: E. Camus et al., US Patent 7,144,947 (December 5, 2006)Assignee: Laboratories d’Hygiene et de Dietetique (Chenove, FR)

SIGNIFICANCE

Amphiphilic copolymers have been prepared that have reduced surface contact anglesand are effective as emulsifying agents or absorbents. These materials were preparedby reacting poly[styrene-b-poly(ethylene-butylene)-g-succinic anhydride-b-polysty-rene)] [Kraton G 1901�] with methoxypolyethylene glycols having Mn’s between2000 and 8000 daltons.

REACTION

OO O O OO O

O O

H3CO OCH3

i

4545

aaba a b

Polyethylene/butylene Polyethylene/butylene

i: Toluene, polyethylene glycol methyl ether, sulfuric acid, ethanol, water

497

EXPERIMENTAL

Preparation of (Polystyrene-b-((Polyethylene-co-Butylene)-g-(DiethyleneglycolSuccinate)-b-Styrene)

A reactor was charged with 150ml of toluene and 20 g poly[polystyrene-b-poly(ethylene-co-butylene-g-succinic anhydride)-b-styrene] containing 2% graftedsuccinic anhydride and then heated until the polymer dissolved. The mixturewas next treated with a solution of 32 g polyethylene glycol methyl ether having aMn of 2000 daltons dissolved in 100ml of toluene containing 20 drops of sulfuricacid and then refluxed for 30 to 40 minutes. The material was isolated byprecipitating in 1.5 liter of water/ethanol, 1:1, at 90�C to 100�C. The rubber wasdried at 40�C to 50�C under vacuum and purified by dissolving in 100 to 150ml oftoluene at 90�C to 100�C and re-precipitating in 1.5 liter of water/ethanol, 1:1; theprocess was repeated until all unreacted polyethylene glycol methyl ether wasremoved.


TABLE 1. Contact angles of selected KratonR-containing amphiphilic pendants.

Entry Polyether*1Contact Angle

(deg)

Kraton G 1901�

(Reference)None 95

2 PEG-200 863 PEG-600 854 PEG-2000 766 PEG-8000 727 PEGME-350 878 PEGME-500 861 PEGME-2000 7510 PEO/PPO/PEO-1900 75

Note: These polyesters were subsequently used in the manufacture of skin care products.*1PEG¼Polyethylene glycolPPO¼Polypropylene oxidePEGME¼Polyethylene glycol monomethyl ether

498 Amphiphilic Copolymers Useful Especially as Emulsifiers

NOTES

1. Wang [1] prepared biocompatible cyclodextrin grafted polymers, (I), consist-ing of hydrophobically modified cyclodextrin with a biocompatible hydrophil-ic polymer backbone that were used as drug delivery agents.

OO

O NH

OO

O

OR1R2O

O

O OR1O

R1O

OR2

a b

6

(I)

1) R1 = R2 = CH3CO

2) R1 = C2H5, R2 = H

2. Ekwuribe [2] prepared amphiphilic mono-dispersed polymers, (II), consistingof polyethylene oxide with one terminus consisting of a hydrophobic ester andthe other containing insulin. These materials were effective at surviving an invitro model of intestinal digestion.

TABLE 2. Emulsion stability of selected amphiphilic copolymers preparedby adding 1.5 g of a selected experimental polymer to an oil/water mixtureand blending at 90�C to 100�C.

Entry Water/Oil Distribution (g) Emulsion Appearance

Kraton G 1901�

(Reference)50/50 Unstable, immediate demixing

1 50/50 Stable, no change after 3 weeks1 25/75 Stable, no change after 3 weeks1 75/25 Stable, no change after 3 weeks6 25/75 Unstable, degrades over time6 75/25 Stable, no change after 3 weeks

Note: The targeted applications for these materials was in moisturizing creams.

Notes 499

O

O

OO

15 8

(II)

Insulin

O

3. Nonionic amphiphilic telechelic polymers consisting of polyethylene oxidewith polyhedral oligosilsesquioxane, POSS, termini were prepared by Mather[3] and used as surfactants and thickening agents. The hydrophobicity of theseamphiphilic telechelics, (III), was controlled by varying the molecular weightof the polyethylene oxide component.

Si NH

OO

HN SiO

POSS

O

O

OPOSS

(III) a = 20, 24, 72, 160, 200

a

4. Nathan [4] prepared poly(monostearoyl glycerol-co-glyceryl monooleate-succinate), (IV), to prepare amphiphilic block polyester microdispersions thatwere bioabsorbable and biocompatible and useful as drug delivery agents.

O

O

C17H35

O

OO

O

O

O

O

C11H23

OO

O

a

b

a:b = 1:1, 1:3

(IV)

References

1. L. Wang et al., US Patent 7,141,540 (November 28, 2006)2. N.N. Ekwuribe et al., US Patent 7,084,114 (August 1, 2006)3. P.T. Mather et al., US Patent 7,067,606 (June 27, 2006)4. A. Nathan et al., US Patent 7,026,374 (August 11, 2006)

500 Amphiphilic Copolymers Useful Especially as Emulsifiers

b. Inverse Emulsion

Title: Anionic Copolymers Prepared in an InverseEmulsion Matrix and Their Use in Preparing CellulosicFiber Compositions

Author: B. Walchuk et al., US Patent 7,250,448 (July 31, 2007)Assignee: Hercules Incorporated (Wilmington, DE)

SIGNIFICANCE

Linear water-soluble anionic poly(acrylamide-co-ammonium acrylate) has beenprepared by a water-in-oil polymerization. These materials are characterized by aHuggins’ constant in brine greater than 0.75 and a storage modulus for a 1.5 wt%actives polymer solution at 4.6 Hz greater than 175 Pa. These agents are particularlyuseful as drainage aids and contamination control aids in papermaking.

REACTION

O

NH2NH2O O NH4O

a b ci

i: Paraffin oil, sorbitan monooleate, fatty acids of poly(ethyleneoxide), acrylamide,acrylic acid, water, ammonium hydroxide, 2,20-azobisisobutyronitrile

501

EXPERIMENTAL

Preparation of Poly(Acrylamide-co-Ammonium Acrylate)

Areaction flaskwas chargedwith an oil phase consisting of paraffin oil and surfactantssorbitan monooleate (4.5 g) and fatty acid esters of poly(ethyleneoxide) (9.0 g) andheated to 37�C. In a separate vessel an aqueous phase was prepared and consisted of53wt% acrylamide solution in water (126.5 g), acrylic acid (68.7 g), deionized water(70.0 g), and Versenex 80 solution (0.7 g). The solution pH was adjusted to pH 5.4using 29.4% ammonium hydroxide solution (33.1 g). The aqueous phase was thenadded to the oil phase while simultaneously mixing with a homogenizer to obtain astable water-in-oil emulsion. This emulsion was mixed while being sparged withnitrogen for 60minutes at 50�C. Thereafter the nitrogen spargewas discontinued; anda nitrogen blanket was implemented. The mixture was next treated with 3wt% 2,20-azobisisobutyronitrile dissolved in toluene (0.213 g) over a period of 2 hours corre-sponding to an initial initiator charge of 250 ppm and stirred for 60 minutes at 62�C.Thereafter an additional 3wt% initiator dissolved in toluene (0.085 g) was added inunder 60 seconds, corresponding to a 2,20-azobisisobutyronitrile charge of 100 ppm,and the temperature was held at 62�C for 2 hours. The reactor was cooled to ambienttemperature, and the product was isolated.

REACTION SCOPING

TABLE 1. Experimental conditions used in preparing poly(acrylamide-co-ammonium acrylate) with sorbitan monooleate as a surfactant.

Entry Acrylic acid (%) Medium pH Initiator

2 50 3.0 2,20-Azobisisobutyronitrile4 50 6.0 2,20-Azobisisobutyronitrile10 50 5.4 t-Butylhydroperoxide11 40 5.4 2,20-Azobisisobutyronitrile

TABLE 2. Performance testing of poly(acrylamide-co-ammonium acrylate).

Entry G0 at 4.4 Hz (Pa)

IntrinsicViscosity(dL/g) Huggins’s Constant

Viscosity AverageMolecular

Weight (daltons)

2 237 32 2.0 3.14 205 43 1.9 7.610 189 50 1.1 12.911 328 42 2.3 6.6

Note: Storage modulus, G0, testing was evaluated using 1.5wt% polymer at 25�C at 4.6Hz.

502 Anionic Copolymers Prepared in an Inverse

NOTES

1. Anionic copolymers consisting of acrylamide and styrene sulfonic acid sodiumwere prepared by Harrington [1] and used as drainage aids for cellulosic fibercompositions. Doherty [2] anionically prepared high molecular weight poly(acrylamide-co-styrene sulfonic acid sodium), which was also effective as adrainage aid.

2. Cationic copolymers consisting of acrylamide and quaternary ammonium saltssuch as [2-(acryloyloxy)ethyl]trimethyl ammonium chloride, (I), prepared byHollomon [3] were effective as drainage aids. In the absence of crosslinkingthese cationic materials were characterized by a Huggins constant greater than0.3 with a storage modulus at 6.3Hz of over 50 Pa.

NH2O OO

a b c

N(I)

Cl

3. Doherty [4] prepared water compatible hydrophobic polymers such as poly(acrylamide-co-t-octylacrylamide), (II), that were used as components incellulosic fiber compositions.

NH2O NHO

a b c

t-C8H17

(II)

References

1. J.C. Harrington, US Patent Application 2006-0185806 (August 24, 2006)2. E.A.S. Doherty et al., US Patent Application 2006-0127351 (June 15, 2006)3. M. Hollomon et al., US Patent Application 2004-0143039 (June 22, 2004)4. E.A.S. Doherty et al., US Patent Application 2006-0266488 (November 30, 2006)

Notes 503

F. Free Radical Polymerization

Title: Perfluorodiacylperoxides as PolymerizationInitiators

Author: W. Navarrini et al., US Patent 7,135,599 (November 14, 2006)Assignee: Solvay Solexis, S.p.A. (Milan, IT)

SIGNIFICANCE

Four perfluorodiacylperoxide free radical initiators were prepared by condensingperfluoroacyl chloride derivatives with hydrogen peroxide and sodium hydroxide.When the product bis(2-fluoro-2-trifluoromethyl-perfluoropropionyl) peroxide wasused to polymerize vinylidene fluoride, a 90% conversion was observed.

REACTION

F3C Cl

F

F 3CO

F3C O

F

F3CO

OCF3

O

CF3

F

i

i: Sodium hydroxide, 1,1,2,-trichloro-1,2,2-trifluoroethane, hydrogen peroxide

EXPERIMENTAL

1. Preparation of bis(2-Fluoro-2-Trifluoromethyl-Perfluoropropionyl)Peroxide

A four-necked flask containing a mechanical stirrer, a solid CO2 condenser, athermometer, and a dropping funnel was charged with NaOH (48.7mmol) and 15ml

504

of distilled water. The solution was then treated with 50ml of 1,1,2,-trichloro-1,2,2-trifluoroethane and cooled to roughly 0�C before being treated with 4.6ml of 57.5%H2O2 (94mmol). Using the dropping funnel, 2-fluoro-2-trifluoromethyl-perfluoro-propionyl chloride (10.2 g)was slowly introduced to control the reaction exothermandthen transferred into a separatory funnel after around 10 minutes. The organic phasewas washed with distilled water until a neutral pH was observed and then dried withNa2SO4. The perfluoro-peroxide assaywas determined using iodometric titration, andthe product was isolated in 70% yield.

2. Preparation of Polyvinylidene Fluoride

The Step 1 product (0.12mmol) dissolved in 1.2ml of 1,1,2,-trichloro-1,2,2-trifluoroethane and 20ml of distilled water were introduced into a 50ml steelreactor equipped with a magnetic stirrer. The reactor contents were cooled withliquid nitrogen and evacuated to 1� 10�3 mbar to remove trace amounts of oxygen.The reactor was next charged with 22 atm of vinylidene fluoride and the reactortemperature, raised to 57�C. Once the autoclave pressure decreased to 15 atm,additional vinylidene fluoridewas added tomaintain the reaction pressure at 20 atm.The polymerization was stopped after 48 hours, and the product was isolated in 90%yield.

DERIVATIVES

TABLE 1. Selected perfluoroalkyl peroxides and their effectiveness in initiatingthe polymerization of vinylidene fluoride.

Entry Fluoro Initiator Polymer conversion (%)

4 [(CF3)2CFCOO]2 906 [(CF3O)(CF3)2CCOO]2 6510 [(CF3O)2CF3CCOO]2 78

12 O

O

O

OF 7

F7

55

Note: 19F-NMR, MS, Td, and IR for each entry were provided by author.

19FNMR (CFCl3¼ 0): �184 ppm 1F; �75 ppm 6FIR (main bands (cm�1): 1853 (m), 1824 (m), 1309 (m), 1264 (s)Mass spectrum (main peaks and intensities): 319 (3), 281 (3), 231 (5), 181 (5), 131 (5), 69(100)Decomposition Constants: Kd (s

�1): 4.4� 10�5 (60�C), 16.21� 10�5 (70�C), and 57.81� 10�5 (80�C)

Derivatives 505

NOTES

1. Perfluoroether monomers 3,5-dioxa-1-heptene, (I), and 3,5,8-trioxa-1-nonene,(II), were prepared by the author [1] and polymerized with tetrafluoroethyleneusing perfluoropropionyl-peroxide as the reaction initiator.

F3CO

CF2

OCF

F

F

F3CO

CF2

OCF2

OCF

F

F

(I) (II)

2. In an earlier investigation the author [2] converted 2,2,5,5-tetrafluoro-4-tri-fluoromethoxy-1,3-dioxolane into the corresponding peroxide initiator, (III),using the method described in Step 1. Brothers [3] converted 3-oxa-perfluor-ohexanoyl fluoride into the corresponding peroxide, (IV), using sodiumpercarbonate.

OO

O

O F2C OCF2

O

CF2O

F2CO

F3CO

OCF3

(III)

n-C3F7O

CF OO CF

On-C3F7

O

O

CF3

CF3

(IV)

3. Fontana [4] prepared the free radical pro-initiator perfluoroethyether acylfluoride, (V), by florination of the precursor alcohol having a Mn of roughly460 daltons with CsF.

F3CO

CF2

F2C

O

F2C

O

F2C F

O

a b

(V)

References

1. W. Navarrini et al., US Patent 7,160,967 (January 9, 2007)2. W. Navarrini et al., US Patent 7,135,599 (November 14, 2006)3. P.D. Brothers et al., US Patent 7,112,314 (September 26, 2006)4. G. Fontana et al., US Patent Application 2004-0147778 (July 29, 2004) andUSPatentApplication 2004-

0147780 (July 29, 2004)

506 Perfluorodiacylperoxides as Polymerization Initiators

G. Macroinitators

a. Photoinitators

Title: Polymeric Photoinitiators

Author: D. E. Herr et al., US Patent Application 2007-0078246 (April 5, 2007)Assignee: National Starch and Chemical Company, Bridgewater, NJ)

SIGNIFICANCE

Akeydrawback for usingphotoinitators is the residual photochemical by-products.Toaddress this problem, polybutadiene photoinitators containing grafted benzophenonehave been prepared where both photoinitiator and photochemical by products arecompletely miscible with hot melt processable resins.

REACTION

O

HO

O

O

O

OSiO

SiH

O

OSiO

SiPolyisobutylene

i ii

iii

i: 4-Hydroxybenzophenone, 2-butanone, potassium carbonate, allyl bromideii: THF, 1,1,3,3-tetramethyldisiloxane, chlorotris(triphenylphosphine) rhodiumiii: Polybutadiene, toluene, platinum 1,3,5,7-tetravinyl-1,3,5,7-tetramethylcy-

clotetrasiloxane

507

EXPERIMENTAL

1. Preparation of 4-Allyloxybenzophenone

A reaction vessel was charged with 4-hydroxybenzophenone (940mmol) dissolvedin 700ml of 2-butanone and then treated with K2CO3 (1.41mol) and heated to 65�C.This mixture was next treated with the dropwise addition of allyl bromide (1.41mol)and stirred for 6.5 hours at 65�C. The slurry was filtered, and the filtratewas extractedwith 500ml of 1% hydrochloric acid. The organic layer was isolated, dried overMgSO4, and concentrated. The product was isolated in 92% yield a pale yellow solid.

2. Preparation of Siloxy-Functionalized Benzophenone

The Step 1 product (840mmol) was dissolved with warming in 150ml of THFand then transferred into an addition funnel. A reaction vessel was charged with1,1,3,3-tetramethyldisiloxane (4.18mol) and 100ml of THF, and the temperaturewas raised to 50�C. This mixture was then treated with chlorotris(triphenyl-phosphine) rhodium (22mg), and 5ml of the Step 1 THF solution. Thereafter thereaction temperature was raised to 60�C, and the mixture was treated with thedropwise addition of the remainder of the Step 1 product. Following this addition,the mixture was stirred an additional 15 minutes, cooled to 35�C, and treated withthree scoops of activated carbon. The slurry was stirred for 30 minutes then filtered,the filtrate concentrated, and 329 g product isolated as a yellow oil.

3. Preparation of Poly(Butadiene)-Grafted Benzophenone

A mixture consisting of polybutadiene (734 g) dissolved in 1100ml toluene and theStep 2 product was placed into an addition funnel. Additional polybutadiene(0.88mol) dissolved in toluene was warmed to 50�C, treated with a solution of 3.0to 3.5wt% platinum 1,3,5,7-tetravinyl-1,3,5,7-tetramethylcyclotetrasiloxane (1.8 g),and then heated to 80�C. This mixture was treated with the dropwise addition ofpolybutadiene and the Step 2 product over 90minutes. The solutionwas then cooled to35�C, treated with 7 small scoops activated charcoal, and then filtered and concen-trated. The product was isolated as a viscous pale yellow oil in quantitative yield.

DERIVATIVES

A thioxanthone, (I), and an amide-containing benzophenone, (II), derivativewere alsoprepared.

O

S

O

NH

OCO2H

Polyisobutylene(I)

(II)

OO

O

SPolyisobutylene

508 Polymeric Photoinitiators

TESTING

Experimental agents were evaluated for their UV curing behavior effectiveness asphotoinitiators using a UV curable composition consisting of tetraallyl bisphenol Aand Tetrathiol 10. The testing results are summarized in Tables 1 and 2, respectively.

NOTES

1. UV- and thermally curable cycloaliphatic vinyl ethers, (III), and maleimidederivatives, (IV), were previously prepared by the author [1,2], respectively,and used in resins as moisture barrier sealants.

O O

(III) (IV)

O O O

O O

N N

O

O

O

O

2. Bradley [3] coated circuit boards with a reactive substrate as a method ofactivating a latent photoinitiator, (V), for subsequent crosslinkable reactions asillustrated below. Multi-layered circuits were also prepared by Kawasaki [4]using benzophenone as the photoinitiator.

TABLE 1. UV curing behavior of the Step 3 product as a photoinitiator in a UVcurable composition consisting of tetraallyl bisphenol A and Tetrathiol 10.

InitiatorTreatmentLevel (wt%) DHp (J/g) Conversion (%) Dt (s)

None –– �18 6 8.4Benzophenone 2 �117 40 7.8Step 3 product 8 �132 45 7.8

TABLE 2. Effectiveness of the Step 3 as a photoinitiator in aUV curable compositionconsisting of tetraallyl bisphenol A and Tetrathiol 10 with a UV cutoff of 300 nm.

InitiatorTreatmentLevel (wt%) DHp (J/g) Conversion (%) Dt (s)

None –– �63 21 6.6Step 3 product 2 �182 69 9.0Step 3 product 8 �244 79 6.0

Notes 509

S

OO

IS

O

+

Short

wavelength

(V)

3. A photosensitive agent, (VI), used as a lithographic printing plate was preparedbyMatsumura [5] as amethod for improving image resolution and print quality.

OO

Br Br

OK

BrBr

CO2C2H5

(VI)

References

1. D.E. Herr et al., US Patent Application 2006-0223937 (October 5, 2006)2. D.E. Herr et al., US Patent Application 2006-0009539 (January 12, 2006)3. G. Bradley, US Patent 7,183,333 (February 27, 2007)4. Y. Kawasaki et al., US Patent 7,178,234 (February 20, 2007)5. T. Matsumura et al., US Patent 7,169,535 (January 30, 2007)

510 Polymeric Photoinitiators

b. Reactivatable Polymerization

Title: Radical PolymerizationMethodPerformed in thePresence of Disulfide Compounds

Author: J.-M. Catala, US Patent 7,214,751 (May 8, 2007)Assignee: Rhodia Chimie (Aubervilliers, FR)

SIGNIFICANCE

A method for preparing isolatable and re-activatable polymethyl methacrylate usingthe chain transfer agent bis(ethoxythiocarbonyl)disulfane with 2,20-azobis(isobutyr-onitrile) is described. Reactivation of this macroinitiator with 2,20-azobisisobutyr-onitrile was then used to prepare block copolymers.

REACTION

OCH3O OCH3O

S

OCH3O

OC2H5

S

OCH3OO

O

a bai ii

i: Benzene, bis(ethoxythiocarbonyl)disulfane, 2,20-azobisisobutyronitrile, 1,10-azobis(cyclo-hexanecarbonitrile)

ii: Benzene, 2,20-azobisisobutyronitrile, vinyl acetate

EXPERIMENTAL

1. Preparation of Reactivatable Poly(Methyl Methacrylate)

A reaction vessel was charged with 50ml of benzene solution containing methylmethacrylate (0.236mol), bis(ethoxythiocarbonyl)disulfane (1.53mmol), 2,20-azo-bisisobutyronitrile (1.18mmol), and 1,10-azobis(cyclohexanecarbonitrile) (1mmol).The mixture was heated for 4 hours at 80�C and cooled, and the polymer was

511

precipitated in heptane. After drying the product was isolated in 97.3% yield having aMn of 11,200 daltons and a polydispersity index of 1.9.

2. Preparation of Poly(Methyl Methacrylate-block-Vinyl Acetate)

The Step 1 product (8 g) was dissolved in 50ml of benzene and then treated with 2,20-azobisisobutyronitrile (14.6mg) and 13.8 g of vinyl acetate and heated to 60�C for72 hours. Themixturewas cooled, and the polymer was precipitated in heptane. Afterdrying the block copolymerwas isolated in 47.8%yield having aMn of 21,500 daltonsand a polydispersity index of 1.6.

DERIVATIVES

Only the single macroinitiator was prepared.

NOTES

1. S,S0-bis-(a,a0-Dimethyl-a00-acetic acid)-trithiocarbonate, (I), previously pre-pared by Lai [1], was effective as a chain transfer agent and used in controlledradical polymerizations.

HO2C S S CO2H

S

(I)

2. The chain transfer activity of dithiocarbamate reagents, (II) and (III), preparedby Chiefari [2] and Charmot [3], respectively, was impacted by the substituentselection, (IV) and (V), and was effective in conferring living characteristics toa free radical polymerization. These agents were also used in introducing novelend group functionalities into polymers.

N

S

S

O

O

(II) (III)

N

S

S CO 2C 2H 5

512 Radical Polymerization Method Performed in the Presence of Disulfide Compounds

N

N

S

S

CN

(IV)

S

CN

S

NN

(V)

3. Polyfunctional dithiocarbamate derivatives, (VI) and (VII), were prepared bycharmot [4] and used as chain transfer reagents in free radical polymerizationreactions.

SS

S O S

S S

S O S

N N

NNNS

SNC

N

N S

S CN

NN

SS

CN

(VI)

(VII)

References

1. J.T. Lai, US Patent Application 2005-0267274 (December 1, 2005), US Patent 7,205,368 (April 17,2007), and US Patent 6,962,961 (November 8, 2005)

2. J. Chiefari et al., USPatentApplication 2004-0024132 (February 5, 2004) andUSPatent 6,747,111 (July8, 2004)

3. D. Charmot et al., US Patent 7,012,119 (March 14, 2006) and US Patent 6,919,409 (July 19, 2005)4. D. Charmot et al., US Patent Application 2004-0019163 (January 29, 2004)

Notes 513

Title: Copolymers of Maleic Anhydride by Stable FreeRadical Polymerization

Author: B. Keoshkerian, US Patent 7,009,011 (March 7, 2007)Assignee: Xerox Corporation (Stamford, CT)

SIGNIFICANCE

A stable free radical polymerization using 2,2,6,6-tetramethyl-1-piperidinyloxy withmaleic anhydride and styrene was used to prepared moderate molecular weightcopolymers with polydispersities less than 1.5. Thermal re-activation of thesecopolymers in the presence of other monomers produced block polymers.

REACTION

aa bOO O OO OOO O

i iiNote 1 Note 2 CN

i: Styrene, 2,2,6,6-tetramethyl-1-piperidinyloxyii: Styrene, acrylonitrile

EXPERIMENTAL

1. Preparation of Poly(Styrene-co-Maleic Anhydride)

A 1-liter reaction vessel was charged with 425ml of styrene, maleic anhydride(100.2 g), and 2,2,6,6-tetramethyl-1-piperidinyloxy (0.0205 moles) and then treateddropwisewith amixture of 72ml of styrene and 2,2,6,6-tetramethyl-1-piperidinyloxy(0.0782 moles). The reaction was heated to 135�C for 45 minutes and cooled, and themixture was dissolved in 500ml of THF. The polymer was precipitated in 3 liter ofhexane, and 125.3 g solid product were isolated having a Mn of 3523 daltons and apolydispersity of 1.48.

514

2. Preparation of Poly(Styrene-co-Maleic Anhydride-b-Styrene-co-Acrylonitrile)

The Step 1 product was dissolved in 118ml of styrene and 47ml of acrylonitrile andthenheated to 135�Cfor 100minutes and cooled.After theworkupdescribed inStep1,the product was isolated having a Mn of 62,000 daltons with a polydispersity of 1.41.

NOTES

1. Additional free radical polymerization regulating agents were provided byAnderson [1], (I)–(III).

HN

Nt-C4H9

Nt-C4 H9

HN

N

O

O O

O

O

(I) (II) (III)

2. Styrene macroinitiator having a Mn of 9300 daltons and terminated with2,2,6,6-tetramethyl-1-piperidinyloxy was thermally re-activated in the pres-ence of styrene to prepare a polymer having a Mn of 178,000 daltons in anearlier investigation by the author [2].

3. Fischer prepared poly(styrene-co-acrylonitrile) and polystyrene by stable freeradical emulsion polymerization using 4-hydroxy-2,2,6,6-tetramethyl-1-piper-idinyloxy with potassium peroxodisulfate at 120�C under elevated pressures.Polystyrene samples prepared in this manner had molecular weights of up to35,000 daltons with polydispersities of less than 1.5.

4. Bifunctional stable free radical polymerization reactions were prepared byGeorges [4] using divinylbenzene.

Initiator

Initiator

Initiator

TEMPO

TEMPO

i

i: 4-Hydroxy-2,2,6,6-tetramethyl-1-piperidinyloxy

Notes 515

References

1. A.G. Anderson et al., US Patent Application 20020061989 (March 23, 2002)2. B. Keoshkerian et al., US Patent 6,156,858 (December 5, 2000) and US Patent 5,739,229 (April 14,

1998)3. M. Fischer et al., US Patent 6,696,533 (February 24, 2004)4. M.K. Georges et al., US Patent 7,045,248 (July 10, 2001)

516 Copolymers of Maleic Anhydride by Stable Free Radical Polymerization

H. Macromolecular Depolymerization Catalysts

Title: Catalysts and Methods for PolymerizingMacrocyclic Oligomers

Author: R. P. Dion et al., US Patent 7,196,160 (March 27, 2007)Assignee: Dow Global Technologies, Inc. (Midland, MI)

SIGNIFICANCE

A method for polymerizing macrocyclic butylene terephthalate oligomers using 1,3-diacetoxy-1,1,3,3-tetrabutyldistannoxane is described.

REACTION

HOOC

O

O

OHb

ab >>i

O

O

O

O

O

O

O

O

a a > 8

Note 1

i: 1,3-Diacetoxy-1,1,3,3-tetrabutyldistannoxane

EXPERIMENTAL

Preparation of Polybutylene Terephthalate

Cyclic butylene terephthalate oligomers were heated for 3 minutes in a bowl of aHaake mixer to 230�C and 100 rpm. This was then treated with 0.003mol of 1,3-diacetoxy-1,1,3,3-tetrabutyldistannoxane permole of cyclic butylene terephthalate.The mixture was heated for 4.5 minutes, and the resulting polymer was recovered.

517

The polymer was then cooled to ambient temperature, crushed, ground to passthrough a 4mm screen, and dried at 90�C.Molecular weight profiles are provided inTable 1.

POLYMERIZATION MOLECULAR WEIGHT PROFILE

NOTES

1. Macrocyclic esters were prepared according to the method of Brunelle [1],which cyclo-oligomerizes terephthaloyl chloride and 1,4-butanediol withtriethylamine dissolved in CH2Cl2.

2. Commercially available polybutylene terephthalate was depolymerized byPhelps [2] and Faler [3] into 96% by weight of the tetramer by heating ino-dichlorobenzene.

3. Winckler [4] andDion [5] polymerized cyclic butylene terephthalate oligomersusing the 1,6-distanna-2,5,7,10-tetraoxacyclodecane derivative, (I), as thedepolymerization and repolymerization catalyst.

(I)

O

OO

O O

OO

Sn

O

O

O O

Sn

O

4. Amethod of re-cycling polytrimethylene terephthalate containing up to 0.5wt%acrolein by depolymerizing at 210�C for 60 minutes to re-generate 1,3-propanediol and terephthalic acid was developed by Kato [6]. In this processthe conversion was 100%.

5. Polyvinyl chloride and polyethylene terephthalatewere re-cycled byGuffey [7]by heating to between 285�C and 360�C for 15 to 60 minutes to re-generate thecorresponding monomers.

TABLE 1. Polymerization ofmarcocyclic butylene terphthalate using 1,3-diacetoxy-1,1,3,3-tetrabutyldistannoxane as catalyst and corresponding molecular weighprofiles.

Catalyst(mol%)

Mn 1� 104


(daltons)Mz 1� 105

(daltons)Mzþ1 1� 105

(daltons)

0.3 4.16 9.58 1.58 2.340.6 2.50 6.17 1.00 1.45

518 Catalysts and Methods for Polymerizing Macrocyclic Oligomers

References

1. D.J. Brunelle et al., US Patent 5,231,161 (July 27, 2003)2. P.D. Phelps et al., US Patent 6,713,601 (March 30, 2004)3. G.R.Faler., US Patent 7,022,806 (April 4, 2006) and US Patent 6,525,164 (February 25, 2003)4. S.J. Winckler et al., US Patent Application 2004-0011992 (January 22, 2004)5. R.P. Dion et al., US Patent Application 2005-0059768 (March 17, 2005)6. J. Kato et al., US Patent 6,867,322 (March 15, 2005)7. F.D. Guffey et al., US Patent 6,861,568 (March 1, 2005)

Notes 519

Title: Catalytic Systems

Author: Y.-F. Wang et al., US Patent 7,186,666 (March 6, 2007)Assignee: Cyclics Corporation (Schenectady, NY)

SIGNIFICANCE

Tetraphenoxyl titanates such as 4-isopropyl-, 2-isopropyl-6-t-butyl-, and 2-di-t-butyl-have been prepared and used as catalysts for the rapid depolymerization andrepolymerization of macrocyclic oligomers. In this manner macrocyclic co-estersconsisting of (butylene terephthalate-co-ethylene terephthalate) were re-polymerizedto molecular weights of up to 120,000 daltons.

REACTION

t-C4H9 OH t-C4H9 O Ti4

i PolymerNote 1

i: Toluene, tetraisopropyl titanateii: Macrocyclic(butylene terephthalate-co-ethylene terephthalate)co-ester

EXPERIMENTAL

1. Preparation of tetra(4-t-Butylphenoxy) Titanate

A reactor was charged with 4-t-butylphenol (199.7mmol) and 100ml of toluene andthen heated to reflux under nitrogen during which time roughly 20ml of toluenewereremoved by distillation. The mixture was then cooled to 100�C, treated with thesyringe-addition of tetraisopropyl titanate (47.43mmol), and refluxed 30 minutes.Isopropanol was then removed by distillation at up to 90�C. Thereafter an additional50ml of isopropanol was distilled over at 140�C, and a dark red liquid was isolated.Upon cooling the liquid crystallized to a red solid at ambient temperature. The crystalswere dried overnight at 80�C, and the product was isolated in 94.8% yield.

520

2. Polymerization of a oligo(Butylene Terephthalate-co-EthyleneTerephthalate) Macrocyclic Co-ester

Macrocyclic(butylene terephthalate-co-ethylene terephthalate) co-ester (8.91mmol)containing about 95mol% butylene terephthalate was charged into a vial and thenheated to 190�Cat 1 torr for 5minutes in an oil bath.Thismixturewas then treatedwith0.30mol%of the Step 1 product. Themixturewas re-heated to themelt phase at 190�Cfor 10 minutes and polymerized for 15 minutes. Thereafter the polymer began tocrystallize, and a white solid product was isolated.

DERIVATIVES AND RESULTS

NOTES

1. The preparation and use of organotin compounds as re-polymerization agentsfor linear polyesters and macrocyclic oligomers is provided by Faler [1] andWinckler [2], respectively.

TABLE 1. Oligomer re-polymerization of macrocyclic oligomers using 0.3mol%tetraphenoxy titanates.

Entry Catalyst OligomerPolymerizationTime (minutes)

PolymerYield (%)

Mw

(daltons)

2

i-C3H7

t-C4H9

O Ti4

Terathane2900*1

16 95 112,900

3t-C4H9

O Ti4

Cyclic Poly(ethylene-co-butylene)diol

15 99 21,200

4t-C4H9

O Tit-C4H9 4

Terathane2900 15 90 107,000

5

O TiC6H5

C6H5

4 Terathane2900 15 90 114,600

Note: Polymerization time represents the time interval when stirring began and ended because of reactionmixture solidification.*1Polytetramethyleneether ester with a Mn of 2,900 daltons

Notes 521

2. Paquette [3,4] re-polymerized macrocyclic butylene terephthalate oligomerscontaining fibers using 1,1,6,6-tetrabutyl-1,6-distanna-2,5,7,10-tetraoxacyclo-decane as the reaction catalyst.

3. Kuhlman [5] re-polymerized macrocyclic ester oligomers in the presence ofdi-n-butyl tin oxalate, which had up to a 2 minute latency period and wasfollowed by a rapid polymerization similar to that of di-n-butyltin glycolate.

References

1. G.R. Faler, US Patent 7,022,806 (April 4, 2006) and US Patent 6,525,164 (February 25, 2003)2. S.J. Winckler et al., US Patent 6,369,157 (April 9, 2002)3. M.S. Paquette, US Patent Application 2006-0004135 (January 5, 2006)4. M.S. Paquette, US Patent Application 2006-0003887 (January 5, 2006) and US Patent Application

2005-0288420 (December 29, 2005)5. R.L. Kuhlman et al., US Patent Application 2005-0288176 (December 29,2005)

522 Catalytic Systems

I. Metallocene Catalysts

Title: Metallocene Catalysts Containinga Cyclopentadienyl Ligand Substituted by a Siloxyor Germiloxy Group Containing an Olefinic Residue

Author: M. Aubert et al., US Patent 7,037,872 (May 2, 2006)Assignee: Borealis Technology Oy (Porvoo, FI)

SIGNIFICANCE

Themetallocene pre-catalyst, ethylene-bis2-(4-butenyldiisopropylsiloxy)-1-indenyl)zirconium dichloride, has been prepared. When blended with co-catalyst methyla-lumoxane forming an aluminum/zirconium ratio of 300:1, respectively, the catalyticmixture had very high ethylene polymerization activity.

REACTION

Br Cl Si Si

Si

Si

Si

Si

ZrCl2

i ii iii

ivvn

523

i: Magnesium, THF, diisopropyldichlorosilane, copper (I) cyanideii: 2-Indanone, 1,8-diazobicyclo[5.4.0]undec-7-ene, benzeneiii: THF, n-butyllithium, 1,2-dibromoethaneiv: Zirconium tetrachloride, diethyl ether, n-butyllithiumv: Methylalumoxane, ethylene

EXPERIMENTAL

1. Preparation of (4-Butenyldiisopropylchloro)Silane

Asuspension ofmagnesium turnings (0.11mol) in 50ml of THFwas treated dropwisewith 4-bromo-1-butene (0.11mol), and the mixture was stirred for 12 hours. Thesolution was then cooled to �10�C, and CuCN (1mmol) was added followedimmediately by the dropwise addition of diisopropyldichlorosilane (0.11mol). Thereaction mixture was then gradually warmed to ambient temperature and stirred for12 hours, filtered, and concentrated; 14.5 g of product were isolated.

2. Preparation of 2-(4-Butenyldiisopropylsiloxy)Indene

Asolution of the Step 1 product (73.2mmol) and 2-indanone (73.2mmol) dissolved in30ml of benzene was added dropwise to a solution of 1,8-diazobicyclo[5.4.0]undec-7-ene (73.2mmol) in 25ml of benzene at ambient temperature, and the reactionmixture was stirred for 12 hours. The mixture was then quenched with water andextracted with diethyl ether. The ethereal solution was dried using MgSO4, concen-trated, and purified using flash chromatography with hexane; 12.9 g of product wasisolated.

3. Preparation of bis-2-(4-Butenyldiisopropylsiloxy)1-Indenyl)Ethane

To a solution of the Step 2 product (43.9mmol) dissolved in 50ml of THF was addeddropwise to n-butyllithium (22mmol; 2.5M in hexane) at�15�C, and themixturewasstirred for 2 hours at ambient temperature. It was then treated with the dropwiseaddition of 1,2-dibromoethane (22mmol) in 10ml of THF at �78�C and stirred anadditional 12 hours at ambient temperature. This solution was quenched by pouringintowater and extracted with diethyl ether. Theworkup was identical to that in Step 2,and 2.0 g of product were isolated.

4. Preparation [Ethylene-bis-2-(4-Butenyldiisopropylsiloxy)-1-Indenyl)]Zirconium Dichloride

A solution of the Step 3 product (3.2mmol) dissolved in 20ml of diethyl ether wasadded dropwise to n-butyllithium (6.4mmol; 2.5M in hexane) at �15�C, and thereactionmixturewas stirred for 2 hours at ambient temperature. Themixturewas thenconcentrated, and ZrCl4 (3.2mmol) was added to the residue. The solid was then

524 Metallocene Catalysts Containing a Cyclopentadienyl Ligand Substituted by a Siloxy

treated with 30ml of cold CH2Cl2, and the suspension was stirred at �80�C for15 minutes before being slowly warmed to ambient temperature and stirred anadditional 12 hours. The suspension was filtered through celite and concentrated,and the product was isolated in 44% yield after re-crystallization in hexane at�78�C.

5. Preparation of Polyethylene

Methylalumoxane (3.32 g) and the Step 4 product (38.2 mmol) were thoroughlymixed and placed in a burette. A stirred 1-liter Buchi autoclave reactor was chargedwith 150ml of toluene andmethylalumoxane, and the Step 4 productmixture added;the aluminium/zirconium ratio was 300. The reaction was conducted under anethylene pressure of 0.3 bar at 20�C for 2 hours. The reactor was then purged withnitrogen to remove ethylene, and the reactor temperature was raised to 80�C.Thereafter 2.85 bar of ethylene pressure was applied, and the polymerization wasconducted for 30 minutes while maintaining the ethylene pressure and temperatureat this level. The ethylene consumption was 0.7082mol, and the product wasisolated having a MP¼ 127�C.

DERIVATIVES

One derivative, (I), was prepared.

Si

Si

(H3C)2Si

ZrCl2

(I)

NOTES

1. Metallocene catalysts of the current invention containing siloxy or germyloxygroup in the 4-, 5-, 6- or 7-indene position, (II), were prepared byEkhom [1] andused in preparing HDPE, LDPE, and LLDPE.

Notes 525

OSi(CH3)2-t-C4H9

t-C4H9-(H3C)2SiO

(II)

(H3C)2Si

ZrCl2

2. Other pre-catalysts have been prepared that are effective in polymerizingethylene and a-olefins to high molecular weights with low crystallinity. Kucha[2] prepared phenoxy/amine derivatives of hafnium, titanium, and zirconium,(III), while Kol [3] and Shih [4] prepared ultra-high activity, (IV) and (V),respectively, pre-catalysts useful in polymerizing a-olefins having very highmolecular weights and low polydispersities.

N

NMOC6H5

t-C4H9

(III)

M = Hf, Ti, ZrN

OZrOt-C4H9

t-C4H9

t-C4H9

t-C4H9

N

(IV)

N

N NFe

ClCl

(V)

526 Metallocene Catalysts Containing a Cyclopentadienyl Ligand Substituted by a Siloxy

3. Metallocene derivatives containing azulenyl rings, (VI), were prepared byIwama [5] and used to polymerized propylene.

Cl

Cl Si(CH3)3

Cl

Cl

(H3C)3Si

Si(CH3)2Cl2Hf

(VI)

4. Monocyclopentadienyl metallocene catalysts, (VII), not requiring methylalu-moxane as a co-catalyst were prepared by Canich [6] and used to prepareethylene/a-olefin copolymers.

(H3C)2SiZr

t-C4H9

B(pfp)4

(VII)

References

1. P. Ekhom et al., US Patent Application 2004-052882 (August 5, 2004)2. M.C. Kuchta et al., US Patent 7,045,583 (May 16, 2006)3. M. Kol et al., US Patent 6,596,827 (July 22, 2003)4. K.-Y. Shih, US Patent 6,943,224 (September 13, 2005)5. N. Iwama et al., US Patent 7,189,790 (March 13, 2007)6. J.A.M. Canich et al., US Patent 7,163,907 (January 16, 2007)

Notes 527

J. Ring-Opening Metathesis Catalyst

Title: Photochromic Polymers and Methodsof Synthesizing Same

Author: N. R. Branda et al., US Patent 7,041,763 (May 9, 2006)Assignee: Simon Fraser University (Burnaby, CA)

SIGNIFICANCE

There are a limited number of photochromic polymers as a result of the relativelyharsh methods used to prepare them. A mild method for preparing these materialsusing ring-opening metathesis polymerization at ambient temperature is described.

528

REACTION

OO

O

O

H

H

NO

O

O

H

H

OH

S SCl Cl S SCl CO2H

S SClN O

O

O

H

H

O

O

S SClN

O

O

H

H

O

O

Intermediate

Intermediate

i

ii iii

iv

H

a

i: 4-Aminophenol, glacial acetic acidii: THF, t-butyllithium, carbon dioxideiii: DMF, CH2Cl2, oxalyl chloride, triethylamine, acetoneiv: CH2Cl2, bis(tricyclohexylphosphine)benzylidine ruthenium(IV)dichloride, ethyl-

vinyl ether

EXPERIMENTAL

1. Preparation of exo-N-(p-Hydroxyphenyl)-3,6-Epoxy-4-Cyclohexene-1,2-Dicarboximide

A mixture consisting of 7-oxa-bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic anhydride(12mmol) and 4-aminophenol (12mmol) were refluxed for 10 minutes in 3ml ofglacial acetic acid after which time a precipitate formed. The reaction mixture wascooled to ambient temperature and the precipitate isolated by filtration. The solid waswashed with water and dried, and the product was isolated in 68% yield as a whitesolid.

Experimental 529

2. Preparation of Acid 1-(2-Methyl-5-Chloro-Thiophen-3-yl)-2-(2-Methyl-5-Hydroxycarboxy-Thiophen-3-yl)Cyclopentene

A solution of 1,2-bis(2-methyl-5-chloro-thiophen-3-yl)cyclopentene (1.17mmol) in50ml ofTHFwas cooled to�78�Cand treatedwith t-butyllithium (1.17mmol); itwasthen stirred for 15 minutes and excess CO2 was bubbled through the solution.Thereafter the reaction mixture was warmed to ambient temperature, quenched withdilute hydrochloric acid, and extracted3 timeswith 50ml of diethyl ether. The etherealsolution was dried, concentrated, purified by column chromatography using silicawith 5% CH3OH/CH2Cl2, and the product was isolated in 80% yield as a pale yellowsolid.

3. Preparation of Acid 1-(2-Methyl-5-Chloro-Thiophen-3-yl)-2-(2-Methyl-5-Hydroxycarboxy-Thiophen-3-yl)Cyclopentyl-3,6-Epoxy-4-Cyclohexene-1,2-Dicarboximide exo-N-(4-Phenylate)

A stirred solution of the Step 2 product (0.4mmol) and 5 drops of DMF in 4ml ofCH2Cl2 at 0

�Cwere treated with the dropwise addition of oxalyl chloride (2.0mmol),dissolved in 6ml CH2Cl2, and then stirred at ambient temperature for 2 hours. Themixture was concentrated and the residue dissolved in 10ml of CH2Cl2; it was thenadded dropwise to a solution of the Step 1 product (0.6mmol) and 0.5ml oftriethylamine dissolved in acetone and cooled to 0�C. The mixture was stirredovernight, concentrated, purified by column chromatography using silica with 2%CH3OH/CHCl3, and the product was isolated in 82% yield as a pale yellow solid.

4. Polymerization Reaction

A0.1M solution of the Step 3 product dissolved in CH2Cl2was charged into a Schlenktube followed by a CH2Cl2 solution of bis(tricyclohexylphosphine)benzylidineruthenium(IV)dichloride (0.04 eq). The solution was then stirred for 14 hours atambient temperature. Excess ethylvinyl ether was added, and the solution was stirredwhile exposed to the atmosphere for 30 minutes. Thereafter the polymer wasprecipitated into cold diethyl ether, and the product was isolated in 75% yield.

1H NMR (CDCl3) d 7.67 (s, 1H), 7.31 (m, 4H), 6.56 (s, 3H), 5.38 (m, 2H), 3.00 (s, 2H), 2.76 (m, 4H), 2.05(m, 5H), 1.87 (s, 3H)

13C NMR (CDCl3) d 175.22, 159.95, 150.56, 144.60, 137.19, 136.78, 136.02, 135.33, 134.75, 134.14,133.36, 129.16, 128.03, 127.62, 126.66, 125.59, 122.38, 81.51, 47.59, 38.61, 38.52, 22.89,14.98, 14.30

ESMS(+ive): 600.0 (M+Na+), 532 (M�Cl)

1H NMR (d6-DMSO) d 9.71 (s, 1H), 6.95 (d, J¼ 8.75Hz, 2H), 6.83 (d, J¼ 8.75Hz, 2H), 6.58 (s, 2H), 5.21(s, 2H), 3.02 (s, 2H)

13C NMR (d6-DMSO) d 175.95, 157.27, 136.53, 127.98, 123.19, 115.38, 80.66, 47.20; EIMS (m/z): 257FTIR (cm�1) 3334 (s, broad), 3143, 3102, 3076, 3049, 3029, 2973, 1697, 1612, 1594

1H NMR (CDCl3) d 7.55 (s, 1H), 6.52 (s, 1H), 2.72 (m, 4H), 1.99 (m, 5H), 1.80 (s, 3H)

530 Photochromic Polymers and Methods of Synthesizing Same

DERIVATIVES

Two additional derivatives were prepared as illustrated below.

a

a

N

O

O

H

H

OS S

N

O

O

H

H

O

O

S SClN

O

O

H

H

O

O

O

H

a

F6

O

HH

NOTES

1. In an earlier investigation by Kim [1] benzothiophene derivatives, (I), wereprepared and used as components in photochromic polymers.

S S

O

O

OO

(I)

FTIR (KBr-cast; cm�1) 3050 (w), 2951 (w), 2843 (w), 1713 (s), 1202 (s).1HNMR (CDCl3) d 7.6 (br s), 7.3 (br s), 6.6 (br s), 6.1 (br s), 5.8 (m), 5.2 (m), 4.6 (m), 3.4 (br s), 2.7 (br s), 2.0

(m), 1.8 (br s)

Notes 531

2. Photochromic polymers, (II), prepared by Kim [2] had a fluorescencequantum yield of 53% at 290 nm as well as excellent solubility in organicsolvents and were used in information processing devices. Tanaka [3]prepared the nonpolymeric analogue, (III), of this agent, which was used inirradiation detectors.

aS S

F6

(II)S S

F6

t-C4H9t-C4H9

(III)

3. Photochromic [1,2-b] naphthopyran derivatives, (IV), prepared by Hughes [4]exhibited absorption in the 400-550 nm (brown) range and were used in graftcopolymer reactions.

H3CO

X

F

H3CO

X = CH2OH; COOCH3

(IV)

N

References

1. E.-K. Kim et al., US Patent 6,479,604 (November 12, 2002)2. E. Kim et al., US Patent 7,135,132 (November 14, 2006)3. Y. Tanaka et al., US Patent 7,101,497 (September 5, 2006)4. F.J. Hughes et al., US Patent 6,863,843 (March 8, 2005)

532 Photochromic Polymers and Methods of Synthesizing Same

Title: Synthesis of A,B-Alternating Copolymersby Olefin Metathesis Reactions of Cyclic Olefinsor Olefinic Polymers with an Acyclic Diene

Author: T.-L. Choi et al., US Patent 6,987,154 (January 17, 2006)Assignee: California Institute of Technology (Pasadena, CA)

SIGNIFICANCE

Ring-opening metathesis polymerization, ROMP, using a cyclic and acyclic olefinmonomerwas used to prepare co-polymerswithmonomer alternation exceeding95%.Monomer-to-ruthenium catalyst studies were also performed to minimize polydis-persities and maximize molecular weights.

REACTION

O Oi

a4Note 1

i: CH2Cl2, 1,4-butanediol diacrylate, 1,3-dimesityl-4,5-dihydroimidazol-2-ylidene)benzylidene-tricyclopentylphosphine ruthenium(II) dichloride, methanol

EXPERIMENTAL

A small flask was charged with 1,4-butanediol diacrylate (0.45mmol) dissolved in2ml of CH2Cl2 then treated with 1,3-dimesityl-4,5-dihydroimidazol-2-ylidene)ben-zylidene-tricyclopentyl-phosphine ruthenium(II) dichloride (2.7mg) and cyclooctene(0.45mmol), the total monomer-to-catalyst ratio being 290:1. The mixture was

533

degassed and the flask refluxed for 6 hours under argon. The reaction contents wereprecipitated in50mlofmethanol, andawhitepolymerwas isolated.Thecrudepolymerwaswashed several timeswithmethanol anddried, and theproductwas isolated in 84%yield with 99% alternation.

DERIVATIVES

TABLE 1. Ring-opening metathesis polymerization cyclic and acyclic monomers inpreparing copolymers using catalyst 1,3-dimesityl-4,5-dihydroimidazol-2-ylidene)benzylidene-tricyclopentylphosphine ruthenium(II) dichloride.

Entry Monomer 1 Monomer 2

Monomer-CatalystRatio

PolymerYield (%)

MonomerAlternation

(%)

Mn

(1� 103

daltons)(PDI)

1A OO

O

O

100 87 95 90.0(1.73)

1B

NHHN

O

O

— 99 97 9.7(1.45)

2 Same 125 75 96 20.3(1.58)

3 Same 125 93 97 14.1(1.80)

MW (GPC)¼ 90,100 daltons1H-NMR (300MHz, CDCl3): d¼ 6.93 (dt, J¼ 7.2, 15.9Hz, 1H), 577 (d,J¼ 15.9Hz, 1H), 4.13 (br s, 2H),

2.12 (m, 2H), 1.73 (m, 2H), 1.43 (m, 2H), 1.30 ppm (m, 2H)13C-NMR (75MHz, CDCl3): d¼ 166.8, 149.6, 121.3, 64.0, 32.5, 29.3, 28.2, 25.8 ppm

(continued)

534 Synthesis of A,B-Alternating Copolymers by Olefin Metathesis Reactions of Cyclic Olefins

NOTES

1. The ROMP catalyst of the current invention, (I), is illustrated below.

N N

RuClCl

(C5H9)3P

(I)

2. In subsequent investigations by the author [1] the catalyst of the currentinvention was used to prepare macrocycles, (II). Morgan [2] observed a similareffect using 1, 5-cyclooctadienes, which underwent a ring-opening cross-metathesis reaction forming linear compounds, (III), without polymerizing asillustrated in the second equation.

TABLE 1. (Continued )

Entry Monomer 1 Monomer 2

Monomer-CatalystRatio

PolymerYield (%)

MonomerAlternation

(%)

Mn

(1� 103

daltons)(PDI)

5 Same

(n-C4H9)3SiO

250 69 94.5 21.4(1.43)

7

OO

OO

100 98 97 25.2(2.06)

Note: 1H- and 13C-NMR product characterization provided by the author.

Notes 535

O O

O

OR

RR+

a b

i a, b = 4 - 12 c = 1 - 7

c

(II)

+ iOCH3

O

OO

OCH3

OCH3

(III)

i: CH2Cl2, 1,3-dimesityl-4,5-dihydroimidazol-2-ylidene)benzylidene-tricyclo-pentylphosphine ruthenium(II) dichloride

3. Using the ROMP catalyst bis(tricyclopentylphosphine)dichloro-(3-methyl-2-butenylidene)-ruthenium, (IV), Piccinelli [3] prepared lowmolecular weightpolynorbornene derivatives functionalized with hydrophilic polyethers, (V),which were subsequently hydrogenated, (VI), as illustrated in the secondequation.

RuCl

P(C5H9)3

P(C5H9)3

Cl

(IV)

OOCH3 O

OCH3

OOCH3

(V)

(VI)

aa

ab

bi ii

a = 3, 7b = 5–15

4. Liaw [4] synthesized norbornene monomers containing crosslinkable sidechains (VII), which underwent a ROMP reaction with a ruthenium-based


catalyst, (VIII), forming polynorbornene, (IX), or forming a polymethacrylatederivative, (X) by free radical polymerization as illustrated below.

O

NHO

OO

a

(X)

RuCl

P(C6H11)3

P(C6H11)3

Cl

C6H5

(VIII)O N

H

O

O

O(VII)

O

HNO

OO

a

(IX)

5. Mather [5] prepared elastomeric materials having excellent shape recoveryproperties by polymerizing cyclooctene using the dihydroimidazolylidene-modified Grubbs catalyst, (I), and then crosslinking the intermediate withdicumyl peroxide.

Notes 537

References

1. T.-L. Choi et al., US Patent 7,034,096 (April 25, 2005) and US Patent Application 2003-0236367(December 25, 2003)

2. J.P. Morgan, US Patent 6,803,429 (October 12, 2004)3. P. Piccinelli et al., US Patent 7,160,969 (January 9, 2007)4. D.-J. Liaw et al., US Patent 7,132,565 (November 7, 2006)5. P.T. Mather et al., US Patent 7,173,096 (February 6, 2006)


K. Ziegler–Natta

Title: High 1,4-cis Polybutadiene-PolyurethaneCopolymer and Preparation Method Thereof

Author: G. H. Kwag et al., US Patent 7,247,695 (July 24, 2007)Assignee: Korea Kumho Petrochemical Co., Ltd. (Chongno-gu, Seoul, KR)

SIGNIFICANCE

1,3-Butadiene has been converted into poly-1,4-(cis-butadiene) in greater than 98.3%by Ziegler–Natta catalysis comprising neodymium versatate, diethyl aluminumchloride, diisobutylaluminum hydride, and triisobutylaluminum. The polymer wasthen converted into a polybutadiene-polyurethane copolymer by reacting with adiisocyanate and diol. This copolymer exhibited low cold flow and high affinity forsilica or carbon black, excellent elasticity, and abrasion resistance.

REACTION

HN O

O NH

O

O

HN

Oi a b e

Note 1

c d

i: Neodymium versatate, diethylaluminum chloride, diisobutylaluminum hydride,triisobutylaluminum, polymethylene diphenyl diisocyanate, ethylene glycol

EXPERIMENTAL

Preparation of Poly-1,4-(cis-Butadiene-co-Urethane)

The Ziegler–Natta catalyst used for the reaction consisted of 1.0% neodymiumversatate dissolved in cyclohexane solution, 1M of diethylaluminum chloride

539

dissolved in cyclohexane solution, 15% diisobutylaluminum hydride in hexanesolution, and 1M of triisobutylaluminum dissolved in heptane solution in a molarratio of 1/25/4/2.5, respectively. Approximately 1.0� 10�4mol of the neodymiumcatalyst mixture was used per 100 g of 1,3-butadiene. A reactor was charged with theZiegler–Natta catalyst mixture and then treated with butadiene (400 g) and polymer-ized at 70�C for 1 hour. This mixture was next treated with polymethylene diphenyldiisocyanate (0.3 phr) and ethylene glycol (0.6 phr) and stirred for 1 hour. Finally, 2,6-di-t-butyl-p-cresol and ethanol were added to terminate the reaction, and the productwas isolated.

REACTION SCOPING

NOTES

1. Jang [1] prepared high cis-1,4-polybutadiene having controlled cold flowwithout causing a significant increase in the Mooney viscosity using theZiegler–Natta catalyst of the current invention. In an earlier investigation by

TABLE 1. Reaction stoichometry used in preparing poly-1,4-(cis-butadiene-co-urethane) at 70�C.

EntryNd Catalyst(�10�4mol)

Molar Ratio ofNd:TIBA:

DIBAL:DIEC*1Added

Isocyanate (phr)*2Added

Alcohol (phr)

1 1.0 1:25:4:2.5 0.3 0.34 1.2 1:20:7:2 0.3 1.27 1.5 1:30:5:3 0.3 0.69 1.5 1:30:5:3 10.0 4.0

*1Neodymium versatate, triisobutylaluminum, diisobutylaluminum hydride, diethylaluminum chloride,respectively*2Parts by weight of resin

TABLE 2. Physical properties of 1,4-cis-poly(polybutadiene-co-urethane) preparedat 70�C using the stoichometry described in Table 1.

EntryPolyisobutylenecis Content (%) Mw (daltons) PDI

UrethaneCopolymer Mw

(daltons) PDI

1 98.7 851,300 2.70 872,500 2.894 98.4 613,500 2.86 664,800 3.807 98.3 583,600 2.64 620,600 2.849 98.3 573,200 2.55 823,700 3.25

540 High 1,4-cis Polybutadiene-Polyurethane Copolymer and Preparation Method Thereof

Jang [2] a Ziegler–Natta catalyst consisting of nickel naphthenate, borontrifluoride dibutylether, and triethylaluminum was used to control 1,2-branch-ing in 1,4-butadiene polymerization.

2. Polybutadiene-co-urea-, (Ia), and co-polyurethane, (Ib), polymers were pre-pared by Wu [3] and Cavallaro [4], respectively, and used as a component inhigh-performance golf balls.

X NH

O

NH

O

a b c ed

(I)

Ia X = NHIb X = O

3. Wu [5] prepared co-urea polyisoprene copolymers consisting of polyisopre-nediamines with 4-methylene-bis(cyclohexyl isocyanate).

References

1. Y.C. Jang et al., US Patent 6,908,975 (June 21, 2005) and US Patent 6,562,917 (May 13, 2003)2. Y.C. Jang et al., US Patent 6,586,542 (July 1, 2003)3. S. Wu et al., US Patent 7,217,764 (May 15, 2007) and US Patent 7,214,738 (May 8, 2007)4. C. Cavallaro et al., US Patent 7,226,368 (June 5, 2007)5. S. Wu et al., US Patent 7,253,242 (August 7, 2007)

Notes 541

Title: Process for Producing Polymer

Author: T. Arai et al., US Patent 7,214,745 (May 8, 2007)Assignee: Denki Kagaku Kogyo Kabushiki Kaisha (Tokyo, JP)

SIGNIFICANCE

rac-Phenylboranediylbis{1-(2-methyl-cyclopenta[1]phenanthryl)}-zirconiumdichloride has been found effective as a high-activity ethylene polymerizationcatalyst when used with triisobutylaluminum co-catalyst in a reduced amount.

REACTION

B BCl2Zr

iii

Note 1

i: Diethyl ether, dichlorophenyl borane, n-butyllithiumii: Toluene, tetrakis(dimethylamino)zirconium, trimethylsilyl chloride

EXPERIMENTAL

1. Preparation of bis(1-(2-Methyl-Cyclopenta[1]Phenanthryl))Phenylborane

Under an argon stream, 50ml of a diethyl ether solution of 1H-(2-methyl-cyclopenta[1]-phenanthrene) (21.7mmol)was cooled to0�Cand then treatedwithn-butyllithiumin hexane solution (21.7mmol) and stirred at ambient temperature for 3 hours. Thissolution was added dropwise to 50ml of a diethyl ether solution of dichlorophenyl

542

borane (10.8mmol) cooled to�75�C and stirred overnight while gradually returningto ambient temperature. Thereafter the mixture was concentrated, and the crudeproduct was isolated in quantitative yield.

2. Preparation of rac-Phenylboranediylbis{1-(2-Methyl-Cyclopenta[1]Phenanthryl)}-Zirconium Dichloride

In an argon atmosphere 40ml of toluene containing the Step 1 product (5.65mmol)was added to a 40ml of the toluene solution containing tetrakis(dimethylamino)zirconium (5.77mmol) and then refluxed for 4 hours. The mixture was concentratedand treated with 80ml of toluene containing trimethylsilyl chloride (92.3mmol) andstirred overnight. The mixture was re-concentrated, and the residue was washed withpentane and extracted with CH2Cl2. The extract was then concentrated, and precipi-tated crystals were collected by filtration. Crystalswerewashedwith diethyl ether anddried under reduced pressure at from 70�C to 120�C. The crystals were re-extractedwith methylene chloride, the solution concentrated, and 0.2 g of a clear yellow solidproduct was isolated.


A10-liter reactorwaschargedwith4.8 liter of toluene, heated to70�C, and treatedwithtriisobutylaluminum (8.4mmol). The temperature was then increased to 90�C, andethylene was introduced. After the pressure was stabilized at 1.1MPa, 50ml of atoluene solution containing the Step 2 product (0.3mmol) and triisobutylaluminum(0.84mmol) were added. The polymerization duration was 5 minutes. Thereafter thereaction was quenched with methanol, and 215 g of product were isolated.

DERIVATIVES

Two additional derivatives were prepared by the author as illustrated below.

NB

R

RCl2Zr i-C3H7

i-C3H7

R = H, CH3

1HNMR (CDCl3) d 1.71 ppm (methyl group s, 6H), 7.26 (d, 2H), 7.12 8.79 ppm (21H)

Derivatives 543

CATALYST REACTIVITY PROFILE

A summary of the 5-minute catalyst scoping polymerization reactions conductedat 90�C using ethylene and triisobutylaluminum is provided in Table 1.

B

R1R1

Zr

R2

Cl Cl

TABLE 1. Catalyst scoping at 90�C with 1.1 MPa ethylene in toluene usingtriisobutylaluminum as co-catalyst for 5-minute polymerization reactions.

Entry R1 R2

Catalyst Amount(mmol)

Polyethylene(g)

Catalyst Activity(g/mol-Zr � h)/106

1 H Phenyl 0.3 215 8,6002 CH3 Di-isopropylamino 1.0 214 2,5683 H Di-isopropylamino 2.1 222 1,269

NOTES

1. rac-Diisopropylaminoboranediylbis(4,5-benz-1-indenyl)zirconium dichlor-ide, (I), was previously prepared by the author [1] using methyl aluminoxaneas a co-catalyst and used to prepare poly(ethylene-co-styrene). Underanalogous reaction conditions, the author [2] terpolymerized ethylene,styrene, and divinylbenzene using rac-dimethylmethylenebis(4,5-benzo-1-indenyl)zirconium dichloride, (II).

NBCl2Zr i-C3H7

i-C3H7

(I)

Cl2Zr

(II)

544 Process for Producing Polymer

2. Fluoroaluminoxane-containing co-catalysts, (III), prepared by Sangokoya [3]were equivalent to or better than nonhalogenated MAO compositions.

AlO O

F

(III)

3. Solid-state hydroxyisobutylaluminoxane co-catalysts prepared byWu [4] wereas effective in activating metallocenes in olefin polymerization as the corre-sponding alkyl aluminoxanes but at a lower aluminum/metal ratio.

References

1. T. Arai et al., US Patent 6,891,004 (May 10, 2005)2. T. Arai et al., US Patent 6,878,779 (April 12, 2005) and US Patent 6,803,422 (October 12, 2004)3. S.A. Sangokoya et al., US Patent 7,193,100 (March 20, 2007)4. F.-J. Wu et al., US Patent 6,812,182 (November 2, 2004)

Notes 545

Title: Polymerization Catalyst Composition

Author: S.W.-Y. Chow et al., US Patent 7,176,158 (February 13, 2007)Assignee: ExxonMobil Chemical Patents, Inc. (Houston, TX)

SIGNIFICANCE

A high-activity ethylene polymerization catalyst [bis(4-allyl-2,6-diisopropylpheny-limino)acenaphtheno]nickel(II) dibromide has been prepared.When used in conjunc-tion with methylalumoxanes, high polymers were produced.

REACTION

OONN

NNNi

BrBr

i ii

aiii

i: 4-Allyl-2,6-diisopropylaniline, acetic acidii: Nickel bromide ethylene glycol dimethyl ether, CH2Cl2iii: Ethylene, toluene, methyl alumoxane

546

EXPERIMENTAL

1. Preparation of bis(4-Allyl-2,6-Diisopropylphenylimino)Acenaphthene

A mixture consisting of acenaphthoquinone (5.5mmol) and 4-allyl-2,6-diisopropy-laniline (11.1mmol) dissolved in 10ml of acetic acid was refluxed one hour and thencooled to ambient temperature and filtered. The solid was washed with 5ml of aceticacid, four timeswith 10ml of hexane, and dried; the productwas isolated in 82%yield.

2. Preparation of [bis(4-Allyl-2,6-Diisopropylphenylimino)Acenaphtheno]Nickel(II)Dibromide

Nickel bromide ethylene glycol dimethyl ether (0.25mmol) and the Step 1 product(0.32mmol) were combined in a Schlenk flask under an argon atmosphere and 20mlof CH2Cl2 added. The mixture was stirred 24 hours at ambient temperature and thenconcentrated. The residue was washed three times with 10ml of diethyl ether anddried; the product was isolated as a dark-red powder in 85% yield.


The Step 2 product was added to a flame-dried Schlenk flask with a stirrer and thenbackfilled three times with ethylene and 50ml of toluene added. Stirring was begun,and methyl alumoxane dissolved in heptane added by syringe. After 30 minutes thereaction was quenched with acidified ethanol, filtered, dried in vacuum at 40�C for 10hours, and the product was isolated.

REACTION SCOPING

Elemental analysisCalcd for C42H48Br2N2Ni: C, 63.11H, 6.05; N, 3.50. Found: C, 63.45; H, 5.60; N, 3.37

1H-NMR (400MHz, CDCl3): d 7.86 (d, 2H, H.sub.o-Ace-C.dbd.N), 7.37 (t, 2H, H.sub.m-Ace-C.dbd.N),7.07 (s, 4H, H–Ar–N.dbd.C), 6.65 (d, 2H, H.sub.p-Ace-C.dbd.N), 6.15 (m, 2H, CH.dbd.C), 5.15(m, 4H,C.dbd.C–H), 3.50 (d, 4H,CH2–C.dbd.C), 3.00 (m, 4H,CH(Me)2),1.22 (d,12H,C(CH3)2),0.96 (d, 12H, C(CH3)2

Elemental Analysis Calcd for C42H48N2: C, 86.86; H, 8.32; N, 4.82. Found: C, 87.75; H, 7.35; N, 4.82

TABLE 1. Ethylene polymerization results using the Step 2 product with an Al/Niratio of 2500.

Entry T (�C)Catalyst Activity

(�106 g PEmol�1Ni h�1)PolyethyleneMn (daltons)

PolyethyleneMw (daltons) PDI

1 25 2.67 110,832 195,796 1.7672 0 3.32 193,660 478,735 2.4723 �15 2.83 221,695 504,193 2.274

Note: All polymerization reactions had a duration of 30 minutes in 50ml of toluene with an ethylenepressure of 0.1MPa.

Reaction Scoping 547

NOTES

1. Phenol imine derivatives, (I), prepared by the author [1] in an earlierinvestigation were used to polymerize styrene when activated with 2,20-azobis(2-methylpropanenitrile).

O NNi

(C6H5)3P

i-C3H7

i-C3H7

(I)

2. Nickel-based azo-phenoxides, (II), prepared by Hinkle [2] and iron-basedpyridinyl diimines, (III), prepared by Razavi [3] were used to synthesize highmolecular weight ethylene and ethylene/1-hexene copolymers, respectively,when activated with methylalumoxane.

N

NNi

O

(C6H5)3Pi-C3H7

i-C3H7

(II)

N

NN

t-C4H9

t-C4H9

Fe

ClCl

(III)

3. a-Diimine transition metal catalysts, (IV), prepared by Zhao [4] and catecho-late derivatives, (V), prepared by Cherkasov [5] were effective as ethyleneoligomerizing agents when activated with methylalumoxane.

548 Polymerization Catalyst Composition

NN

M

n-C4H9n-C4H9

(IV)X X

M XNi BrPd Cl

NiNi

N

O

O

(V)

References

1. S.W.-Y. Chow et al., US Patent 7,119,155 (October 10, 2006)2. P.V. Hinkle et al., US Patent 7,094,848 (August 22, 2006)3. A. Razavi et al., US Patent 7,176,950 (February 13, 2007)4. B. Zhao et al., US Patent 7,161,018 (January 9, 2007)5. V.K. Cherkasov et al., US Patent Application 2006-0047094 (March 2, 2006)

Notes 549

Title: Synthetic Polyisoprenes and a Process for TheirPreparation

Author: P. Laubry, US Patent 6,992,157 (January 31, 2007)Assignee: Michelin Recherche et Technique S.A. (Granges-Paccot, CH)

SIGNIFICANCE

A synthetic method for preparing polyisoprene having a cis-1,4 linkage of 99.0% orgreater using diethylaluminium chloride with the rare earth salt neodymium tris(bis(2-ethylhexyl)phosphate) is described. Reproducible Mooney viscosities of 85 andhigher were also observed.

REACTION

a

i

i: Cyclohexane, acetylacetone, N-1,3-dimethylbutyl-N0-phenyl-p-phenylenedia-mine, neodymium tris(bis(2-ethylhexyl)phosphate), diethylaluminium chloride

EXPERIMENTAL

1. Preparation of cis-1,4-Polyisoprene

A 250-ml reaction vessel was used as the polymerization reactor. Each polymeri-zation reaction was carried out either under static conditions in a freezer, where thecontainer was placed in a bath of glycol, or dynamically, by subjecting the containerto agitation in a tank of glycol. Isoprene monomer having a purity of 99.2% wasused. All polymerizations were conducted in 10-g containers and cyclohexane at�15�C with a solvent/monomer mass ratio of 9. In a typical polymerization theneodymium catalyst/diethyl aluminium chloride base varied from 150 to 500 mmolper 100 g of isoprene.

550

At the end of polymerization the mixture was treated with an additional 100ml ofcyclohexane solvent to fluidify themedium, 1ml of 1Macetylacetone in cyclohexaneadded to stop the reaction, and N-1,3-dimethylbutyl-N0-phenyl-p-phenylenediamine(0.02 g) added as an antioxidant. Polyisoprene was then extracted by steam strippingfor 30minutes in the presence of calcium tamolate. Each extraction was then dried forapproximately 18 hours in an oven at 50�C under 200 mmHg vacuum for 72 hours.Reaction scoping results are provided in Table 1.


NOTES

1. Polybutadiene and random copolymers of butadiene and isoprene both havingcis-1,4-isoprene content exceeding 95% were prepared by the author [1,2],respectively, using the catalytic composition of the current invention.

2. Polybutadiene chloride having a cis-1,4-content of not less than 90%was previously prepared by Sone [3] using methylaluminoxane, hydrogenated diisobutylaluminum, neodymium tris(bis(2-ethylhexyl)phosphate),and magnesium.

3. Low molecular weight high cis-butadiene content oligomers were prepared byMiller [4] usingmethylaluminoxane, neodymium(III) versetate, and diisobutylaluminum hydride.

References

1. P. Laubry et al., US Patent 7,169,870 (January 7, 2007) and US Patent 7,115,693 (October 3, 2006)2. P. Laubry et al., US Patent 7,056,998 (June 2, 2006)3. T. Sone et al., US Patent 6,255,416 (July 3, 2001) and US Patent 6,130,299 (October 10, 2000)4. H.J. Miller et al., US Patent 6,437,205 (August 20, 2002)

TABLE 1. Dynamic reaction scoping results for the polymerization of isoprene usinga solvent/molar ratio of 9 with the rare catalyst neodymium tris(bis(2-ethylhexyl)-phosphate) diethylaluminium chloride.

Entry

Quantity ofNeodymium

Catalyst (mmol)ReactionTime (h)

ConversionRate (%)

InherentViscosity(dl/g)

MooneyViscosity

cis-1,4-ContentUsing MIR

(%)

1 130 48 100 –– 97 ––2 300 18 100 7.6 97 99.03 700 1.5 50 –– –– ––4 700 18 100 6.0 86 99.0

Note: Entry 1 had an Mn of 930,299 daltons with a polydispersity index of 2.46.

Notes 551

Title: Polymerization Catalyst

Author: S. M. Green et al., US Patent 7,163,990 (January 16, 2007)Assignee: BP Chemicals, Ltd. (London, GB)

SIGNIFICANCE

AZiegler–Natta polymerizing procatalyst consisting of a transitionmetal and a ligandcontaining at least two nitrogen donor atoms forming a five-membered heterocyclicintermediate has been prepared. When these bisiminidato metal complexes wereactivated with trimethylaluminium, they were effective as high-activity 1-olefinpolymerization catalysts.

REACTION

NN

NH2

NN

NN

N

NN

FeCl

NN

NN

N

NN

i ii

n-C4H9

iva b

NN

NN

N

NN

Fe

ClAl(CH3)3Cl

iii

c

Cl

i: Acetic acid, diacetylpyridine, 4-amino-1,3,5-trimethylpyrazole, ethanol,petroleum ether

ii: Iron (II) chloride, THFiii: Trimethylaluminium, tolueneiv: Ethylene, 1-hexane

552

EXPERIMENTAL

1. Preparation of 2,6-Di-(1,3,5-Trimethyl-4-Pyrazolyl)EthanimidoylPyridine

A catalytic amount of glacial acetic acid was added to a solution of diacetylpyridine(1mmol) and 4-amino-1,3,5-trimethylpyrazole (4mmol) in 10ml of absolute ethanoland then refluxed 16 hours in a test tube containing a suspended Soxhlet thimble filledwith activated 3A molecular sieves. The mixture was next concentrated, and an oilyorange solid was isolated. The crudematerial was triturated with petroleum ether, andthe product was isolated as a sandy-colored solid.

2. Preparation 2,6-Di-(1,3,5-Trimethyl-4-Pyrazolyl)Ethanimidoyl PyridineIron Dichloride

Under a nitrogen atmosphere the Step 1 product (0.05mmol) was mixed with FeCl2(0.05mmol), and 2ml of THF was added. The mixture was then stirred for 1 hour atambient temperature. The reaction solventwas removed under reduced pressure, and alight green powder was isolated.

3. Preparation 2,6-Di-(1,3,5-Trimethyl-4-Pyrazolyl)Ethanimidoyl PyridineIron Chloride Chlorotrimethylaluminium

A0.5-ml aliquot (0.004mmol) ofa stirred suspensionof theStep2product and6.25mlof toluene was transferred to a Schlenk tube and treated with 0.5ml of 10%trimethylaluminium in toluene. The resulting pink solution was further diluted with20ml of toluene and used directly.

4. Preparation of Poly(Ethylene-co-1-Hexene)

A Schlenk tube was weighed before being evacuated and refilled with the Step 3product, ethylene, and 1-hexane. The gas mixture supply was regulated to 1 barpressure while being polymerizing for 1 hour. After this time a weight gain of 4.79 gwas observed, corresponding to an activity of 1198 g/mmol � hour � bar. The reactionmixture was quenched using acidified methanol, and a white solid polymer productwas isolated.

GPC Mn¼ 500 daltons, Mw¼ 1500 daltons, Mw/Mn¼ 2.913C NMR (1000C): C2H5 branches 2.2; C4H9 branches 1.4; internal olefin branches 2.0

Experimental 553

DERIVATIVES AND CATALYST ACTIVITY

NN

NN

N

NN

MCl

Al(CH3)3Cl

R R

NOTES

1. The Ziegler–Natta catalyst 2,6-diacetylpyridinebisiron(II) chlorotrimethylalu-minium, (I), and procatalyst 2,4-{[N-(2,6-dimethylphenyl)]phenylimidoyl}6-methyl pyrimidine iron dichloride, (II), were prepared by Kimberley [1] andGibson [2], respectively, and used as high-activity 1-olefin polymerizationcatalysts.

Al(CH3)3Cl

NN N

Fe

Cl

(I)

N

N

N N

Fe

Cl Cl(II)

TABLE 1. Catalyst activity for metal complexes used in the polymerizationof ethylene and ethylene/1-hexene.

Entry R Metal Support Monomer(s)Catalyst Activity

(g/mmol � hour � bar)1 H Fe None C2H4/C6H12 11982 H Fe None C2H4 11236 H Fe Silica C2H4 7867 H Co None C2H4 709 C6H5 Fe None C2H4 61410 C6H5 Fe None C2H4/C6H12 860

554 Polymerization Catalyst

2. Thorman [3] observed that when di-sec-butyldimethoxysilane, (III), cyclohex-ylmethyl-dimethoxysilane, (IV), or dicyclopentyldimethoxysilane, (V), wereused as external electron donors for titanium-based Ziegler–Natta catalystswith triethyl aluminum as the co-catalyst, catalyst activities ranged between31,000 g/g/h and 44,000 g/g/h. Representative homopolymerization results forpropene are provided in Table 2.

3. Zhao [4] prepared pro-catalysts, (VI) and (VII), consisting of a transition metaland two nitrogen donor atoms forming five-membered heterocyclic intermedi-ates. When the pro-catalysts were activated with trimethylaluminium, theywere used to prepare ethylene dimers and oligomers.

NNN NM

XX

NNN NNi

BrBr

M XNi BrPd Cl

(VI) (VII)

4. Boussie [5] prepared five-membered heterocyclic titanium pro-catalysts,(VIII), that were activated with methylaluminoxane and used to polymerizedstyrene and ethylene.

TABLE 2. Homopolymerization of propene using a titanium-based Ziegler–Natta catalyst with triethyl aluminum as co-catalyst and dialkyldimethoxysilanes as electron donors.

Silane Al/Si PolydispersityActivity(g/g/h)

III 10 7.5 31,000III 50 6.5 34,500IV 10 6.7 32,300IV 50 6.7 46,000V 10 — 48,600V 50 7.8 45,800

N

NTi

Cl

N

Cl

(VIII)

Notes 555

References

1. B.K.Kimberley et al., USPatent 7,148,304 (December 12, 2006) andUSPatent 6,657,026 (December 2,2003)

2. V.C. Gibson et al., US Patent 6,828,398 (December 7, 2004)3. J. Thorman, US Patent 7,163,905 (January 16, 2007) and US. Patent 7,078,468 (July 18, 2006)4. B. Zhao et al., US Patent 7,160,834 (January 9, 2007)5. T.R. Boussie et al., US Patent 7,157,400 (January 2, 2007)

556 Polymerization Catalyst

Title: Use of Stannylenes and Germylenesas Polymerization Catalysts for Heterocycles

Author: A. Dumitrescu et al., US Patent 7,084,237 (August 1, 2006)Assignee: Societe de Conseils de Recherches et d’Applications Scientifiques (FR)

Centre National de la Recherche Scientifique (FR)

SIGNIFICANCE

Di-[di-(trimethylsilyl)amine]stannate has been used to prepare biocompatible poly(lactide-co-glycolide) containing up to an 88% lactide composition. When the molarratio of catalyst/lactidewas 41.9:17.9, respectively, a polymerwas formedwhich had amolecular weight of 164,700 daltons having a polydispersity of 1.8. All other ratiosgenerated molecular weights less than 78,000 daltons.

REACTION

O

OO

O n 3n

iO

O

O

O

Note 1

i: Di-[di-(trimethylsilyl)amine]stannate, glycolide, mesitylene

EXPERIMENTAL

1. Preparation of Poly(Lactide-co-Glycolide)

A Schlenk tube was charged with di-[di-(trimethylsilyl)amine]stannate(0.05mmol), d,l-lactide (39.3mmol), glycolide (13.1mmol), and 15ml of mesi-tylene and then heated to 160�C for 3 hours. 1H-NMR analysis indicated that theconversion was complete and that the copolymer consisted of 75% d,l-lactide and25% glycolide. GPC analysis indicated the product had aMw of 77,500 daltons witha polydispersity of 1.67.

557

REACTION SCOPING

NOTES

1. In a subsequent investigation by the author [1] di-[di-(trimethylsilyl)amine]zinc was prepared and used to polymerize d,l-lactide.

2. Chang [2] prepared the thermosensitive biodegradable block copolymer poly[ethylene glycol-b-(lactide-co-glycolide)] end-capped with cholic acid, (I),using catalytic amounts of Snþ2 ion. The product showed improved biode-gradability when implanted into the human body with diminished overallpolymer cytotoxicity.

aO

OO

O

O

O

C12H25

O(I)

Cholic acid

b c

3. Heller [3] prepared bioerodible block copolymers using pyridinium p-toluenesulfonate consisting of ortho esters and ethylene glycol, (II), end-capped with triethylene glycol monoglycolide.

a b

C2H5 C2H5

O

O

O

C2H5

O

O O

C2H5

O O

O

O

(II)

Triethylene glycol monoglycolide

TABLE 1. Scoping reactions for preparing random poly(lactide-co-glycolide)copolymers using the experimental catalyst di-[di-(trimethylsilyl)amine]stannate.

Entryd,l-Lactide(mmol)

Glycolide(mmol)

Catalyst(mmol)

d,l-LactideComposition

(%)

GlycolideComposition

(%)Mw

(daltons) PDI

1 33.9 13.1 0.05 25 75 77,500 1.672 17.9 –– 41.9 –– –– 164,700 1.83 54.7 –– 54.7 50 50 39,000 1.74 55 55 0.36 47 53 39,400 1.55 14 –– 0.09 88 12 21,500 1.896 34 –– 0.11 50 50 33,140 1.71

558 Use of Stannylenes and Germylenes as Polymerization Catalysts for Heterocycles

4. Seo [4] prepared poly(d,l-lactide-b-e-caprolactone), (III), and poly(d,l-lactide-b-ethylene glycol) using stannous octanate. Both polymers were usedas Paclitaxel� delivery agents.

O

HN

O

O

a b

(III)

5. Hayes [5] prepared a five component biodegradable blend that was used inmeltblown containers consisting of bis(2-hydroxyethyl)-terephthalate, (IV), lacticacid, tris(2-hydroxyethyl)-trimellitate, (V), ethylene glycol, and poly(ethyleneglycol) using manganese (II) acetate tetrahydrate and antimony(III) oxide asinitiators.

O O

OO

OH

HO

O O

OO

OH

HO

O

OH

O

(IV) (V)

References

1. A. Dumitrescu et al., US Patent 7,169,729 (January 30, 2007)2. K.-Y. Chang et al., US Patent 7,179,867 (February 20, 2007)3. J. Heller et al., US Patent 7,163,694 (January 16, 2007)4. M.-H. Seo et al., US Patent 7,153,520 (December 26, 2006)5. R.A. Hayes,US Patent 7,144,972 (December 5, 2006)

Notes 559

Title: Process for Producing Polar Olefin Copolymerand Polar Olefin Copolymer Obtained Thereby

Author: Y. Inoue et al., US Patent 7,053,159 (May 30, 2006)Assignee: Mitsui Chemicals, Inc. (Tokyo, JP)

SIGNIFICANCE

Poly(ethylene-co-norbornene-2,3-dicarboxylic acid anhydride) was prepared byco-polymerizing the respective monomers with the transition metal catalyst,di(3-t-butyl-2-hydroxy-1-(N-phenylimino)benzene) titanium(IV). The polymeriza-tion was conducted at ambient temperature using methylaluminoxane as co-catalyst.After a 10 minute polymerization reaction scoping period 0.02mol% of norbornene-2,3-dicarboxylic acid anhydride was incorporated into the co-polymer.

REACTION

a b

OO O

CHO

OH

t-C4H9OH

t-C4H9

N

O

t-C4H9

NTi

Cl

Cl

i ii iii

2

a >> b

i: Ethanol, anilineii: Diethyl ether, n-butyllithium, titanium tetrachlorideiii: Ethylene, norbornene dicarboxylic acid anhydride, methylaluminoxane,

isobutanol

560

EXPERIMENTAL

1. Preparation of 3-t-Butyl-2-Hydroxyl-1-(N-Phenylimino)Benzene

A reactor was charged with 40ml of ethanol, aniline (7.62mmol), and 3-t-butylsa-licylaldehyde (7.58mmol) and then stirred 24 hours at ambient temperature andconcentrated. The residue was purified using silica gel chromatography, and theproduct was isolated in 95% yield as an orange oil.

2. Preparation of Di(3-t-Butyl-2-Hydroxy-1-(N-Phenylimino)Benzene)Titanium(IV) Dichloride

The Step 1 product (7.05mmol) was dissolved in 100ml of diethyl ether and thencooled to�78�Cand treatedwith4.78mlofn-butyllithium(1.55Minhexane solution;7.40mmol) dropwise for over 5 minutes. Themixturewas slowly returned to ambienttemperature and stirred for 4 hours. This solution was then re-cooled to �78�C andtreated with the dropwise addition of 7.05ml of titanium tetrachloride (0.5M inheptane solution; 3.53mmol) and 40ml of diethyl ether. The solution was thengradually warmed to ambient temperature, stirred for another 8 hours, and filteredthrough a glass filter. The solid was dissolved in 50ml of CH2Cl2, and insolubles wereremoved. The filtrate was concentrated and the residue re-crystallized in 10ml ofCH2Cl2 and 70ml of pentane. The product was isolated as reddish brown crystals in61% yield after filtration and drying.

3. Preparation of Poly(Ethylene-co-Norbornene Dicarboxylic AcidAnhydride)

A glass autoclave was charged with 250ml of toluene, the liquid and gas phasesaturated with norbornene-2,3-dicarboxylic acid anhydride (0.5mmol), and100 liter/h of ethylene. Methylaluminoxane (2.50mmol) and the Step 2 product(0.005mmol) were then added to initiate the polymerization. The reaction wasconducted at 25�C for 10 minutes in an ethylene gas atmosphere at atmosphericpressure and terminated using isobutanol. After the polymerization was com-pleted, the reaction product was precipitated by pouring into methanol. Hydro-chloric acid was then added, and the mixture filtered through a glass filter. Theresulting polymer was washed with methanol and dried to obtain 1.15 g of apolymer. Analytical evaluation indicated that the copolymer contained 0.02mol%of norbornene-2,3-dicarboxylic acid anhydride.

1H-NMR(CDCl3): d 1.35(s,18 H), 6.82 7.43(m,16H) 8.07(s, 2H)IR(KBr, cm�1): 1550, 1590, 1600MS 622 (Mþ)Elemental analysis: Ti, 7.7% (7.7); C, 65.8% (65.5); H, 6.0% (5.8); N, 4.5% (4.5).

1H-NMR(CDCl3): d 1.47(s, 9H), 6.88(dd,1H), 7.24 7.31(m,4H), 7.38 7.46(m,3H), 8.64(s,1H), 13.95(s,1H)IR(neat; cm�1): 1575, 1590, 1610MS: 253 (Mþ)

Experimental 561

DERIVATIVES

NOTES

1. High-activity analogues of the current invention were previously prepared bySuzuki [1] and used in the homopolymerization of ethylene as provided inTable 2.

O

t-C4H9

N

R

Ti

Cl

Cl2

TABLE 1. Imine ligand derivatives used in preparing titanium procatalysts.

Entry N-Phenylimino Ligand Derivatives Step 1 Yield (%)

3 HN

N 66

6 N HN

85

7 NOH

98

11OH

t-C4H9

NN

61

562 Process for Producing Polar Olefin Copolymer and Polar Olefin Copolymer Obtained Thereby

2. In a subsequent investigation by the author poly(ethylene-co-norbornene dicar-boxylic acid anhydride) containing 0.03mol% norbornene-2,3-dicarboxylicacid anhydride was prepared using the Step 2 vanadium analogue, (I).

O

NV

3

(I)

3. Bidentate ligands prepared byMackenzie [3,4], (II) and (III), respectively, wereeffective in preparing highly branched polyethylene.

S S

N NC6H5 C6H5

t-C4H9 t-C4H9

t-C4H9 t-C4H9

(II)

(III)

S S

N N

i-C3H7

i-C3H7 i-C3H7

i-C3H7

Pd

Cl

Ni

[B(C6F5)4]

OO

4. Moody [5,6] prepared highly branched ultra-high molecular weight polyeth-ylene using the bidentate ligard, (II). Branched oligomeric ethylene was alsoprepared using an N-pyrrolyl substituted an imino derivative, (IV).

TABLE 2. Selected high-activity Ziegler–Natta titanium catalysts used in thehomopolymerization of ethylene.

Entry RActivity (g/mmol

Ti � hour)5 Phenyl 57846 2,6-Dimethylphenyl 12047 Pentafluorophenyl 1150

Notes 563

t-C4H9

t-C4H9N NO

(IV)

Ni

(C6H5)3P P(C6H5)3

References

1. Y. Suzuki et al., US Patent 7,009,014 (March 7, 2006)2. Y. Inone et al., US Patent Application 2006-0063898 (March 23, 2006)3. P.B. Mackenzie et al., US Patent 7,056,996 (June 6, 2006)4. P.B. Mackenzie et al., US Patent Application 2005-0090630 (April 28, 2005)5. L.S. Moody et al., US Patent 6,946,532 (September 20, 2005)6. L.S. Moody et al., US Patent Application 2006-0178490 (August 10, 2006)

564 Process for Producing Polar Olefin Copolymer and Polar Olefin Copolymer Obtained Thereby

Title: Carborane Trianion-Based Catalyst

Author: Y. Zhu, US Patent 7,053,158 (May 30, 2006)Assignee: Agency for Science, Technology and Research (SG)

SIGNIFICANCE

The Ziegler–Natta catalyst trimethylammonium o-methyl-1-(2-hydroxylcyclohexyl)-carborane zirconium chloride has been prepared and affixed to a Merrifieldresin. When used as a polymerization catalyst for vinyl chloride, t-butyl acrylate,styrene, or ethylene, oligomers with molecular weights <6000 daltons wereobtained.

REACTION

HO

HO

OZr

(CH3)3NHi ii iii

OZr

ivv

Cl

Note 1

a

a

565

i: Diethyl ether, n-butyl lithium, cyclohexene oxideii: Potassium hydroxide, ethanol, trimethylamine hydrochloride, hydrochloric acidiii: Sodium hydride, zirconium tetrachloride, THFiv: THF, n-butyl lithium, Merrifield resinv: THF, vinyl chloride

EXPERIMENTAL

1. Synthesis of o-Methyl-1-(2-Hydroxylcyclohexyl)Carborane

A solution of methyl carborane (6.32mmol) dissolved in 20ml of diethyl ether wascooled to�78�Cand then treatedwith 4.20ml n-BuLi (6.72mmol; 1.6M in n-hexane)and stirred for 30minutes.Themixturewaswarmed to ambient temperature, stirred for4 hours, and treatedwith cyclohexene oxide (6.80mmol) at 0�C. It was then stirred for6 hours and quenched with 10ml of water. The organic phase was separated, and theaqueous phase extracted twice with 25ml of diethyl ether. The combined organicswere dried using MgSO4 and concentrated. The residue was re-crystallized inn-hexane, and the product was isolated in 86%yield, MP¼ 101–103�C

2. Synthesis of Trimethylammonium o-Methyl-1-(2-Hydroxylcyclohexyl)Carborane

The Step 1 product (5.85mmol) was dissolved in a solution of potassium hydroxide(32.08mmol) in40mlof 95%ethanol and then refluxed for 16hours andconcentrated.The residue was dissolved in 20ml of water and neutralized with hydrochloric acid.Next it was treated with trimethylamine hydrochloride (17.55mmol) in 7ml of water.Awhite precipitate formed which was filtered and dried, and the product was isolatedin 77% yield, MP >200�C.

3. Preparation of Trimethylammonium o-Methyl-1-(2-Hydroxylcyclohexyl)-Carborane Zirconium Chloride

The Step 2 product (4.92mmol) was dissolved in 75ml of dry THF and then cooled to0�Cand treatedwith sodiumhydride (29.52mmol; 60%dispersion inmineral oil). Themixture was next stirred at ambient temperature for 30 minutes and refluxed for 3hours.Complete removal of trimethylaminewas achievedbypassing a streamofargonover the solution and through the condenser during the final 30 minutes of refluxing.Once at ambient temperature stirring was stopped and the clear THF solution wasdecanted under argon to another vessel. This solution was then treated with ZrCl4(4.93mmol) and stirred for 72 hours at ambient temperature. Themixturewas filtered

1H-NMR (400MHz in CDCl3) d 3.40 (CH–O), 1.80 (–CH.sub.3), 0.63 2.90 (BH, CH, OH)IR (KBr pellet, cm�1), 3062(s), 2588(vs), 1447(m), 1390(m), 1229(w), 1133(m), 1094(m), 1017(s),

934(m), 722(s)

566 Carborane Trianion-Based Catalyst

and concentrated. The residue was re-crystallized in a mixture of CH2Cl2/n-pentane,1:1, and the product was isolated in 79% yield.

4. Preparation of Polystyrene-Supported Trimethylammonium o-Methyl-1-(2-Hydroxyl-Cyclohexyl)-Carborane Zirconium Chloride

The Step 3 product (4.00mmol) was dissolved in 100ml of THF and then cooled to�78�C and treated with 2.7ml of n-BuLi (4.32mmol; 1.6M in hexane). It wasstirred for 30 minutes, followed by 4 additional hours of stirring at ambienttemperature, and then concentrated. The residue was washed twice with 15mlof n-hexane, dissolved in 150ml of THF containing 1% Merrifield’s resin (2.0 g;3.94mmol Cl), and stirred at ambient temperature for two days. The mixture wasrefluxed for 4 hours and then quenchedwith 3.0 ml ofmethanol and re-concentrated.The residuewas washed twicewith 10ml of deionizedwater and twicewith 20ml ofn-hexane. The solid was dried, and 2.40 g polystyrene-supported ortho-carboranewere isolated as a pale yellow solid.

5. Preparation of Polyvinyl Chloride

The polymerization of vinyl chloride catalyzed by the Step 4 product in THF wasperformed at ambient temperature without the use of a co-catalyst. The reactionconversion was 43.8%.

DERIVATIVES


CATALYST SCOPING

1HNMR (400MHz in DMSO, ppm) d 3.10 (CH–O), 1.66 (–CH3), �0.43 1.90 (BH, CH, OH)IR (KBr pellet, cm�1), 3413(s), 2919(vs), 2851(s), 1637(m), 1457(s), 1305(s), 963(m), 423(m)

TABLE 1. Effectiveness of polystyrene-supported zirconium-ortho-carboraneas a polymerization catalyst for selected monomers.

MonomerCatalyst Activity

(kg polymer/mol catalyst � hr) Mw 1� 103 (daltons) PDI

Vinyl chloride 40 5.6 1.6t-Butyl acrylate 35 4.2 1.6Polystyrene 64 3.6 1.8Ethylene 33 2.7 1.7

1H-NMR (400MHz in DMSO, ppm) d 9.4(NH), 3.56(OH), 3.18(CH–O), 2.52(NCH3), 2.00 0.95(BH),�2.81(BH)

IR (KBr pellet, cm�1), 3524(vs), 3040(m), 2931(s), 2857(s), 2497(vs), 1477(s), 1449(s), 1388(s), 1273(m),1212(m), 1036(vs), 978(s), 860(m), 472(m)

Catalyst Scoping 567

NOTES

1. An alternative method for preparing carborane anions using n-butyl lithium orsodium hydride in dimethyl ether or diglyme is described by Frankel [1].

2. Tinker [2] prepared 1,3-, (I), and 1,3,5-triacarborane benzene derivatives thatwere useful as hydrogenation catalysts.

(I)

Rh(P(C6H5)3)3Rh(P(C6H5)3)3

References

1. A. Frankel et al., US Patent 7,161,040 (January 9, 2007) and US Patent 6,180,829 (January 30, 2001)2. N.D. Tinker et al., US Patent 6,492,570 (December 10, 2002) and US Patent 6,423,199 (January 23,

2002)

568 Carborane Trianion-Based Catalyst

Title: Catalyst for Polymerization of Norbornene

Author: J.-H. Lipian, US Patent 7,148,302 (December 12, 2006)Assignee: The Goodyear Tire and Rubber Company (Akron, OH)

SIGNIFICANCE

Norbornene and norbornenemethyl ester have been polymerized forming a polymerthat lacks backbone carbon–carbon double-bond unsaturation. The polymerizationcatalyst mixture consisted of palladium acetate, a phosphine such as tricyclohex-ylphosphine, a Lewis acid such as dimethyl zinc, and hexafluoroisopropanol.Polynorbornenes prepared in this manner typically had Mn’s> 200,000 daltonswith polydispersies less than 2, while poly(norbornene methyl ester) had Mn’s ofroughly 100,000 daltons.

REACTION

a

Notes 1,2

i

i: Palladium acetate, tricyclohexylphosphine, dimethyl zinc, hexafluoroisopropa-nol, toluene

EXPERIMENTAL

Preparation of Polynorbornene Generic Procedure

In a typical experiment a reactorwas chargedwithpalladiumacetate (8.5� 10�6mol),tricycle-hexylphosphine (8.5� 10�6mol), and norbornene (0.0213mol). The com-ponents were dissolved in 5ml of toluene and then treated with dimethyl zinc(2.5� 10�5mol) where a color change was observed. This mixture was next treated

569

with hexafluoroisopropanol (2.12� 10�4mol), and rapid polymerization occurredwith a high exotherm. The mixture was concentrated, and the product was isolated in100% yield.

POLYMERIZATION STUDIES

a

a

OH3CO

OH3CO

TABLE 1. Effect of varying the Lewis acid and hexafluoroisopropanol catalystcompositions on the polymerization of norbornene while keeping both palladiumacetate and tricyclohexylphosphine concentrations constant at 8.5� 10�6mol.

Entry Lewis AcidLewis Acid

(mol)Hexafluoroisopropanol

(mol)Conversion

(%)

1 Dimethyl zinc (2.5� 10�5) 2.12� 10�4 1002 Tri-isobutyl

aluminum(2.5� 10�5) 2.12� 10�4 100

3 None –– 2.12� 10�4 965 Dimethyl zinc (2.5� 10�5) None 011 nickel octanoate (2.5� 10�5) 1.01� 10�3 Not quantified

TABLE 2. Effect on the polymerization of norbornene methyl ester by varyingthe catalyst composition ratios of hexafluoroisopropanol and palladium acetate whilekeeping di-t-butylcyclohexylphosphine and diethyl zinc levels constant.

EntryHexafluoroisopropanol/Palladium Acetate Ratio Conversion (%) Mn (1� 103) Mw (1� 103)

53 2714:1 Trace — —55 3619:1 Trace — —56 4071:1 86 84 5458 4976:1 91 104 59.559 5881:1 96 134 78.5

Note: The monomer ratio of norbornene methyl ester-to-di-t-butylcyclohexylphosphine was 10,000:1.25,respectively.

570 Catalyst for Polymerization of Norbornene

NOTES

1. Additional catalyst compositions utilizing di-t-butyl- and di(2-norbonyl)-phosphine as the phosphine component and titanium tetrabutylrate as theLewis acid are described by the author [1] in an earlier investigation.

2. Grubbs [2] quantitatively prepared polynorborene, (I), containing 90% transunsaturation from norborene using the high yielding ring-opening metathesispolymerization catalyst, benzylidene di(triphenylphosphine)rutheniumdichloride, RuCl2(¼CH–C6H4X)(P(C6H5)3)2, (II).

(I)a

i

i: CH2Cl2, benzylidene di(triphenylphosphine)ruthenium dichloride, (II)

RuCl

ClP(C6H5)3

P(C6H5)3

XX = H N(CH3)2 OCH3 CH3 F, Cl NO2

(II)

3. Taguchi [3] polymerized the cyclopentadiene-itaconic anhydride Diels–Alderaddition product, (III), using the ring-opening metathesis polymerizationcatalyst benzylidene(1,3-dimesitylimidazolydin-2-ylidene)(tricyclohexylpho-sphine)ruthenium dichloride. The polyunsaturated intermediate, (IV), wasthen hydrogenated using bis(tricyclohexylphosphine)benzylidenerutheniumdichloride obtaining the polynorborene diacid derivative, (V), having a Mw

of roughly 18,000 daltons.

aaaO

O

i ii

(III) (V)

aa

O

O

O CO2H

CO2H

O

(IV)

Notes 571

i: THF, benzylidene(1,3-dimesitylimidazolydin-2-ylidene)(tricyclohexyl-phosphine)ruthenium dichloride

ii: Bis(tricyclohexylphosphine)benzylideneruthenium dichloride, hydrogen,ethyl vinyl ether, toluene

4. Weck [4] prepared photoluminescent polynorborene derivatives, (VII), bypolymerizing aluminum-8-hydroxyquinoline-functionalized norborene, (VI),using benzylidene (1,3-dimesitylimidazolydin-2-ylidene)-(tricyclohexylpho-sphine)ruthenium dichloride.

HN

NO

Al

O

O

NN

HN

NO

Al

O

O

NN

66

(VI) (VII)

i

a

i: Benzylidene (1,3-dimesitylimidazolydin-2-ylidene)-(tricyclohexylphosphine)ruthenium dichloride.

5. Milne [5] prepared polypyrrolidine, (VIII), by the cyclopolymerization of 1,10-(di-N,N-diallyl)decane by UV or thermal radiation.

NH NHHN NH

1010

(VIII)

572 Catalyst for Polymerization of Norbornene

References

1. J.-H. Lipian, US Patent 7,122,611 (October 17, 2006)2. R.H. Grubbs et al., US Patent 7,102,047 (September 5, 2006)3. K. Taguchi et al., US Patent 7,037,993 (May 2, 2006)4. M. Weck et al., US Patent 7,105,617 (September 12, 2006)5. P.E. Milne et al., US Patent 6,608,120 (August 19, 2003)

Notes 573

XX. REGULATORS

A. Chain Transfer Agents

a. Poly(2-Hydroxyethyl Methacrylate)

Title: Method for the Production of Homo-, Co-,and Block Copolymers

Author: I. Stefan et al., US Patent 7,199,200 (April 3, 2007)Assignee: Construction Research and Technology GmbH (Trostberg, DE)

SIGNIFICANCE

A method for preparing polymers in a narrow molecular weight distribution bycontrolled radical polymerization in an aqueous solution using b-cyclodextrin as themacroinitiator intermediate and 1,1-diphenylethylene as the regulator is described.Since thismethod requires considerably lower amounts of both initiator and regulator,polymers contain limited amounts of regulator and initiator decomposition products.

REACTION

O

O

OH

O O

OH

ai

i: Water, hydroxypropylated b-cyclodextrin, 1,1-diphenylethylene, ammoniumperoxodisulfate


575

EXPERIMENTAL

Preparation of Poly(2-Hydroxyethyl Methacrylate)

An aqueous solution of 17.68ml of water and hydroxypropylated b-cyclodextrin(1.6mmol) was treated with 1,1-diphenylethylene (1.6mmol). This solution wasthen treated with 150 g of water and 2-hydroxyethyl methacrylate (538mmol),heated to 85�C, and further treated with the dropwise addition of ammoniumperoxodisulfate (4.8mmol) dissolved in 10 g of water. The solution temperaturewas next raised to 90�C, and the mixture was reacted for 5 hours. A clear orangesolid was obtained having a Mw of 5200 daltons with a polydispersity of 1.21.

DERIVATIVES

NOTES

1. Rogers [1] and Blokzijl [2] used substituted polysaccharides as macroinitiatorintermediates for the preparation of polysaccharide graft polymers and in thepreparation of macroinitiators. The polysaccharide graft polymers were de-signed to impart soil release and/or fabric care benefits to laundry detergent orfabric treatment compositions.

2. A controlled free radical polymerization process used by White [3] entailedpreparing the monofunctional iniferter 2,3-dicyano-2,3-dimethyl butane bythermally decomposing azobisiso-butyronitrile and then heating the inifertersufficiently to form two carbon centered radical residues. In this mannerpolymers were prepared having moderate molecular weights but narrowpolydispersities.

References

1. S.H. Rogers et al., US Patent 7,041,730 (May 9, 2006)2. W. Blokzijl et al., US Patent 7,153,821 (December 26, 2006)3. D. White et al., US Patent 6,875,832 (April 5, 2005)

TABLE 1. Effect of varying reaction components and treatment levels on themolecular weight and polydispersities of selected polymers.

Entryb-Cyclodextrin

(mmol)Regulator(mmol)

Monomer(g)

Initiator(mmol)

Mw

(daltons) PDI

2 Methylated(2.2)

1,1-Diphenylethylene(2.2)

Acrylic acid (40) Ammoniumperoxodisulfate(5.0)

28,900 1.4

4 Methylated(1.5)

1,1-Diphenylethylene(1.5)

2-Hydroxyethylmethacrylate (35)

AIBN (3) 14,900 1.7

6 Hydropropylated(2.22)

1,1,2,2-Tetraphenyl-1,2-dicyanoethane (1.8)

2-Hydroxyethylmethacrylate (60)and Styrene (10)

AIBN (3.7) 6,400 1.6

576 Method for the Production of Homo-, Co-, and Block Copolymers

b. 1-Benzyl-2,5-Cyclohexadiene-1-Carboxylic Acid

Title: Method for Radical Polymerizationin the Presence of a Chain Transfer Agent

Author: W. Gaschler, US Patent 7,196,150 (March 27, 2007)Assignee: BASF Aktiengesellschaft (Ludwigshafen, DE)

SIGNIFICANCE

1-Benzyl-2,5-cyclohexadiene-1-carboxylic acid is a new chain transfer agent that wasused to modulate the emulsion terpolymerization of styrene, butadiene, and acrylicacid. Its use resulted in 7% less gel formation than in an equivalent terpolymerizationlacking this additive.

REACTION

OHOi

a b c

Note 1

i: Water, sodium disulfonated monododecyl diphenyl ether, sodium dodecylbenze-nesulfonate, 1-benzyl-2,5-cyclohexadiene-1-carboxylic acid, butadiene, acrylicacid, sodium hydroxide, sodium peroxodisulfate

EXPERIMENTAL

Preparation of Poly(Styrene-co-Butadiene-co-Acrylic Acid) by EmulsionPolymerization

A polymerization vessel was charged with water (300 g), 33% polymer styrene latex(62 g, d50 of 30 nm), 10% of the initiator solution, and sodium peroxodisulfate andthen heated to 95�C. Using two separate feeds, the monomer emulsion present in

577

feed 1 and the initiator solution in feed 2 were simultaneously introduced into thepolymerizationvessel for over 2.5 hours at 95�C. A description of feed 1 and feed 2, isprovided below.

Feed 1

400 g deionized water

33 g emulsifier solution

45wt% sodium disulfonated monododecyl diphenyl ether

7 parts of 15wt% sodium dodecylbenzenesulfonate solution

0.8 g 1-benzyl-2,5-cyclohexadiene-1-carboxylic acid [chain transfer agent]

675 g styrene

310 g butadiene

30 g acrylic acid

10 g 25% strength by weight aqueous sodium hydroxide solution

Feed 2

10.2 g sodium peroxodisulfate in 200 g of water

When both feed lines were empty, the mixture temperature was cooled to 70�C,and an aqueous solution of 4 g of t-butyl hydroperoxide dissolved in 40ml of waterand a solution of acetone (1.7 g) and sodium disulfite (2.8 g) dissolved in 38ml ofwater were added over 2 hours at 70�C. Thereafter 22% aqueous NaOH (22 g) wasadded, and the mixture was cooled to ambient temperature. The solid content of thedispersion was approximately 50wt% having a light transmission of 70% with aparticle size of 124 nm, a pH of 6.8, and a product Tg of 27

�C.

DERIVATIVES

Emulsion polymerization with the chain transfer agent 1-benzyl-2,5-cyclohexadiene-1-carboxylic acid was also used to prepare poly(ethyl acrylate-co-methacrylic acid).Poly(N-vinylpyrrolidone) was prepared using the chain transfer agent 1-i-propyl-2,5-cyclohexadiene-1-carboxylic acid.

NOTES

1. Additional regulators were identified by the author [1] in a subsequentinvestigation and used in emulsion polymerization reactions:

Methyl 1-methyl-2,5-cyclohexadiene-1-carboxylate1-Isopropyl-2,5-cyclohexadiene-1-carboxylic acid1-t-Butyl-2,5-cyclohexadiene-1-carboxylic acid

578 Method for Radical Polymerization in the Presence of a Chain Transfer Agent

1-Allyl-2,5-cyclohexadiene-1-carboxylic acid1-Cyanomethyl-2,5-cyclohexadiene-1-carboxylic acid

2. g-Terpinene, (I), terpinolene, and a-methyl styrene dimer were used byManders [2] as chain transfer agents in the emulsion polymerization of styrene,butadiene, and acrylic acid. In a subsequent investigation by Gaschler [3] thesethree chain transfer agents were used in the emulsion polymerization of styreneand butadiene.

i-C3H7

(I)

3. Chain transfer functionalization of cysteinewas used by Brennan [4] to preparemacromonomer polybutyl acrylate end-functionalized with cysteine, (II),which was then polymerized with 4-aminobenzoic acid (III).

CO2HH2N

S

Polybutyl acrylate

HN

S

Polybutyl acrylate

O

HNO

i

(II) (III)

a

i: 4-Aminobenzoic acid, triphenylphosphine, lithium chloride, N-methyl-2-pyrrolidinone, pyridine

4. Organotungsten reversible addition-fragmentation chain transfer reagents,(IV), prepared by Lo [5] were used with AIBN to polymerize isobutyl acrylate.

(OC) 5WS

O

S

O

W(CO) 5

(IV)

5. Hayashi [6] prepared styryl alkoxyamine comonomers, (V), that behavedas high molecular regulators by releasing CO2 and 2,2,6,6-tetramethyl-4-hydroxy-1-piperinyloxy at elevated temperatures.

Notes 579

OOO

O

N

OH

(V)

References

1. W. Gaschler, US Patent Application 2006-0058478 (March 16, 2006)2. L. Manders et al., US Patent 7,196,146 (March 27, 2007)3. W. Gaschler et al., US Patent Application 2004-0242767 (December 2, 2004)4. A.B. Brennan et al., US Patent 7,169,853 (January 30, 2007)5. Y.-H. Lo et al., US Patent 7,132,491 (November 7, 2006)6. M. Hayashi et al., US Patent 6,919,481 (July 19, 2005)

580 Method for Radical Polymerization in the Presence of a Chain Transfer Agent

c. Polymercaptopolyols

Title: Use of C4-C6-Polymercaptopolyols as Regulatorsin Solution or Precipitation Polymerization

Author: K. Michl et al., US Patent 7,084,224 (August 1, 2006)Assignee: BASF Aktiengesellschaft (Ludwigshafen, DE)

SIGNIFICANCE

1,4-Dimercaptobutane-2,3-diol has been used to control the molecular weight ofpolymers during free radical polymerization. Polymers having1,4-dimercaptobutane-2,3-diol incorporated into their structure had weak “mercaptan” odors.

REACTION

aO

OH OHO

i a ~ 100

i: Sodium hydroxide, sodium persulfate, water, 1,4-dimercaptobutane-2,3-diol

EXPERIMENTAL

A reactor was filled with water (350 g) and heated to 90�C. Over the course of 5 hoursthree separate feeds of methacrylic acid (200 g), 50% solution of NaOH (55 g), water(350 g), sodium persulfate dissolved in water (100 g) and a mixture of 1,4-dimercap-tobutane-2,3-diol and water (100 g) were added. When the feeds were emptied, themixturewaspolymerized for 90minutes at 95�C, resulting in a clear solutionwith 18%solids and a pH of 4.7. After the workup the polymer was isolated, having an Mw of15,000 daltons.

581

RESULTS

NOTES

1. Tamura [1] used thiiranes, (I), to control the polymerization rate of bis(b-epithiopropyl) derivatives, (II), whichwere subsequently converted into opticalmaterials.

S S

B

S

A

(I) (II)

A = H, CH3, Cl, Br, I B = O, S

2. Thiocarbamate derivatives, (III), prepared by Rink [2] were effective as freeradical regulators in the 2,2-azobisisobutyronitrile-initiated polymerization ofstyrene.

NHHNS

O OS

HO OH(III)

3. Emulsion terpolymerization of t-butyl acrylate, methacrylic acid, and dimethi-cone in the presence of n-decanethiol resulted in an odorless product that wasused in cosmetic formulations by Drohmann [3].

4. Bremser [4] free radically copolymerized methacrylate and acrylic acid using1,1-diphenylethylene and mercaptoethanol as regulators.

TABLE 1. Effect on molecular weights and odor using selected thiol derivativesas polymerization regulators.

Entry Monomer Regulator InitiatorMercaptan

OdorMw

(daltons)

1.1 Acrylic acid 1,4-dimercaptobutane-2,3-diol

AIBN Weak 7,700

1.2 Acrylic acid Mercaptoethanol Na2S2O7 Strong 8,4001.3 Acrylic acid Dodecylmercaptan Na2S2O7 Strong 790,0002.1 Methacrylic acid 1,4-dimercaptobutane-

2,3-diolNa2S2O7 Weak 15,000

2.2 Methacrylic acid None Na2S2O7 — 80,0002.3 Vinylimidazole 1,4-dimercaptobutane-

2,3-diolAIBN Weak 40,000

582 Use of C4-C6-Polymercaptopolyols as Regulators in Solution or Precipitation Polymerization

5. Imino-N-alkoxy-polyalkyl-piperidine derivatives, (IV), prepared by Nesvadba[5] were effective as regulators in the free radical polymerization of styrene.

O

N

NOR

(IV)

R = H, CH3, t-C4H9

References

1. M. Tamura et al., US Patent Application 2005-261467 (November 24, 2005)2. H.-P. Rink et al., US Patent 7,153,917 (December 26, 2006)3. C. Drohmann et al., US Patent 7,147,842 (December 12, 2006)4. W. Bremser et al., US Patent 7,151,130 (December 19, 2006)5. P. Nesvadba et al., US Patent 7,199,245 (April 3, 2007)

Notes 583

d. S-(a,a0-Disubstituted-a00-Acetic Acid) Derivatives

Title: S-(a,a0-Disubstituted-a00-Acetic Acid)Substituted Dithiocarbonate Derivatives for ControlledRadical Polymerizations, Process, and Polymers MadeTherefrom

Author: J.T.-Y. Lai, US Patent 7,205,368 (April 17, 2007)Assignee: Noveon, Inc. (Cleveland, OH)

SIGNIFICANCE

A single-step method for preparing S-(a, a0-disubstituted-a00-acetic acid) substituteddithiocarbonate derivatives is described. These agents are effective as modulators infree radical polymerization reactions.

REACTION

a

HO2C S S CO2H

S

i OOiiCS2

i: Acetone, CCl3H, tetrabutylammonium bisulfate, toluene, sodium hydroxideii: 2,20-Azobisisobutyronitrile, 2-ethylhexylacrylate, acetone

EXPERIMENTAL

1. Preparation of S,S0-bis-(a, a0-Dimethyl-a00-Acetic Acid)-Trithiocarbonate

A 500-ml jacketed flask was charged with carbon disulfide (22.9 g), tetrabutylam-monium bisulfate (2.0 g), and 100ml of toluene and then treated with the dropwiseaddition of 50% sodium hydroxide solution (168 g) at such a rate the temperature did

584

not exceed 30�C. After the addition the mixture was further treated with acetone(43.6 g) and chloroform (89.6 g) at such a rate the temperature remained between20�Cand 30�C. This mixture was then stirred overnight at ambient temperature and treatedwith 500ml of water. The two layers were separated, and the aqueous layer wasacidified with concentrated hydrochloric acid to precipitate the product as a yellowsolid. The solid was washed with 50ml of toluene and filtered, and 22.5 g of productwas isolated.

2. Preparation of Poly(2-Ethylhexyl)Acrylate (Generic Procedure)

S-(a,a0-Dimethyl-a00-acetic acid) dithiocarbonate (5.33mmol), 2-ethylhexylacrylate(135.7mmol), 2,20-azobisisobutyronitrile (0.3mmole), and 25ml of acetone weremixed and stirred for 7 hours at 52�C. Thereafter the solution was filtered andconcentrated, and the product was isolated.


DERIVATIVES

S CO2HS

C2H5O C2H5O S CO2H

S N S CO2H

S

N S CO2H

S

N NS

OS

SHO2C CO2H

C2H5 C2H5

TABLE 1. Percent conversion for selected monomers using a Step 1 reactionregulator and 2,20-azobisisobutyronitrile as the free radical initiator.

EntryPolymerization

MonomerReaction

Time (min)Mn

(daltons)Mw

(daltons)Conversion

(%)

5 2-Ethylhexylacrylate 420 1614 2059 26.97 n-Butylacrylate 360 3532 4066 65.79 Styrene 360 2537 2956 84.5

Derivatives 585

NOTES

1. Tougheners for thermsettable polymers using polymeric thiocarbonate deri-vatives, (I), were previously prepared by the author [1].

S S

S

PolyacrylatePolyacrylateHO2C CO2H

(I)

2. Favier [2] used t-butyl dithiobenzoate, (II), as the chain transfer agent with 2,20-azobisisobutyronitrile to prepare poly(N-acryloyl morpholine), (III), having aMn> 200,000 daltons with a polydispersity of 1.4.

nO

O

O

SS ONO

O

(II)

(III)

3. Polystyrene was prepared by Benicewicz [3] by bulk polymerization with 2,20-azobisisobutyronitrile and had a polydispersity of 1.07 using either the lowodorthioester, (IV), or thiourethane, (V), as chain transfer agents.

S

S CN

N S

S CN

(IV) (V)

4. Rink [4] prepared thiocarbamate derivatives, (VI), that were used as regulatorsin the (co)polymerization of styrene using 2,20-azobisisobutyronitrile as thefree radical initiator.

586 S-(a,a0-Disubstituted-a0 0-Acetic Acid) Substituted Dithiocarbonate Derivatives

HN S

HN

O

S

O

HO

OH

(VI)

References

1. J.T.-Y. Lai et al., US Patent 6,894,116 (January 30, 2007)2. A. Favier et al., US Patent 7,205,362 (April 17, 2007) and US Patent Application 2007-0073011 (March

29, 2007)3. B. Benicewicz et al., US Patent Application 2007-0088140 (April 19, 2007)4. H.-P. Rink et al., US Patent 7,153,917 (December 26, 2006)

Notes 587

B. Chain Transfer Processes

a. Reversible Addition-Fragmentation Chain Transfer

Title: Chain Transfer Agents for RAFT Polymerizationin Aqueous Media

Author: C. L. McCormick et al., US Patent 7,179,872 (February 20, 2007)Assignee: University of Southern Mississippi (Hattiesburg, MS)

SIGNIFICANCE

Reversible addition-fragmentation chain transfer (RAFT) polymerization using2,20-azobisisobutyronitrile and either N,N-dimethyl-S-thiobenzoylthiopropionamideor N-dimethyl-S-thiobenzoylthioacetamide as chain transfer agents has been used toprepare low polydispersity poly(N,N-dimethylacrylamide). The chain transfer agentswere unusually effective in suppressing free radical termination reaction, therebymimicking a “living” polymerization reaction.

REACTION

N

O

N O

aiNote 1

i: 2,20-Azobisisobutyronitrile, benzene, N,N-dimethyl-S-thiobenzoylthiopropiona-mide or N,N-dimethyl-S-thiobenzoylthioacetamide

EXPERIMENTAL

Preparation of Poly(N,N-Dimethylacrylamide)

1.93M N,N-Dimethylacrylamide dissolved in benzene was free radically polymeri-zed at 60�C in a flame-sealed ampoule equipped with a magnetic stir bar using

588

2,20-azobisisobutyronitrile (1.0mmol) and either N,N-dimethyl-s-thiobenzoylthio-propionamide (5.0mmol) or N,N-dimethyl-s-thiobenzoyl-thioacetamide (5.0mmol)as the chain transfer agent. Prior to polymerization the ampoulewas subjected to threefreeze-pump-thaw cycles to remove oxygen. The polymerization reaction wasterminated by initially freezing the reaction in a dry ice/acetone bath followed byprecipitation in hexane.

REACTION SCOPING

TABLE 1. RAFT polymerization of N-N0-dimethylacrylamide using selected chaintransfer agents in benzene at 60�C with a chain transfer agent/AIBN ratio of 5:1,respectively.

Entry

ChainTransferAgent

ReactionTime (h)

Conversion(%)

Mn 1� 105


(daltons) PDI

1a S

S

14.5 80 3.2 5.1 1.22

1a S

S

36.6 90 3.6 5.1 1.22

1b S

S

8.1 59 2.4 3.6 1.25

1b S

S

36.6 86 3.4 4.6 1.24

1c S N

O

S

19.0 78 3.3 3.5 1.14

1c S N

O

S

36.6 82 3.7 4.3 1.14

Note: The targeted Mn for poly(N,N-dimethylacrylamide) was 40,000 daltons.

Reaction Scoping 589

NOTES

1. Structural depictions for N,N-dimethyl-S-thiobenzoylthiopropionamide, (I),andN,N-dimethyl-S-thiobenzoylthioacetamide, (II), respectively, are providedbelow.

S

S

X

N(I) X = O(II) X = S

2. Dithioester-terminated macromolecular transfer agents, (III), were previouslyprepared by the author [1] and used to modify metallic nanoparticle surfaces.

S PolydimethylacrylamideS

S Polydimethylacrylamide

(III)

Gold nanoparticle

SPolydimethylacrylamide

i

i: Sodium borohydride, water, gold nanoparticle

3. Moderately highmolecular weight polymerswith narrow polydispersities wereprepared by Lo [2] using tungsten-containing organometallic RAFT reagents,(IV) and (V).

P

(CO)3WS

S CNP

(CO)3WS

S CN

OO

t-C4H9

(IV) (V)

a a > 2

4. Using the RAFT chain transfer agent dibenzyltrithiocarbonate with oleic acid,tripotassium phosphate, potassium hydroxide, and potassium persulfate, Parker[3] prepared polystyrene by emulsion polymerization. The polystyrene latexwasobtained in roughly 90 minutes and had a solid content of 20.6%, while purifiedpolystyrene had a Mn of 54,000 daltons with a PDI of 1.17.

5. Mercapto-terminated block copolymers and block terpolymers prepared byTsuji [4] such as poly(acrylonitrile-b-butyl acrylate) and poly(acrylonitrile-b-butyl acrylate-b-ethyl acrylate), respectively, used the RAFT chain transferagent cumyl dithiobenzoate. The block copolymer had aMw of 48,600 daltons,

590 Chain Transfer Agents for RAFT Polymerization in Aqueous Media

Mn of 34,500 daltons, and a polydispersity index of 1.41, while the terpolymerhad a Mw of 48,700 daltons, Mn of 31,300 daltons, and a polydispersity indexof 1.56.

6. In a subsequent investigation by the author [5], N,N-dimethyl-s-thioben-zoylthioacetamide, (VI), was prepared as a RAFT chain transfer agent andused in the polymerization of N,N-dimethyl-acrylamide.

S SN

S

(VI)

References

1. C.L. McCormick et al., US Patent 7,157,534 (November 21, 2006)2. Y.-H. Lo et al., US Patent 7,132,491 (November 7, 2006)3. D.K. Parker et al., US Patent 7,098,280 (August 29, 2006) and US Patent 6,992,156 (August 29, 2005)4. R. Tsuji et al., US Patent 7,094,833 (August 22, 2006)5. C.L. McCormick et al., US Patent 7,186,786 (March 6, 2007)

Notes 591

b. Nitroxide-Mediated Polymerization

Title: Hindered Spiro-Ketal Nitroxides

Author: M. Jawdosiuk et al., US Patent 7,132,540 (November 7, 2006)Assignee: Nova Molecular Technologies, Inc. (Janesville, WI)

SIGNIFICANCE

Spiro-ketal nitroxides have been prepared that are effective as regulators in nitroxidemediated polymerizations. These agents have high hydrocarbon and monomersolubility over existing nitroxides, particularly in styrene, and are also effective asregulators in vinyl acetate and acetonitrile polymerizations.

REACTION

NH

OO

N

OO

O

Notes 1, 2

i

i: Methanol, hydrogen peroxide, sodium tungstate dehydrate

EXPERIMENTAL

Preparation of 1,5-Dioxa-9-Aza-8,8,10,10-Tetramethylspiro[5,5]Undec-9-Yloxy

A 500-ml Erlenmeyer flask was charged with1,5-dioxa-9-aza-8,8,10,10-tetramethyl-spiro[5,5]-undecane (0.04mole) dissolved in150mlofmethanol and then treatedwith40ml of 35% aqueous hydrogen peroxide followed by sodium tungstate dehydrate(0.4 g). Themixturewas left for 3 days at ambient temperaturewhere after one day thecolor became dark orange. It was then extracted with three 50-ml portions of t-butylmethyl ether anddriedwith an anhydrousNa2SO4.The solutionwas concentrated, and

592

9 gofadarkorange solidproductwas isolated,MP¼ 59–62�C.Theuseof thismaterialand related nitroxide regulators in polymerization reactions are provided in Table 1.

DERIVATIVES

TABLE 1. Effectiveness of nitric oxide polymerization regulators on thepolymerization of vinyl acetate and acetonitrile at 70�Cusing 10ml ofmonomer, 0.35 gof benzoyl peroxide, and 0.1 g of selected nitroxide regulators.

Entry Regulator

Inhibition Timefor Vinyl AcetatePolymerization (min)

Inhibition Timefor Acetonitrile

Polymerization (min)

— None 8 4

1

N

HN

O

O

205 40

2

N

O

O

O

145 60

3

N

O

O

>300 305

4 Step 1 product 250 135

5N

O

385 60

6

t-C4H9N

O

t-C4H9

130 180

Derivatives 593

NOTES

1. The Step 1 reagent 1,5-dioxa-9-aza-8,8,10,10-tetramethylspiro[5,5]-undecanewas prepared according to the method of Murayama [1].

2. Nesvadba [2] used both aromatic and cyclohexene spiro-ketal derivatives, (I)and (II), respectively, as free radical polymerization reaction regulators.

N

OO

O

(I)

N

OO

O

(II)

3. Polystyrene having a Mw of 61,00 daltons and Mn of 35,000 daltons wasprepared by Parker [3] by emulsion polymerization mediated by phenyl t-butylnitrone. Under identical experimental conditions a Mw of 860,000 and a Mn of440,000 were observed in the absence of this regulator.

4. Nitroxide mediated polymerization using 1- and 2-nitroso-naphthol were usedby Ma [4] to regulate the free radical polymerization of styrene.

References

1. K. Murayama et al., US Patent 3,790,525 (February 5, 1974)2. P. Nesvadba et al., US Patent Application 2006-0149011 (July 6, 2006)3. D.K. Parker et al., US Patent Application 2006-0241258 (October 26, 2006)4. Q. Ma et al., US Patent Application 2006-0283699 (December 21, 2006)

594 Hindered Spiro-Ketal Nitroxides

Title: Controlled Polymerization

Author: D. K. Parker et al., US Patent 6,992,156 (January 31, 2006)Assignee: The Goodyear Tire and Rubber Company (Akron, OH)

SIGNIFICANCE

The controlled emulsion polymerization of styrene using nitroxide-mediatedpolymerization (NMP), reversible addition-fragmentation transfer polymerization(RAFT), stable free radical polymerization (SFR), and atom transfer radical poly-merization (ATRP) methods is described. The chain transfer agent associated witheach process was phenyl-t-butylnitrone, nitric oxide, dibenzyl trithiocarbonate, 1,1-diphenylethylene, and ethyl 2-bromo-isobutyrate, respectively. Polydispersitiesbetween 1.17 and 1.80 were observed.

REACTION

a

EXPERIMENTAL

1. Controlled Polymerization of Styrene Using Phenyl-t-Butyl Nitrone and4,4-Azobis(4-Cyanovaleric Acid) [Nitrooxide-Mediated Polymerization; NMP]

In a typical reaction a 750-ml reactor was chargedwith styrene (962mmol), oleic acid(21.2mmol), and phenyl-t-butyl nitrone and then flushed with nitrogen. The mixturewas treated with a solution of K3PO4 (18.8mmol), KOH (29.3mmolþ 2mmol KOHper initator), and 4,4-azobis(4-cyanovaleric acid) (2.62mmol) dissolved in 400ml ofwater. In all cases an emulsion formed immediately. Reactors were flushed withnitrogen, sealed, and circulated on a rotating wheel in a water bath at 75�C, and the

595

reaction extendwasmonitored hourly. The solid polymerwas obtained by coagulating100ml of the latex with dilute hydrochloric acid, filtering, washing with water, andthen air-drying at 25�C. Reaction scoping results are provided in Table 1.

2. Controlled Polymerization of Styrene Using In situ Generated Nitric Oxide[Nitrooxide-Mediated Polymerization; NMP]

A reactor was charged with styrene (0.48mol), dodecylbenzenesulfonic acid(0.0092mol), and 1ml of distilled water. This mixture was stirred and treatedwith sodiumnitrite (0.002485mol), and themixture immediately turned a light blue-green color that faded to pale yellow within minutes. It was then treated with anaqueous solution comprising water (200 g), K2S2O8 (0.00762mol), K3PO4

(0.01mol), and 87.5% pure KOH (0.0115mol), whereupon a fine microemulsionimmediately formed. The mixture was rapidly heated with stirring to 75�C wherecomplete conversion to a stable emulsion occurred in 3 hours. After isolation theproduct had a Mn of 97,000 daltons, a Mw of 147,000 daltons, and a PDI of 1.51.

3. Controlled Polymerization of Styrene Using Dibenzyltrithiocarbonate[Reversible Addition-Fragmentation Transfer Polymerization; RAFT]

A reactionvesselwas chargedwith styrene (1000 g), oleic acid (60.0 g), and dibenzyl-trithiocarbonate (7.2 g) and then flushed with nitrogen. The mixture was next treatedwith an aqueous solution comprisingwater (4000 g),K2S2O8 (40.0 g),K3PO4 (40.0 g),and KOH (16.4 g), whereupon a fine microemulsion instantly formed. The reactionmixture was heated to 65�C where complete conversion to a stable, slightly yellowpolystyrene latex was achieved in roughly 90minutes; solids comprised 20.6%. Afterworkup the polymer had an Mn of 54,000 daltons with a PDI of 1.17.

4. Controlled Polymerization of Styrene Using 1,1-Diphenylethyleneas Controlling Agent [Stable Free Radical Polymerization; SFR]

A reaction flask was charged with styrene (0.48mol), oleic acid (0.0106mol) and1,1-diphenylethylene (0.002485moles) and then flushed with nitrogen. The mixturewas next treated with water (200 g), K2S2O8 (0.00762mol), K3PO4 (0.01mol), and87.5%KOH (0.0143mol), whereupon a finemicroemulsion formed. Themixturewasrapidly heated with stirring to 75�C where complete conversion to a stable emulsionoccurred in 2 hours. After isolation the product had a Mn of 51,000 daltons, a Mw of92,000 daltons, and a PDI of 1.80.

5. Controlled Polymerization of Styrene Using n-Butyl Acrylate and 1-Hexene[Atom Transfer Radical Polymerization; ATRP]

Areactorwas chargedwith 1-hexene (25 g), n-butyl acrylate (25 g), dipyridyl (0.38 g),oleic acid (4.0 g), and ethyl 2-bromoisobutyrate (0.47 g) and then stirred untilhomogeneous. The mixture was next treated with 85% KOH (1.7 g) dissolved in

596 Controlled Polymerization

139ml of water, whereupon an emulsion immediately formed. After approximately2 minutes, 1% CuSO4�5H2O (60.9 g) was added and formed a bluish emulsion. Thiswas then treated with 2 drops of hydrazine hydrate, and the mixture was heated toaround 67�C for 90 minutes where solids comprised 10.9%. After workup 27.5 g ofproduct were isolated.

REACTION SCOPING

NOTES

1. In a subsequent investigation by the author [1] additional controlled polymeri-zation reactions for preparing homo-, A-B diblock, and A-B-A triblock styrenepolymers by emulsion polymerization are disclosed.

2. In another investigation by the author [2] a selected bis-oxathiazaphospholinederivative, (I), was prepared and used as a free radical regulator in aqueous andnonaqueous emulsion polymerizations of styrene.

N

NO

i-C3H7

Oi-C3H7 S

PSS

PSH3CO OCH3

NO

PS PS

ON

i-C3H7 i-C3H7

H3CO OCH3(I)

+_

+

_

+ i

i: THF

3. The author [3] developed a method for preparing cyclic trithiocarbonates,(II), using epoxides in the ionic solvent 1-butyl-3-methylimidazolium

TABLE 1. Reaction scoping for styrene polymerization conducted at 75�C using962mmol styrene monomer and phenyl-t-butyl nitrone as the reaction regulator.

EntryPhenyl-t-ButylNitrone (mmol)

Ratio Initiator/Phenyl-t-Butyl

Nitrone

Ratio Styrene/Phenyl-t-Butyl

NitroneMn

(daltons)

1 4.24 3.5 227 53,7802 5.65 3.5 170 39,9104 7.06 3.5 136 39,4906 4.24 2.62 227 59,840

Note: The initiator in all cases was 4,4-azobis(4-cyanovaleric acid).

Notes 597

hexafluorophosphate. Trithiocarbonates were subsequently used as RAFTchain transfer agents in the controlled emulsion polymerization of styrene.

OS S

S

i

(II)

i: 1-Butyl-3-methylimidazolium hexafluorophosphate, carbon disulfide, pota-ssium thiocyanate, water

4. The author [4] prepared surfactant pairs as provided in Table 3 for the RAFTpolymerization of styrene using dibenzyltrithiocarbonate as the chain transferagent.

TABLE 3. Selected emulsion surfactant pairs used in the controlled RAFTpolymerization of styrene monomer with dibenzyltrithiocarbonate as the chaintransfer agent.

Entry Latent Surfactant Surfactant Activator

1 Palmitoyl chloride KOH2 Palmitoyl chloride Diethanolamine/KOH3 Palmitoyl chloride glycine5 Palmitoyl chloride 2-Aminopropanesulfonic acid/KOH7 Hexadecylamine succinic anhydride9 Hexadecylamine HCl13 4-Dodecylphenol KOH14 dodecanol Maleic anhydride/KOH

5. Wunderlich [5] utilized nitroxyether derivatives, (III), as free radical transferagents for controlling the molecular weight of polymers during free radicalpolymerization.

NRO O

(III)

R = H, CH3CO

598 Controlled Polymerization

References

1. D.K. Parker et al., US Patent Application 2006-0241258 (October 26, 2006)2. D.K. Parker et al., US Patent Application 2006-0160774 (July 20, 2006)3. D.K. Parker et al., US Patent Application 2006-0004210 (January 5, 2006) and US Patent 7,038,062

(May 2, 2006)4. D.K. Parker et al., US Patent Application 2005-0256253 (November 17, 2005) and US Patent 7,098,280

(August 29, 2006)5. W. Wunderlich et al., US Patent 7,074,860 (July 11, 2005)

Notes 599

Title: N-Alkoxy-4,4-Dioxy-Polyalkyl-Piperidinesas Radical Polymerization Inhibitors

Author: F. Fuso et al., US Patent 7,235,663 (June 26, 2007)Assignee: Ciba Specialty Chemicals Corp. (Tarrytown, NY)

SIGNIFICANCE

Free radical polymerization inhibitors have been prepared by reacting tetramethylpi-peridive oxyl derivatives with selected glycidyl intermediates. When used as astyrene polymerization regulator in 1.0mol% and 0.1mol% at 120�C, molecularweights of 2400 and 43,400 daltons, respectively, were obtained.

REACTION

N OH N OO

OiO

O

O

O

i: 2-(4-Ethylphenoxymethyl)-oxiran, copper(II)chloride, t-butylhydroperoxide

EXPERIMENTAL

Preparation of 7,7,9,9-Tetramethyl-8-[1-(4-Oxiranylmethoxy-Phenyl)-Ethoxy]-1,4-Dioxa-8-Aza-Spiro[4.5]Decan

A mixture of 7,7,9,9-tetramethyl-1,4-dioxa-8-aza-spiro[4.5]decan-8-oxyl (50 g)and 2-(4-ethylphenoxymethyl)oxiran (124.75 g) was heated to 60�C and thentreated with of 0.32 g of copper(II) chloride dissolved in 1.6ml of ethanol.This mixture was further treated with the dropwise addition of 70% aqueous t-butylhydroperoxide (45 g), reacted for 16 hours at 60�C, and cooled to ambienttemperature. Excess t-butylhydroperoxide was decomposed by the dropwise addi-tion of 20% aqueous sodium pyrosulfite solution. The mixturewas then treated with100ml of EtOAc, and the organic and aqueous phases were separated. The organic

600

phase was washed twice with 200ml of saturated NaCl solution, dried, andconcentrated. Excess 2-(4-ethylphenoxymethyl)oxiran was removed by distilla-tion; the residue was dissolved in hexane, filtered over aluminium oxide, and re-concentrated. The product was isolated as white crystals after re-crystallizationfrom hexane having a MP¼ 73.5–74.2�C.

DERIVATIVES

TABLE 1. Experimental N-alkoxy-4,4-dioxy-polyalkyl-piperidine regulatorsand corresponding melting points.

Entry Structure Mp (�C)

1 N OO

O

O

O124–125

2 N OOH

O

O133–134

5 N OO

OO

O88.5–93

7 N OO

OO

O56–59

8 N OO

OO

O64.5–67

REGULATOR SCOPING PROFILE

N OO

OO

O

Regulator

Regulator Scoping Profile 601

NOTES

1. Additional nitroxyl ether derivatives of the current invention are provided byDeDecker [1].

2. Wunderlich [2] and Nesvadba [3] prepared long alkyl chain 2,2,6,6 tetraalk-ylpiperidine-N-oxy radicals and N-alkoxy derivatives, (II), and (III), respec-tively, that were effective as polymerization regulators.

NO

C17H35

O

(II)

. NO O

NH

O

(III)

C18H37

3. Nesvadba [4] prepared 4-imino-piperidine-N-oxyl derivatives, (IV) and (V), foruse as polymerization regulators.

N

O

NO

P OC2H5O

OC2H5

N

O

NO

(IV)

(V)

TABLE 2. Effect on the free radical polymerization of styrene in the presenceof the free radical regulator, 7,7,9,9- tetramethyl-8-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-1,4-dioxa-8-aza-spiro-[4.5]decan.

Temperature (�C) Inhibitor (mol%) Polymer Yield (%) Mn (daltons) PDI

120 1.0 20 2,400 1.25120 0.1 41 43,400 1.59130 1.0 41 4,700 1.29130 0.1 55 58,000 1.39

602 N-Alkoxy-4,4-Dioxy-Polyalkyl-Piperidines as Radical Polymerization Inhibitors

4. Dimeric piperidine-N-oxyl derivatives, (VI), were prepared by Roth [5] tocontrol the molecular weight of polypropylene.

N

O O

O ON

OO

(VI)

References

1. M.N. DeDecker et al., US Patent 6,967,228 (November 22, 2005)2. W. Wunderlich et al., US Patent 6,864,313 (March 8, 2005 and US Patent 6,569,940 May 22, 2003)3. P. Nesvadba et al., US Patent 7,199,245 (April 3, 2007)4. P. Nesvadba et al., US Patent 7,160,966 (January 9, 2007)5. M. Roth et al., US Patent 7,030,196 (April 18, 2006)

Notes 603

C. PHOTOLYTIC REGULATING AGENTS

C. Photolytic Regulating Agents

Title: Method for Producing Polymers with ControlledMolecular Weight and End-Group Functionality UsingPhotopolymerization in Microemulsions

Author: A. Scranton et al., US Patent 7,226,957 (June 5, 2007)Assignee: University of Iowa Research Foundation (Iowa City, IA)

SIGNIFICANCE

A method for producing oligomeric butyl acrylate having a controlled molecularweight containingdiethanolamine termini byphotopolymerization inmicroemulsionsis described. The sensitizer consisted of methylene blue while the photoinitiatorconsisted of the diethanolamine free radical.

REACTION

S

N

ClS

N

Cl

NOH

OH

NHO

OH

N

OO

C4H9

OH

OH

* .

n

i

i: N-Methyldiethanolamine, butyl acrylate, water, sodium dodecylsulfate

604

EXPERIMENTAL

Oil-in-water microemulsions were prepared using butyl acrylate as the monomer,sodium dodecylsulfate as surfactant, and 1-pentanol as co-surfactant. In a typicalreaction, methylene blue and N-methyldiethanolamine were irradiated at 31�C, andthe product characterized by GPC.

SCOPING EXPERIMENTS

NOTES

1. In an earlier investigation by the author [1] a method was developed foreliminating singlet oxygen in the free radical polymerization of 2-hydroxy-ethylmethacrylate using 9,10-dimethylanthracene as the singlet oxygentrapper.

2. Fukushige [2] developed a method of microemulsion photopolymerizationusing organic dyes, (I) and (II).

OC6H13O OC6H13

N

O

S

(I)

H3CO2C

H3CO2C N

NO C2H5

C2H5O

(II)

References

1. A. Scranton et al., US Patent 7,141,615 (November 28, 2006)2. Y. Fukushige et al., US Patent 7,229,737 (June 12, 2007)

TABLE 1. Effect of sensitizer concentration on the molecular weight of polybutylacrylate using 0.0349M N-methyldiethanolamine as the photoinitiator.

EntryConcentration of Methylene

Blue (M� 105)PolybutylacrylateMn (daltons)

1 2.246 7402 2.635 5403 2.951 3904 3.209 160

Notes 605

Title: Ring-Opened Azlactone Photoinifertersfor Radical Polymerization

Author: K. M. Lewandowski et al., US Patent 7,041,755 (May 9, 2006)Assignee: 3M Innovative Properties Company (St. Paul, MN)

SIGNIFICANCE

Dithiocarbamic-5-oxo-4,5-dihydro-oxazole derivatives have been prepared that areuseful in controlled free radical polymerization reactions. When these azlactonephotoiniferterswere used in the polymerization of styrene ormethylmethacrylate, theMn as a function of reaction time was constant.

REACTION

H2NOH

ONH

OH

O

OCl

N

OOCliii iii

N

OOS N

S

S

O

N

S

N

O

ivn

Note 1

i: Sodium hydroxide, water, chloroacetyl chloride, hydrochloric acidii: Triethylamine, acetone, ethyl chloroformateiii: Diethyl dithiocarbamate, acetonitrileiv: Styrene

EXPERIMENTAL

1. Preparation of 2-(2-Chloro-Acetylamino)-2-Methyl Propionic Acid

A reaction vessel containing 2-aminoisobutyric acid (1.61mol), sodium hydroxide(1.61mol), and 800ml of water was cooled to 5�C and treated with chloroacetyl

606

chloride (1.77mol) and 143ml of aqueous sodium hydroxide (1.77mol) whilemaintaining the temperature between 5�C to 10�C. The reaction mixture was thenwarmed to ambient temperature, and the solution was acidified with 165ml of 12MHCl. The precipitated solid was filtered and dried under vacuum, and the product wasisolated in 62% yield.

2. Preparation of 2-Chloromethyl-4,4-Dimethyl-4H-Oxazol-5-One

Amixture consisting of the Step 1 product (0.100mol), triethylamine (0.110mol), and100ml of acetone was cooled in an ice bath and then treated with ethyl chloroformate(0.110mol) over a period of 10minutes. The reactionmixturewas warmed to ambienttemperature and stirred for 2 hours. The mixture was filtered and the filtrate concen-trated. The residuewas treatedwith 200ml of hexane, re-filtered, and re-concentrated.It was distilled, and the product was isolated as a colorless oil in 82% yield, BP¼59–60�C at 7mmHg.

3. Preparation of Diethyl-Dithiocarbamic Acid 4,4-Dimethyl-5-Oxo-4,5-Dihydro-Oxazol-2-Ylmethyl Ester

Amixture of 10 g of sodium diethyl dithiocarbamate trihydrate dissolved in 100ml oftoluene was dried using a Dean–Stark trap and then concentrated, and anhydrousdithiocarbamate was isolated. The anhydrous dithiocarbamate (0.039mol) was thenadded to a solution of the Step 2 product (0.037mol) dissolved in 130ml ofacetonitrile, and the mixture was stirred 2 hours at ambient temperature. The mixturewas then filtered and the filtrate concentrated. The residue was distilled, and theproduct was isolated in 74% yield as a yellow-green oil, BP¼ 170–180�C at0.25mmHg.

4. Preparation of Polystyrene [Az-Polystyrene-DC]

A solution of the Step 3 product (0.00044mol) dissolved in styrene (0.384mol) wasprepared and then divided into five equal 8.0 g portions. The solutions were placed invials with screw caps having an integral valve and rubber septum. The solutions weredegassed by three successive freeze-pump-thaw cycles and then placed on rollersunder aUV lamp (SylvaniaF40/350BL-blacklight) 10 cmfrom thebulb.Eachvialwasthen irradiated for 2.5, 6, 10, 16, and 20 hours with a light intensity of 1.25mW.Scoping results are summarized in Table 1.

DERIVATIVES

A second derivative, (I), was also prepared and used in reaction scoping studies for thepreparation of methyl methacrylate star polymers. Testing results are summarized inTable 2.

Derivatives 607

NH

N

OHN

S N

O

S

3

(I)

REACTION SCOPING

NOTES

1. In an earlier investigation by the author [1] poly(styrene-b-methymethacrylate)was prepared by postreacting polystyrene with methyl methacrylate in thepresence of selected azlactones

2. Fansler [2] used the bromomethyl analogue, (II), of the Step 2 product in theatom transfer radical polymerization ofmethyl methacrylate. Lewandowski [3]prepared the tribromomethyl analogue, (III), by reacting with trimethylolpro-pane and then used this reagent to preparemethylmethacrylate star polymers. Areaction profile is provided in Table 3.

TABLE 1. Physical properties of polymers in the controlled polymerizationof styrene using the Step 3 product.

Tube Reaction Time (h) Conversion (%) Mn 1� 104 (daltons)

1 2.5 7.3 1.552 6 16.4 1.773 10 23.2 2.234 16 32.7 2.785 20 36.1 3.10

TABLE 2. Physical properties of polymers in the star polymerization of methylmethacrylate using the trifunctional photoiniferter, (I).

Tube Reaction Time (h) Conversion (%) Mn 1� 105 (daltons)

1 1 1.2 1.832 2 6.5 2.493 4 12.2 2.974 6 15.1 3.045 8 20.3 3.24

Note: Star azlactone were prepared by reacting the Step 2 product with tris(2-aminoethyl)amine.

608 Ring-Opened Azlactone Photoiniferters for Radical Polymerization

O

N

OBr

O

O

O

Br

(II) (III)

3

3. Lusten [4] prepared macroiniferter polymers, (IV), that were used in electronicdevices and in molecular recognition.

S

N

S

ab

(IV)

4. Destarac [5] polymerized 4-vinylbenzeneboronic acid using O-ethyl S-(1-methoxycarbonyl)-ethyl xanthate, (V), as the free radical polymerisationcontrolling agent.

C2H5O SOC2H5

O

OCH3S

(V)

TABLE 3. Reaction profile for controlled free radical polymerizationof methyl methacrylate using the star atom transfer radical agent, (III),prepared by Lewandowski [3].

Reaction Time (min) Mw 1� 103 (daltons) Mn 1� 103 (daltons) PDI

10 1.87 1.73 1.0820 2.86 2.45 1.1730 2.97 2.38 1.2540 3.29 2.57 1.2850 3.51 2.71 1.2960 3.95 3.05 1.2970 5.10 3.90 1.31

Notes 609

References

1. K.M. Lewandowski et al., US Patent 6,908,952 (June 21, 2005)2. D.D. Fansler et al., US Patent 6,992,217 (January 31, 2005)3. K.M. Lewandowski et al., US Patent Application 2005-0065300 Application (May 9, 2005)4. L. Lutsen et al., US Patent Application 2006-0079648 (April 13, 2006)5. M. Destarac et al., US Patent Application 2005-0203256 (September 15, 2005)

610 Ring-Opened Azlactone Photoiniferters for Radical Polymerization

XXI. PHOTORESISTS

A. Fluorine Containing

a. Fluorine Acetals

Title: Monomer Having Fluorine-Containing Acetalor Ketal Structure, Polymer Thereof, and Chemical-Amplification-Type Resist Composition as Well asProcess for Formation of Pattern with Use of the Same

Author: K. Maeda et al., US Patent 7,232,639 (June 19, 2007)Assignee: NEC Corporation (Tokyo, JP)

SIGNIFICANCE

Perfluoroacetal or perfluoroketal polymethacrylates containing norbornene substi-tuents and having improved transparency were prepared and were suitable for use inphotolithographywith far-ultraviolet light at awavelength of 180 nmor shorter. Thesematerials are particularly useful in the formation of a fine resist patterns.

REACTION

F3C CHF2

OHO

O

CHF2

O

F3C

OO

CHF2

O

F3C

ai ii

i: Hexane, diethyl ether, 2-norbornanemethanol, pentafluoroisopropanol, n-butyl-lithium, hydrochloric acid,

ii: Hexane, 2,20-azobisisobutyronitrile


611

EXPERIMENTAL

1. Preparation of Methacrylate Intermediate

A flask containing 70ml of THF and 8.56 g of pentafluoroisopropanolwas cooled to�78�C and then treated dropwise with 67ml of 1.6M n-butyllithium hexane andstirred for 1 hour at 0�C. The mixture was next treated with 2-norbornanemethanol(5 g) dissolved in dry THF and stirred 4.5 hours at ambient temperature. It waspoured into ice-water and made acidic with dilute hydrochloric acid. The organiclayer was extracted with diethyl ether, washed with saline solution, dried, andconcentrated. The residue (2 g) was dissolved in 20ml of dry CH2Cl2 containingtriethylamine (2.56 g) and phenothiazine (8mg). Under ice cooling this solutionwastreated with the dropwise addition of methacryloyl chloride (2.21 g) dissolved in4ml of CH2Cl2 and stirred 4 hours at ambient temperature. The mixture was dilutedwith 100ml of diethyl ether, sequentially washed with 0.5M hydrochloric acid, 3%aqueous NaHCO3 solution, saline solution, and dried over MgSO4; the product wasisolated in 65% yield.

2. Preparation of Polymethacrylate Ketal

A50-ml eggplant-shaped flaskwaschargedwith theStep1product (6.4 g)dissolved in16ml of dry toluene and then treated with 2,20-azobisisobutyronitrile (123mg). Thismixture was stirred 12 hours at 80�C, cooled, and poured into 200ml of hexane. Theprecipitate was collected by filtration and further purified by re-precipitation. Theproduct was isolated in 10% yield having a Mw of 7800 daltons and polydispersityindex of 1.98.

DERIVATIVES

R1

O

O

CHF2

OR2

F3C

1HNMR (CDCl3) d 0.52 1.82 (9H,m), 1.97 (3H, s), 2.05 2.32 (2H,m), 3.35 3.83 (2H,m), 5.78 (1H, s), 6.27(1H, s), 6.57 (1H, t)

FTIR (KBr; cm�1): 2874, 2958 (C–H), 1749 (C¼O) 1638 (C¼C), 1210, 1180, 1141, 1118, 1041

612 Monomer Having Fluorine-Containing Acetal

NOTES

1. Additional polymerizable perfluoromethacrylates and polybornenes, (I) and(II), respectively, were prepared by Inoue [1] and used in photoresistcompositions.

TABLE 2. Selected Step 1 norbornene pentafluoroketal derivatives that wereconverted into the correspondingpolybornene derivative using di-l-chlorobis[(g-allyl)palladium(II)]and silver hexafluoroantimonate.


6 O

O

O

CHF2F3C

—

8

O

O

O

CHF2F3C

24

9

O

O

O

CHF2F3C

24

TABLE 1. Selected monomers prepared by condensing pentafluoropropyl alcoholwith methacryloyl or acryloyl chloride.

Entry R1 R2 Yield (%)

1 Methyl Benzyl 672 Methyl 2-Norbornanemethyl 653 Hydrogen Isobutyl 184 Hydrogen Methyl 32

Note: Polymers were free radically prepared using 2,20-azobisisobutyronitrile.

Notes 613

O

FF

O

O

O

F3C

OHCF3

(I) (II)

2. Polymerizable polycyclic perfluoromonomers, (III), prepared by Sumida [2]were suitable as resist components having high transparency in the ultravioletregion and near-infrared light region.

O

CF3

F3C OO

CF3F3C

(III)

3. Polymerizable perfluorinated methacrylates, (IV), prepared by Khojasteh [3]were effective as photoresist materials with improved etch resistant properties.

OO

O

F3CCF3

OH

a a = 2 - 6

(IV)

4. Polymerizable perfluoromonomers, (V), prepared by Feiring [4] had high UVtransparency at 157 nm and were used in lithography.

O CF3

CF3OH

(V)

614 Monomer Having Fluorine-Containing Acetal

References

1. K. Inoue, US Patent Application 20030059710 (March 27, 2003)2. S. Sumida et al., US Patent 7,232,917 (June 19, 2007)3. M. Khojasteh et al., US Patent 7,217,496 (May 15, 2007)4. A.E. Feiring et al., US Patent 7,217,495 (May 15, 2007)

Notes 615

b. Fluoro Vinylsulfones

Title: Polymers, Resist Compositions, and PatterningProcess

Author: Y. Harada et al., US Patent 7,169,869 (January 30, 2007)Assignees: Shin-Etsu Chemical Co., Ltd. (Tokyo, JP)

Matsushita Electric Industrial Co., Ltd. (Kadoma, JP)Central Glass Co., Ltd. (Ube, JP)

SIGNIFICANCE

Novel terpolymer compositions containing 4-(di-trifluoromethyl-hydroxymethyl)-1-(di-trifluoromethy)methyl)cyclohexyl] vinylsulfonate have been prepared havingexcellent transparency, substrate adhesion, and plasma etching resistance. Theintroduction of perfluoronorbornene resulted polymers that were especially suitablefor deep UV lithography.

616

REACTION

F3C CF3HO

OF3C

O2S

F3C

F3C CF3OH

OF3C

O2S

F3C

F3COH

CF3

CF3

OO

t-C4H9

ba c d

i

i: 5-(2,2-Trifluoromethyl-2-hydroxy)ethyl-norbornene, t-butyl trifluoromethyla-crylate, 1,4-dioxane azobisisobutyronitrile

EXPERIMENTAL

1. Preparation of [4-(di-Trifluoromethyl-Hydroxymethyl)-1-((di-Trifluoromethy) Methyl)-Cyclohexyl] Vinylsulfonate Terpolymer

A 300-ml flask was charged with 4-(di-trifluoromethyl-hydroxymethyl)-1-((di-tri-fluoromethyl) methyl)cyclohexyl] vinylsulfonate (7.00 g), 5-(2,2-trifluoromethyl-2-hydroxy)ethyl-norbornene (7.58 g), and t-butyl trifluoromethylacrylate (5.42 g)dissolved in 1,4-dioxane (5.0 g). This mixture was then treated with 2,20-azobisiso-butyronitrile (0.34 g) and polymerized at 60�C for 24 hours. The reactionmixturewaspoured into 1 liter of hexane, and the precipitated was isolated. The polymer waspurified by dissolving in THF and re-precipitating in hexane, this process beingrepeated twice, and 12.5 g of a white polymer product were isolated.

Mw (light scattering method)¼ of 5100 daltonsPDI¼ 1.41H-NMR (monomer ratio, a:b:c)¼ 16:43:41

Experimental 617

DERIVATIV

ES

TABLE

1.Summaryof

perfluorom

onom

ersusedin

the2,20-azobisisob

utyronitrile

initiatedfree

radical

terpolym

erization

andthecorrespon

dingpolym

erphysical

properties.

Polym

er

Entry

Mon

omer

1Mon

omer

2Mon

omer

3

Mon

omers

1:2:

3Ratio

inPolym

erM

w1�10

3

(daltons)

PDI

1

F3C

CF 3

HO

OF

3CO

2S

F3C

F3C H

O

CF

3

CF

3

OO t-

C4H

9

16:43:41

5.1

1.4

2

F3C

CF 3

HO

OF

3CO

2S

F3C

F3C H

OC

F3

CF

3

OO

17:42:41

5.2

1.4

618

3

F3C

CF 3

HO

OF

3CO

2S

F3C

CF

3F

3C HO

CF

3

OO t-

C4H

9

20:42:38

9.3

1.6

4

F3C

CF 3

HO

OF

3CO

2S

F3C

CF

3F

3C HO

CF

3

OO

19:41:40

9.9

1.6

5

F3C

CF 3

HO

OF

3CO

2S

F3C

F3C

CF

3H

OC

F3

CF

3O

H

CF

3

OO t-

C4H

9

19:41:40

9.3

1.6

(continued)

619

TABLE

1.(C

ontinued)

Polym

er

Entry

Mon

omer

1Mon

omer

2Mon

omer

3

Mon

omers

1:2:

3Ratio

inPolym

erM

w1�10

3

(daltons)

PDI

6

F3C

CF 3

HO

OF

3CO

2S

F3C

F3C

CF

3H

OC

F3

CF

3O

H

CF

3

OO

18:41:41

9.5

1.6

7

F3C

CF

3

HO

OF

3CO

2S

F3C

F3C

CF

3H

OC

F3

CF

3O

H

CF

3

OO t-

C4H

9

18:41:41

9.5

1.6

Note:In

allcases

theinitialm

onom

erfeed

ratioof

mon

omers1,2,and3was

20:40:40,respectively.A

dditionalp

erfluo

romon

omersaredescribedby

theauthor

[1]in

asubsequent

investigation.

620

TESTING

NOTES

1. In other investigations by the author [2,3] polymer resist compositions contain-ing perfluoro oxetene, (II), and cyclohexane, (III), monomers were alsoeffective on the transmission of 157 nm from an F2 laser.

OCF3

CF3

CF3

OO

O O

CF3

CF3OH

F3C

CF3HO

(II) (III)

2. Hatakeyama [4] and Harada [5] polymerized monomers containing a-trifluor-omethylacrylic carboxylates having acid labile groups, (IV) and (V), respec-tively, that were used as polymer resists with high surface adhension and alkalidissolution sensitive to high-energy radiation below 200 nm.

TABLE 2. Effect of resist polymers on the transmission of 157 nm from an F2 laser.

Entry248 nm

Transmission (%)193 nm

Transmission (%)157 nm

Transmission (%)

1 99 93 692 99 83 653 99 10 604 99 10 575 99 11 666 99 11 607 99 11 55Comparative Polymer 1*1 90 5 15Comparative Polymer 2*2 82 6 17

Note: All experimental entries were assessed as favorable.*1Polyhydroxystyrene, Mw¼ 10,000 daltons, polydispersity index¼ 1.1*2Novolak resin, meta/para¼ 40/60, Mw¼ 9,000 daltons, polydispersity index¼ 2.5

Notes 621

CF3

OO

OO

CF3

OO

O

O

(V)(IV)

3. Hatakeyama [6] reduced the number of alcohol groups by approximately 50%in perfluoro terpmonomer resists to modify surface adhesion and transparencyby postreacting with methoxymethyl chloride.

F3C

HO

CF3

O

F3C

F3CHO

CF3

CF3OH

O

CF3

F3C

HOCF3

O

F3C

F3CHO

CF3

F3COH

O

CF3

(VI) (VII)

a b

F3C

HOCF3

O

F3C

F3CHO

CF3

F3CO

O

CF3

F3C

O

CF3

O

F3CCF3

HO

CF3

CF3

O

O

CF3

OCH3H3COOCH3

a b c d

i

(VIII)

+

(IX)

ii

i: 1,4-Dioxane, 2,20-azobisisobutyronitrileii: THF, methoxymethyl chloride

References

1. Y. Harada et al., US Patent Application 2006-0269871 (November 30, 2006)2. Y. Harada et al., US Patent 7,125,643 (October 24, 2006)3. Y. Harada et al., US Patent 7,125,641 (October 24, 2006)4. J. Hatakeyama et al., US Patent 7,005,228 (January 30, 2007)5. Y. Harada et al., US Patent Application 2006-0177765 (August 10, 2006)6. J. Hatakeyama et al., US Patent Application 2005-0084796 (April 21, 2005)

622 Polymers, Resist Compositions, and Patterning Process

c. Fluoro Norbornene

Title: Fluorine-ContainingPolymerizableCyclicOlefinCompound

Author: T. Watanabe et al., US Patent 7,012,161 (March 14, 2006)Assignee: Shin-Etsu Chemical Co., Ltd. (Tokyo, JP)

SIGNIFICANCE

Hydrophobic fluorine-containing polymerizable cyclic olefin derivatives have beenprepared that are transparent to irradiation at 160 nm or less. These monomers haveexcellent development characteristics and appear useful as components in a base resinof photoresist compositions.

REACTION

CHO

F2C

F3C

OH

OHHO

F2C

F3C

OH

O

i iiNote 1

i: 1,1,1,3,3,3-Hexafluoro-2-propanol, THF, butyllithiumii: Toluene

623

EXPERIMENTAL

1. Preparation of 1-(5-Norbornene-2-yl)-2,2,4,4,4-Pentafluorobutane-1,3,3-Triol

A reaction vessel containing 1,1,1,3,3,3-hexafluoro-2-propanol (168 g) and THF(1200 g) at �70�C was treated with 1290ml of 1.6M of butyllithium, and thetemperature was gradually increased to 0�C. The mixture was stirred at this tempera-ture for 30 minutes and then treated with of 5-norbornene-2-carboxaldehyde (134 g)and stirred for an additional 60 minutes. After quenching with dilute hydrochloricacid, the mixture was subjected to standard aqueous workup. The crude product waspurified by silica gel column chromatography, and the product was isolated in 80%yield.

2. Preparation of 1-Hydroxy-1-(5-Norbornene-2-yl)-2,2,4,4,4-Pentafluorobutane-3-One

Amixture consisting of the Step 1 product (288 g) and toluene (1500 g) was refluxed,and water was removed during this period. The mixture was cooled and concentrated,and the product was isolated in quantitative yield.

1H-NMR (d6-DMSO): d 0.72 (1H, m), 1.18 (1H, br.d, J¼ 8.0Hz), 1.29 (1H, br.d, J¼ 8.0Hz), 1.74(1H, ddd, J¼ 12.0, 9.0, 3.7Hz), 2.44 (1H, m), 2.77 (1H, m), 3.02 (1H, m), 3.52 (1H, ddd,J¼ 22.0, 10.6, 7.4Hz), 6.02 (1H, dd, J¼ 5.7, 2.8Hz), 6.19 (1H, dd, J¼ 5.7, 3.0Hz), 6.29 (1H, d,J¼ 7.4Hz), 7.37 (1H, s), 7.96(1H, d, J¼ 1.9Hz).

19F-NMR (CDCl3): d �130.0 (1F), �120.6 (1F), �82.0 (3F)FTIR (KBr cm�1) 3409, 3288, 3062, 2979, 2946, 2923, 2879, 1486, 1454, 1423, 1338, 1311, 1255, 1241,

1207, 1172, 1153, 1112, 1076, 1025, 900, 842, and 711

13C-NMR (d6-DMSO) 182.3 (C¼O)FTIR (film cm�1) 1785

624 Fluorine-Containing Polymerizable Cyclic Olefin Compound

DERIVATIVES

TABLE 1. Selected perfluoro alcohols and corresponding Step 1 product yields.

Entry StructureStep 1

Product Yield (%)

2F2C

F3C

OH

OHHO

65

4F2C

F3C

OH

SCH3HO

100

6F2C

F3C

OH

NHSO2CH3HO

100

7

F2C

F3C

OH

OH

91

8F2C

F3C

OH

OH

93

Derivatives 625

NOTES

1. Fluorine-containing photosensitive polymers, (I), containing a gemdiol com-ponent were prepared by Yoon [1] and used in resist compositions.

CF2

CF3

OH

HO

HO

CF3

O

O

t-C4H9

F3C CF3OH

(I)

a b c

2. Photoresist compositions consisting of pentafluoromethylvinyl carbonate de-rivatives, (II), were prepared by Yoon [2] and used in photosensitive polymersfor exposure to light sources having a dominantwavelength of less than 157 nm.Perfluorovinyl ether, (III), monomerswere prepared byDiPietro [3] and used inlithographic photoresist polymer compositions.

F

F

CF3

O

O Ot-C4H9

(II)

O

CF3

CF3

OH

(III)

References

1. K.-S. Yoon et al., US Patent 6,800,418 (October 5, 2004)2. K.-S. Yoon et al., US Patent 7,202,011 (April 10, 2007)3. R.A. DiPietro et al., US Patent 7,150,957 (December 19, 2006)

626 Fluorine-Containing Polymerizable Cyclic Olefin Compound

d. Fluoroacrylates

Title: Photoresist Composition

Author: R.D. Allen et al., US Patent 7,135,595 (November 14, 2006)Assignee: International Business Machines Corporation (Armonk, NY)

SIGNIFICANCE

A new family of perfluoroacrylate and methacrylate based positive and negative tonephotoresist compositions activated at 193 nmhas been prepared by free radical homo-or co-polymerization of acrylate or methacrylate derivatives. Polymeric agentsprepared in this manner hadMn’s between 5,000 and 50,000 daltons and were readilysoluble in organic solvents.

REACTION

F3C

CF3

OHF3C

CF3

OHF3C

CF3

OH

OH

OH

F3C

CF3

OH

O

O

Separatei

ii

+

Preferred

iiiOO

CF3

HO

F3C

OO

OH

a b

i: Borane-dimethylsulfide complex, 1,1,1-trifluoro-2-trifluoromethyl-4-penten-2-ol, THF, hydrogen peroxide, diethyl ether,

ii: n-Butyllithium, methacryloyl chloride, THFiii: 2,20-Azobisisobutyronitrile, THF, 2-(6-hydroxylmethyl)naphthalene methacry-

late ester

627

EXPERIMENTAL

1. Preparation of 1,1,1-Trifluoro-2-Trifluoromethyl-2,5-Pentanediol(Preferred) and 1,1,1-Trifluoro-2-Trifluoromethyl-2,4-Pentanediol

A flask was charged with 974ml of borane-dimethylsulfide complex (1.95mol; 2.0Min THF) and treated with 1,1,1-trifluoro-2-trifluoromethyl-4-penten-2-ol (1.7mol)dissolved in400mlofanhydrousTHFat sucha rate that the temperature didnot exceed15�C. The mixture was stirred at ambient temperature for two days, cooled, andquenched with 750ml of 3M NaOH. The solution volume was reduced by co-evaporation twice with 500ml of diethylether, and an oil was isolated. The residuewas dissolved in 300ml of cooled THF, slowly treated with 250ml of 30% hydrogenperoxide, and stirred overnight at ambient temperature. The mixture was diluted with1 liter of diethyl ether, and the pHwas lowered to 6 with 5%HCl. The ether layer wasseparated, and the aqueous layer was extracted twicewith 500ml of diethyl ether. Thecombined organic phaseswerewashed twicewith 500ml of saturated aqueousNH4Cland brine and then dried with MgSO4. The residue was concentrated, and a 379 gmixture of a 45 : 55, 2�/1� alcohol mixture, respectively, was isolated and purified bydistillation through a 1200 Vigreux. The 2� alcohol had BP¼ 47�C at 1.0 mmHg andwas a lowmelting solid, while the preferred 1� alcohol had a BP¼ 55�C at 1.0mmHg,which was isolated as a viscous oil.

2. Preparation of 1,1,1-Trifluoro-2-Trifluoromethyl-2-Hydroxy-5-PentylMethacrylate

A reaction vessel containing n-butyllithium (0.944mol; 1.6M in hexane) was treatedwith the Step 1 product dissolved in 300ml of THF at such a rate that the reactiontemperature did not exceed 15�C and then stirred 2 hours. Methacryloyl chloride(0.52mol) dissolved in 200ml of anhydrous THF was added dropwise over 1 hour at10�C, and the mixturewas stirred overnight at ambient temperature. The mixture wasnext diluted with 500ml of diethyl ether, washed twice with 500ml of saturatedaqueous NH4Cl and brine, and dried with MgSO4. The product was isolated in 79%yield by distillation at 74�C at 1.0mmHg (0.5 g of phenothiazinewas added to the potprior to distillation).

3. Preparation of Poly(1,1,1-Trifluoro-2-Trifluoromethyl-2-Hydroxy-5-PentylMethacrylate-co-2-Methacryloxy-6-Hydroxymethylnaphthalene)

A reactionvessel was chargedwith the Step 2 product (0.018mol), 2-methacryloxy-6-hydroxymethyl naphthalene (0.002mol), 15ml of THF, and 2,20-azobisisobutyr-onitrile (0.8mmol) and then refluxed 18 hours. The solution was poured into 500mlhexanes from which the polymer precipitated. The precipitated polymer wasfiltered, washed twice with 50ml hexanes and dried at 60�C, and the product wasisolated.

628 Photoresist Composition

MONOMER DERIVATIVES

O

OCF3

CF3OHO

OCF3

CF3OH

OHF3C

CF3

O

O

OO

O O

O

O

O

(I) (II) (III)

(IV) (V) (VI)

Polymeric positive and negative tone photoresists activated at 193 nm wereprepared using methacrylate monomers, (I–VI), and are illustrated in Table 1.

NOTES

1. In a subsequent investigation by the author [1] molecular positive tonephotoresist blends consisting of nonpolymeric octakis(dimethylsilyloxy)sil-sesquioxane, (VII), and acid-labile bulky substiutents including 2-t-butyltetracyclo-dodec-3-ene-5-carboxylate, (VIII), N-(2-tetrahydro-2H-pyran-2-yloxy)-5-norbornene-2,3-dicarboximide, (IX), and norbornene anhydride,(X), were prepared and activated at 248 nm, 193 nm, 157 nm, and 134 nm,respectively.

TABLE 1. Selected polymeric positive and negative tone ptotoresists activatedat 193 nm prepared by free radical polymerization using selected methacrylatemonomers.

Entry Photoresist Tone Polymer Composition

6 Positive III-co-I-co-V7 Negative I-co-VI8 Negative II-co-VI13 Negative III15 Positive II19 Negative III-co-IV20 Positive IV-co-V-co-VI

Notes 629

O

SiO Si

O

SiOSi

O

Si

O SiOSi

OSi

R

O

R

O

R R

R

OR

RR

O(CH3)2SiO

O

O-t-C4H9

N

O

O

OO

O

O

O

O(CH3)2SiO

O(CH3)2SiO

(VII)

(VIII)

(IX)

(X)

Entry R

2. Carr [2] prepared positive tone photoresists activated below 200 nm bycopolymerizing fluorinated bridged carbocyclic compounds, (XI) and (XII),with other fluorinated unsaturated bridged carbocyclic monomers.

630 Photoresist Composition

(XI)

O

CF3

CF3OH

CF3

CF3OC2F5

C2F5HO

C2F5a

(XII)

a = 0 - 4

3. Positive tone photoresist resins activated below 200 nmwere prepared by Inoue[3] by copolymerizing polycyclic monomers, (XIII) and (XIV), with t-butyl-trifluoromethyl acrylate, (XV).

S S

F3C CF3

OX

CF3

O

O-t-C4H9X= O,S

(XIII) (XIV) (XV)

4. Kodama [4] andWada [5] prepared positive photosensitivematerials consistingof poly(3-hydroxyadamantyl) methacrylate, (XVI), and terpolymers, (XVII),respectively, that were activated at 193 nm.

O O

OO

O O O

OH

42 31 27

(XVII)

OH

OO

20

(XVI)

References

1. R.D. Allen et al., US Patent 7,141,692 (November 28, 2006)2. R.V.C. Carr et al., US Patent 7,138,550 (November 21, 2006)3. K. Inoue, US Patent Application 2003/0059710 (March 27, 2003)4. K. Kodama, US Patent Application 2006/0204890 (September 14, 2006) and US Patent Application

2005-0287473 (December 29, 2006)5. K. Wada et al., US Patent Application 2005-123859 (January 9, 2005)

Notes 631

B. Norbornene

a. Norborene Lactones and Sultones

Title: Norbornene-Type Monomers and PolymersContaining Pendent Lactone or Sultone Groups

Author: X. Wu et al., US Patent 7,101,654 (September 5, 2006)Assignee: Promerus LLC (Brecksville, OH)

SIGNIFICANCE

Anorbornene terpolymer containing a lactone or sulton substituent has been preparedthat is effective in photoresist compositions in the 193 and 157 nm ranges inphotolithography. An improvement in etch resistance was also observed.

REACTION

O

O2S

OH

O

O2S

OH

OSO2

OO

t-C4H9

i ii

a b

Note 1

i: THF, n-butyl lithium, 5-norbornene-2-carboxaldehyde, ethyl acetateii: t-Butyl 5-norbornene-2-carboxylate, bis(toluene)bis(perfluorophenyl) nickel (II)

EXPERIMENTAL

1. Preparation of Hydroxyl Containing Sultone Norbornene

A reactor containing 4-butane sultone (0.20mol) dissolved in 150ml of THF wascooled�70�C and treated dropwise with 21.0ml of 10M n-butyl lithium followed by

632

the slow addition of 5-norbornene-2-carboxaldehyde (0.20mol) by syringe. Thereaction mixture was stirred overnight at ambient temperature and then poured intowater and extracted with EtOAc. It was dried usingMgSO4 and concentrated, and theresiduewas purified by re-crystallization inEtOAc.Theproductwas isolated in 40.6%yield with an endo/exo isomer ratio of 89:11, respectively.

2. Preparation of Poly(t-Butyl 5-Norbornene-2-Carboxylate-co-Carboxy-t-Butoxy Sultone Norbornene)

In a 100-ml crimped vial, t-butyl 5-norbornene-2-carboxylate (17.5mmol) and theStep 1 product (7.5mmol) were dissolved in 40ml of toluene and then sparged withnitrogen for 30minutes. Themixturewas next treatedwith the slowaddition of freshlyprepared bis(toluene)bis(perfluoro-phenyl) nickel (II) catalyst (0.5mmol) in 10ml ofdry toluene and stirred overnight. The polymer was precipitated into hexane andfiltered, and 3.5 g of white powder were isolated.

DERIVATIVE

The lactone terpolymer, (I), was also prepared.

OO

c

OSi(CH 3)3

CF3

a b

O OF3C

OH

(I)

ETCH RESISTANCE TESTING

A 25% solution of terpolymer (I) dissolved in propylene glycol methylether wasprepared and thin films spun onto 4-inch silicon wafers to test for etch resistance andphotolithography performance. Etch resistance testing was conducted in a plasma

1H-NMR (500MHz, CDCl3) [endo isomer]: 6.20 (dd, 1H), 6.04 (dd, 1H), 4.47 (m, 2H), 3.73 (m, 1H), 3.08(m, 1H), 3.04 (m, 1H), 2.84 (m, 1H), 2.2 2.35 (m, 3H), 1.97 (m, 2H), 1.74 (m, 1H), 1.46 (m, 1H),1.24 (m, 1H), 0.5 (d, 1H)

13C-NMR (125MHz, CDCl3) [endo isomer]: 138.06, 132.63, 74.21, 70.86, 62.32, 49.22, 44.15, 42.46,41.51, 28.87, 24.40, 21.94

FI-MS m/e [endo isomer]: 258

13C-NMR (125MHz, CDCl3): (173.4, (C¼O); 79.24, (t-C of t-butyl ester); 62 78 (br),m, (3C-alcohol, andC next to sultone), 43.7 (br), 28.52 s, t-butyl groups)

GPC: Mn¼ 12,460 daltons, Mw¼ 18,100 daltons.

Etch Resistance Testing 633

therm reactive ion etching unit operating at 150W and 50mTorr using a CHF3/O2

etchant. The gas flow rates for CHF3 and O2 were 22.5 and 2.5 standard cubiccentimeters per minute, respectively. Testing results are provided in Table 1.

NOTES

1. Additional norbornene copolymers, (II), effective in photoresist compositionsin the 193 and 157 nm ranges were prepared by the author [1] in a subsequentinvestigation.

(II)O

SO2

HC

OO

a b c

2. Amoroso [2] prepared norbornene co-polymers, (III) and (IV), whichwere usedin photosensitive dielectric resin compositions and as films in electronic andoptoelectronic devices.

OH

n = 0,1

CF3

a b

F3COH O

nHOHN

a b

O

OH

O

(IV)

(III)

TABLE 1. Testing results for etching rates for experimental terpolymer (I) and tworeference agents. Higher etching levels are preferred.

Entry Description Etch Rate (A�=minÞ Etch/Novolac Ratio

Terpolymer (I) Experimental Agent 604.91 1.35Reference 1 Novolac 447.17 1.00Reference 2 SiO2 104.89 0.23

634 Norbornene-Type Monomers and Polymers Containing Pendent Lactone or Sultone Groups

3. Sato [3] and Koyama [4] prepared lactone copolymers, (V) and (VI), respec-tively, that were effective in positive resist compositions suitable for use insuper-microlithography processes such as the manufacture of super-LSI andhigh-capacity microchips.

O

O

O O O O

a b

(VI)

O-t-C4H9

O O

O

O

ba

(V)

4. Methacrylate-styryl terpolymers, (VII), and perfluoronorbornene copolymersprepared by Taylor [5] were used in photoresist compositions and wereeffective at 157 nm and used in short wavelength imaging.

OH

O O

C5F11 C5F11

F5 F4

a b c

(VII)

5. Photoresists prepared by Afzali-Ardakani [6] consisting of crosslinkable calix[4]arenes had resolutions of less than 100 nm.

References

1. X. Wu et al., US Patent Application 2005-00153240 (July 14, 2005)2. D. Amoroso et al., US Patent Application 2006-0008734 (January 12, 2006)3. K. Sato et al., US Patent Application 2007-0042291 (February 22, 2007)4. H. Koyama et al., US Patent Application 2006-0281022 (December 14, 2006)5. G. N. Taylor et al., US Patent 7,132,214 (November 7, 2006)6. A. Afzali-Ardakani et al., US Patent 7,037,638 (May 2, 2006)

Notes 635

b. Norborene Silsesquioxanes

Title: Photoresists Containing SulfonamideComponent

Author: S. Kanagasabapathy et al., US Patent 7,189,490 (March 13, 2007)Assignee: Shipley Company, L.L.C. (Marlborough, MA)

SIGNIFICANCE

Photoresist compositions have been prepared that consist of silsesquioxanes contain-ing sulfonamide substituents. These materials are useful in multilayer resist systemsthat provide contrast upon exposure to photogenerated acid.

REACTION

H2N HNSO2CF3

HNSO2CF3

SiCl3

i ii

t-C4H9-OO

t-C4H9-OO

SiCl3

Intermediate

iviiiIntermediate

SiO

O SiO

O

O-t-C4H9

OHNSO2CF3

i: THF, pyridine, trifluoromethanesulfonylchloride,ii: Platinum-divinyltetramethyldisiloxane, toluene, trichlorosilaneiii: Palladium acetate, triphenylphosphene, trichlorosilane, toluene,iv: Diethyl amine, water, toluene, potassium hydroxide

636

EXPERIMENTAL

1. Preparation of 5-Norborene- 2-Aminomethyltrifluorosulfonamide

A dry 250-ml flask was charged with 80ml of THF, pyridine (9.7 g), and norborneneamine (12.3 g) and then cooled to 0�C, treated with trifluoromethanesulfonylchloride(16.9 g) and stirred 4 hours. The mixture was filtered and the THF evaporated. Theresidue was dissolved in diethyl ether and washed with 3.5% hydrochloric acid,followed by water until a pH of 7 was obtained. Diethyl ether mixture was dried usingNa2SO4 and concentrated, and an oily material was isolated.

2. Preparation of Norbornyl-1-Trichlorosilyl-3-Aminomethyltrifluorosulfonamide

A100-ml flask was flushedwith nitrogen, chargedwith platinum-divinyltetramethyl-disiloxane (200mg) and 25ml of toluene, and then stirred at ambient temperature.This mixture was treated with the Step 1 product (10.0 g) followed by the dropwiseaddition of trichlorosilane (20 g) at ambient temperature. The reaction mixture wasstirred at 50�C for 48 hours and distilled, and the product was isolated in >95% yield.

3. Preparation of t-Butyl-Norbornyl-1-Trichlorosilyl-3-Carboxylate

A100-ml flaskwas flushedwith nitrogen and chargedwith palladium acetate (60mg),triphenylphosphene (180mg), 25ml of toluene, and norbornene t-butylester (10.0 g)and then stirred at ambient temperature. This mixture was next treated with thedropwise addition of trichlorosilane (20 g) and stirred at 50�C for 48 hours. Afterdistillation the product was isolated in >95% yield.

4. Preparation of Poly(t-Butyl-Norbornyl-1-Siloxy-3-Carboxylate)-co-Norbornyl-1-Siloxy-3-Aminomethyltrifluorosulfonamide)

A flask was charged with diethyl amine (11 g), 17ml of water, and 10ml of toluene,and the temperature lowered to between 0�C and �5�C. This mixture was treatedwith the Step 2 and Step 3 products followed by the dropwise addition of toluene(40 g). Thereafter the mixture was warmed to ambient temperature and stirred for90 minutes. The two layers were separated by the addition of extra water to dissolvethe quaternary ammonium salt. Oily materials/residue present in the mixture weredissolved in toluene upon heating to 50�C. The toluene layer waswashed three timeswith 1500ml of water, oncewith 50ml of 10% acetic acid, and additional water untila pH of 7 was obtained. The toluene layer was added into a 250-ml flask and treatedwith KOH (0.21 g) dissolved in 1ml of water followed by a 1-ml water rinse. Themixture was refluxed for 2 hours to azeotrope off the water and washed twice with50ml of 20% acetic acid and de-ionized water until a pH of 7 was obtained. Thetoluene solution was washed with IRN-150 for 2 hours to remove toluene, and theproduct was isolated.

Experimental 637

DERIVATIVES

The terpolymer, (I), was also prepared.

a b c

SiO

O SiO

O Si

O-t-C4H9

OHNSO2CF3

O

CH3

O

(I)

TESTING

Photoresist Preparation and Lithographic Processing (Darkfield Formulation)

A resist formulation solution was prepared by dissolving terpolymer (I) derivative(1.79 g), triphenylsulfonium perfluorobutanesulfonate (0.082 g), Troeger’s base(0.013 g), and surfactant (0.002 g) in 2-heptanone (17.9 g) and then filtering througha 0.1 micron teflon filter. Using a TEL ACT 8Coater/Developer Track, the resist wascoated onto 8 inch silicon wafers, which were coated with a 510-nm underlayer andheated to 90�C for 60 seconds to form a 150-nm resist film. The coated wafers werethen exposed through a mask pattern using an ASM PAS 5500/1100 193 nm scanner.Theexposedwaferswereheated to90�Cfor120 seconds anddeveloped for60 secondsat 20�C using 0.26M aqueous alkaline developer solution. Finally, the wafers wererinsed with deionized water and dried. Extremely good focus latitude of thisphotoresist for 90-nm contact holes were reported by the author.

NOTES

1. Silsesquioxane oligomers, (II), were prepared by Barclay [1] and used inoptoelectronics, particularly waveguides including polarizers, spectral filters,and wavelength division multiplexing structures. Polymerizable silsesquiox-ane cage structures containing 8, 10, or 12 components, (III), were preparedby Morita [2] as a method for forming an insulating film having desirabledielectric characteristics. Polymeric silsesquioxane cubanes, (IV), preparedby Hatakeyama [3] demonstrated improved alkali solubility under the actionof an acid. In addition the material remained sensitive to high-energyradiation and had high sensitivity and resolution up to 300 nm.

638 Photoresists Containing Sulfonamide Component

Si

Si

Si

Si

Si

Si

Si

Si

O O

O

O

OO

O

O

OO

O

O

C5H9

C5H9

C5H9

C5H9

C5H9

C5H9

C5H9

O SiO

SiO

SiOSi

OSiO

Si

O Si

O

Si

O

Si

OSi

O

Si

O

Si

O

O

O

O

O

(III)

SiO

Si

O

OSi

O

OH

O

HO

Si Si SiHOO

R R R

R RR

OH

R = Norbornyl

(II)

(IV)

2. Photoresist compositions containing fluorinated silicon components within asilsesquioxane resin, (V), were prepared by the author [4] and Barclay [5] thatexhibited reduced outgasing when exposed to laser radiation, including ArFexposures.

Notes 639

SiO

O SiO

O

O-t-C4H9

O

CF3

(V)

F3C

HO

3. A positive resist composition containing a silsesquioxane resin, (VI), wasprepared by Tamura [6] that exhibited increased alkali solubility under theaction of acid.

SiO3/2 SiO3/2 SiO3/2.... ............

HO O

O

(VI)

4. Norbornene photoresist monomers, (VII), effective for deep UV applicationswere prepared by Rahman [7].

O

O

OO

(VII)

640 Photoresists Containing Sulfonamide Component

References

1. G.G. Barclay et al., US Patent 7,008,750 (March 7, 2006)2. K. Morita et al., US Patent Application 2007-0054135 (March 8, 2007)3. J. Hatakeyama et al., US Patent 6,994,946 (February 7, 2006)4. S. Kanagasabapathy et al., US Patent Application 2004-0229159 (November 18, 2004) and US Patent

Application 2004-0224255 (November 11, 2004)5. G.G. Barclay et al., US Patent Application 2004-0209187 (October 21, 2004)6. K. Tamura et al., US Patent Application 7,094,849 (August 22, 2007)7. M.D. Rahman, US Patent 7,189,491 (March 13, 2007)

Notes 641

C. Adamantane

a. Adamantane Methacrylates

Title: Tertiary (Meth)Acrylates Having LactoneStructure, Polymers, Resist Compositions,and Patterning Process

Author: F. Watanabe et al., US Patent 7,037,995 (March 2, 2006)Assignee: Shin-Etsu Chemical Co., Ltd. (Tokyo, JP)

SIGNIFICANCE

A terpolymer consisting of approximately equal ratios of norbornane-2,6- carbo-lactone and 1- and 2-adamantly derivatives was free radically prepared using N,N0-azobisisobutyronitrile. These materials had improved transparency at the exposurewavelength of an excimer laser and dry etching resistance. Positive resist compo-sitions comprising this polymer were sensitive to high-energy radiation and lendthemselves to micropatterning with electron beams or deep-UV radiation.

642

REACTION

CO2CH3

OO

OO

OH

OO

OO

OO

OO OO OO

HO

0.35 0.35 0.30

iiiiiiNote 1

i: THF, methylmagnesium chlorideii: CH2Cl2, triethylamine, methacryloyl chlorideiii: 2-Ethyl-2-adamantyl methacrylate, 3-hydroxy-1-adamantyl methacrylate,N,N0-

azobis isobutyronitrile, THF

EXPERIMENTAL

1. Preparation of 3-(1-Hydroxy-1-Methylethyl)-2,6-Norbornanecarbolactone

While stirring under nitrogen at 0�C, a THF solution containing methylmagnesiumchloride (860mmol) was added to a solution of methyl 2,6-norbornanecarbolactone-3-carboxylate (80 g) dissolved in 500ml of THF and then stirred for one hour. Themixturewas quenchedwith an aqueous solution of NH4Cl followed by a conventionalaqueous workup. The product was isolated after distillation of the solvent.

2. Preparation of 3-(1-Methacryloyloxy-1-Methylethyl)-2,6-Norbornanecarbolactone

Under ice cooling a reactor was charged with the entire Step 1 product, triethylamine(70 g), and CH2Cl2 (400 g) and then treated with methacryloyl chloride (55 g) andstirred 12 hours at ambient temperature. The reaction was quenched by adding waterfollowed by a conventional aqueous workup. The mixture was concentrated, and theresidue was washed with hexane and dried; 86 g of product were isolated.

FTIR (KBr, cm�1) 2971, 2960, 2951, 1763, 1711, 1637, 1463, 1450, 1388, 1373, 1331, 1311, 1273, 1203,1167, 1144, 1126, 1115, 1049, 1012, 968, 957, 945

1H-NMR (270MHz inCDCl3)d1.32 (3H, s), 1.50 (1H,m), 1.54 (3H, s), 1.651.80 (2H,m), 1.90 (3H,m), 2.20(1H, m), 2.45 (1H, m), 2.53 (1H, m), 3.05 3.15 (2H, m), 5.03 (1H, m), 5.57 (1H, m), 6.17 (1H, m)

Experimental 643

3. Preparation of Poly(3-(1-Methacryloyloxy-1-Methylethyl)-2,6-Norbornanecarbolactone-co-2-Ethyl-2-Adamantyl Methacrylate-co-3-Hydroxy-1-Adamantyl Methacrylate)

A reactor was charged with the Step 2 product (9.2 g), 2-ethyl-2-adamantyl methac-rylate (7.4 g), 3-hydroxy-1-adamantyl methacrylate (8.3 g), N,N0-azobisisobutyroni-trile (60mg), and 80ml of THF and then stirred 20 hours at 60�C. After cooling thereaction mixture was added dropwise to 2 liter of methanol, and the precipitate wasisolated by filtration. The solids were washed with methanol and dried; 19.9 g ofproduct were isolated having a Mw of 9800 daltons with a polydispersity of 1.80.

DERIVATIVES

No additional derivatives prepared.

TESTING

Polymer Transparency

The Step 3 product was dissolved in cyclohexanone (6.0 g) and filtered through a0.2 mm pore diameter teflon filter. The solution was then spin-coated onto a quartzsubstrate and heated 60 seconds at 90�C, forming a 500 nm thick film. Transmittancewas measured at 193 nm using a UV-visible spectrophotometer where it was deter-mined the film had a transmittance of 78% per 500 nm thickness. This resultdemonstrates that this material was sufficiently transparent for use as a photoresistbase polymer in excimer laser photolithography.

Resist Pattern Formation Using Polymer

A resist material was prepared consisting of:

1. 80 parts by weight of the Step 3 product,

2. 1.0 part by weight of triphenylsulfonium trifluoromethanesulfonate as aphotoacid generator,

3. 480 parts by weight of propylene glycol monomethyl ether acetate as a solvent,and

4. 0.08 part by weight of tributylamine as a basic compound.

The mixture was initially filtered through a 0.2 mm pore diameter teflon filter. Itwas spin-coated onto a silicon wafer previously sprayed with hexamethyldisilazaneand baked for 40 seconds at 90�C and 90 seconds at 110�C, forming a 500 nm resistfilm. The resist film was exposed to ArF excimer laser light, heat treated for90 seconds at 110�C, and cooled to ambient temperature. It was then dipped in2.38% aqueous tetramethylammonium hydroxide solution for 60 seconds for devel-opment where it formed a 1 : 1 line-and-space pattern. The wafer as developed was

644 Tertiary (Meth)Acrylates

observed under SEM, which showed that patterns down to a line width of 0.13 mmwere left unstripped and thus resolved. This demonstrates that the photoresistmaterial has improved substrate adhesion and resolution.

NOTES

1. Additional positive resist adamantyl polymers, (I), were prepared by the author[1] in a subsequent investigation.

O

OO

OO OO OO

HO

0.40 0.20 0.20

O O

0.20

(I)

2. In other investigations by the author [2,3] additional positive resists composi-tions were prepared containing either imidazole, (II), or tertiary amine deri-vatives, (III), respectively, and then blended with the select copolymer, (IV), asillustrated.

OH

O O

N

O

O

O

O

O

O

(II)

NN CO2CH3

(IV)

0.73 0.27

(III)

Notes 645

3. A positive resist silicon-containing polymer, (V), was prepared by Kinsho [4]having a resolution wavelength of less than 300 nm that was resistant to oxygenplasma etching.

OO

OO

Si(CH3)3

OO

O

Si(CH3)3 Si(CH3)3

OO

Si(Si(CH3)3)3

0.4 0.5 0.1

(V)

4. Positive resist terpolymeric ester derivatives, (VI), prepared by Hasegawa [5]were sensitive to high-energy radiation while having improved sensitivity,resolution, and etch resistance. They were especially useful in micropatterningwith electron beams or deep-UV radiation.

OO

OO OO

0.30 0.35

O O

0.35

OH

O

(VI)

References

1. T. Watanabe et al., US Patent 7,135,270 (November 14, 2006)2. T. Watanabe et al., US Patent Application 2005-0008968 (January 13, 2005)3. T. Watanabe et al., US Patent 7,084,303 (August 1, 2006)4. T. Kinsho et al., US Patent 7,192,684 (March 20, 2007)5. K. Hasegawa et al., US Patent 7,132,215 (November 7, 2006)

646 Tertiary (Meth)Acrylates

b. Adamantane 4-Hydroxyphenyl Methacrylates

Title: Chemical Amplification Type Positive ResistComposition

Author: A. Yamada et al., US Patent 7,202,010 (April 10, 2007)Assignee: Sumitomo Chemical Company, Ltd. (Osaka, JP)

SIGNIFICANCE

As a consequence of needing higher integration in existing integrated circuits arequirement for formation of submicron patterns has become necessary. Chemicalamplification using positive resist resins containing adamantane have been preparedthat have particularly good resolution to meet this latest requirement with only anominal cost increase.

REACTION

O

O

O

O

O O

OH

O O

0.7 0.30.7 0.3

i ii

EXPERIMENTAL

1. Preparation of Poly(2-Ethyl-2-Adamantyl Methacrylate-co-p-Acetoxystyrene)

A reaction flask was charged with 2-ethyl-2-adamantyl methacrylate (0.24mol),p-acetoxystyrene (0.56mol), and isopropanol (279 g) and then heated to 75�C. Thismixturewas next treated with dimethyl-2,20-azobis(2-methylpropionate) (0.048mol)dissolved in isopropanol (22.11 g), stirred 20 minutes, and finally refluxed for

647

12 hours. The solution was diluted with acetone and then precipitated in methanol;250 g of the copolymer were isolated.

2. Preparation of Poly(2-Ethyl-2-Adamantyl Methacrylate-co-p-Hydroxystyrene)

The entire Step 1 product was mixed with 4-dimethylaminopyridine and 239 g ofmethanol and then refluxed 20 hours. After cooling the mixture was neutralized withglacial acetic acid (0.133mol) and precipitated inwater. The precipitatewas dissolvedin acetone and then re-precipitated in water, the process being repeated three times.The precipitatewas dried, and 102.8 g of polymer product were isolated, consisting of70% p-hydroxystyrene and 30% 2-ethyl-2-adamantyl methacrylate with a Mw of8200 daltons and polydispersity of 1.68.

DERIVATIVES

Three additional p-hydroxylstyrene copolymers were prepared.

OOH

O O

0.8 0.2 0.69 0.31

HO OO

0.65 0.35

HO

NOTES

1. In an earlier investigation by the author [1] a sulfonium salt pair, (I), was used asa chemical amplification type resist that utilized the catalytic action of an acidgenerated from a sulfonium salt. In a subsequent investigation by Kamabuchi[2] an acid generator salt pair, (II), was prepared andwas effective as a chemicalamplification type positive resist.

OO

O O

S

O

S

(I)

(II)

Pair #1

t-C4H9 I t-C4H9

OO

OO

O

OO OO

1 2 1

O

Pair #2

648 Chemical Amplification Type Positive Resist Composition

2. Ester derivatives of 4-hydroxyl polystyrene, (III), prepared by Suetsugu [3]were effective as chemical amplification type positive photoresists.

OO

0.24 0.76

HO

OCH3(III)

3. Positive photoresist amplifier perfluoro polymers, (IV), (V), (VI), and (VII),prepared by Kanna [4], Hohle [5], DiPietro, [6], and Allen, [7], respectively,were effectivewith an exposed light source of 160 nmand thus usablewith an F2excimer laser beam.

b

F2C

F

HO

F3CCF3

F2C

O O

t-C4H9

50 25 25

(VI)

FF

F

OHF3C CF3

(VII)

O

OH

CF3F3C

OO

O

HO

O O

F3C CF3

HO

aa

a

(IV)(V)

Notes 649

References

1. A. Yamada et al., US Patent 7,160,669 (January 9, 2007)2. A. Kamabuchi et al., US Patent 7,135,268 (November 14, 2006)3. M. Suetsugu et al., US Patent 6,828,079 (December 7, 2004)4. S. Kanna et al., US Patent 7,202,015 (April 10, 2007)5. C. Hohle et al., US Patent 7,169,531 (January 30, 2007)6. R.A. DiPietro et al., US Patent 7,150,957 (December 19, 2006)7. R.D. Allen et al., US Patent 7,014,980 (March 21, 2006)

650 Chemical Amplification Type Positive Resist Composition

D. Diamantane Acrylate

Title: Positive Photosensitive Compositionand Pattern-Forming Method Using the Same

Author: F. Nishiyama et al., US Patent Application 2007-0072118 (March 29, 2007)Assignee: Fuji Photo Film Co., Ltd. (Tokyo, JP)

SIGNIFICANCE

When an emitting light at a wavelength of 200 nm is used as the light source, asatisfactory pattern cannot be formed using photosensitive compositions containingaromatic substituents. To address this concern, non-aromatic photosensitive poly-meric compositions containing diamantane have been prepared.

REACTION

OH O

O

i

OO

O

O

OOO

OH

O O

2040

2020

ii

O

Note 1

i: Methacrylic anhydride, sulfuric acid, tolueneii: Propylene glycol monomethyl ether acetate, propylene glycol monomethyl

ether, 3-hydroxyadamantane methacrylate, 2-methyl-2-adamantyl methacrylate,g-butyrolactone methacrylate

651

EXPERIMENTAL

1. Preparation of Diamantyl Methacrylate

Hydroxydiamantane (9.8 g),methacrylic anhydride (3.7 g), and 0.5 g of 18MH2SO4

were dissolved in 150ml of toluene and refluxed for 2 hours. The reaction solutionwas then washed with aqueous NaHCO3, dried using Na2SO4, and concentrated.The residue was purified by column chromatography, and 6.3 g of product wereisolated.

2. Preparation of Diamantyl-Containing Positive Photoresist Resin

A reaction kettlewas chargedwith propylene glycol monomethyl ether acetate (5.1 g)and propylene glycol monomethyl ether (3.4 g) and then heated to 80�C. This mixturewas next treated dropwise with the Step 1 product (2.7 g), 3-hydroxyadamantanemethacrylate (4.7 g), 2-methyl-2-adamantyl methacrylate (7.0 g), g-butyrolactonemethacrylate (6.8 g), and the free radical initiator V-601. Thereafter the reactionproceeded for 2 hours at 80�Candwas then cooled and poured into a 720mlmixture ofhexane containing 80ml of EtOAc. The precipitatewas collected, and 18 g of productwere isolated having a Mw of 10,700 daltons with a polydispersity of 1.81.

DERIVATIVES

OO O OO

OH

O O

2040

2020

O

OH

OO (I)

OO O OOO O

1040

4010

O

OO

OH

O

O

OO

(II)

652 Positive Photosensitive Composition

OO O OOO OH

2030

4010

O

OH

OO

(III)

NOTES

1. Terpolymer photoresist devoid of diadamantyl or aromatic components butcontaining adamantyl substituents, (IV), were prepared by Tarutani [1] andwere effective at 157 and 193 nm.

OO

O

O

OOO

OH

2040

40

O

(IV)

2. Eda [2] cyclopolymerized 1,6-perfluorohepadiene derivative, (V), to prepare aphotoresist copolymer composition having the repeat unit, (VI), and it waseffective at 157 and 193 nm.

a

CF2

CFF2C

F3C CF3HO

CF2

CF

F2C

F3C CF3HO

(VI)(V)

Notes 653

3. Choi [3] prepared photoresist resins useful at 157 and 193 nm containingpolyhedral silsesquioxane substituents as illustrated (VII) below.

OHO O O

OH

O O

a b c

Silicon Cage

(VII)

4. Chemical amplification type positive resist compositions provided in Table 1were prepared by Takemoto [4] and were suitable for excimer laser lithographyusing ArF and KrF lasers.

TABLE 1. Aromatic-free photoresists suitable for excimer laser lithography usingArF and KrF lasers prepared by Takemoto [4].

EntryMonomer

ID StructurePolymer Composition and

Monomer Ratio Mw (daltons) PDI

1 AOO

A/C/D/E¼ 25/25/25/25 10,030 1.87

2 BOO

A/C/D/F¼ 25/25/25/25 9,610 1.74

3 COO

A/C/DE/F¼ 20/25/30/20/5 9,897 1.88

4 DOO

O OA/C/DE/F¼ 30/15/30/20/5 9,240 1.54

654 Positive Photosensitive Composition

References

1. S. Tarutani, US Patent Application 2007-0077519 (April 5, 2007)2. M. Eda et al., US Patent Application 2007-0083021 (April 12, 2007)3. S.-J. Choi et al., US Patent Application 2007-0082297 (April 12, 2007)4. I. Takemoto et al., US Patent 7,205,090 (April 17, 2007)

5 EOO

OO

A/C/DE/F¼ 20/25/30/15/10 8,600 1.44

6 FOO

OH

A/H/DE/F¼ 20/20/30/15/15 7,590 1.64

7 GOO

B/G¼ 50/50 7,860 1.77

8 HOO

A/G¼ 50/50 9,920 1.95


EntryMonomer

ID StructurePolymer Composition and

Monomer Ratio Mw (daltons) PDI

Notes 655

XXII. SEPARATIONS

A. Gases

Title: Dithiolene Functionalized Polymer Membranefor Olefin/Paraffin Separation

Author: W. J. Koros et al., US Patent 7,160,356 (January 9, 2007)Assignee: Board of Regents, The University of Texas System (Austin, TX)

SIGNIFICANCE

Blended polyimide composites containing 11% neutral dithiolene nickel(II) deriva-tiveswere selective for propene inpropene/propane stream feeds.Evidenceofpropeneabsorptionwas indicated by a color change of the composite. The selectivity ratiowasbetween about 1.1 and 2.0.


657

REACTION

CF3F3C

OO

O

O

O

O CF3F3C

NN

O

O

O

OCF3

CF3

CF3F3C

NN

O

O

O

OF3C CF3

S

S SNi

S

SS

F3C CF3

a

a

i ii

Blend

SNi

HS

S

HS CF3

F3C

F3C

CF3

iii

Olefinic complex in blend

Note 1

i: 4,40 (Hexafluoroisopropylidene)dianiline, DMAc, triethylamine, acetic anhy-dride, CH2Cl2

ii: bis[(1,2-Trifluoromethyl)ethylene-1,2-dithiolato] nickel(II), tolueneiii: Toluene, propene/propane

EXPERIMENTAL

1. Preparation of Poly[(4,40-(Hexafluoroisopropylidene)-(4,40-(Hexafluoroisopropylidene)-Phthalimide]

4,40-Hexafluoroisopropylidene dianiline was dissolved in DMAc and then treatedwith the dropwise addition of 4,40-hexafluoroisopropylidene diphthalic anhydride atambient temperature. The20 to 25wt% solutionwas next stirred 6 to 8 hours until highmolecular polyamic acidswere formed. Themixturewas treatedwith a large excess oftriethylamine and acetic anhydride and dehydrated by heating to 50�C for 2 to 3 hoursand at 100�C to 110�C for 10 to 20 minutes then cooled to ambient temperature. Theviscous solution was slowly poured into methanol, and the precipitate was homoge-nized in a blender. It was then filtered and washed several times with fresh methanol.The material was dried for 12 hours at ambient temperature and 24 hours undervacuum at 250�C, and the product was isolated.

658 Dithiolene Functionalized Polymer Membrane for Olefin/Paraffin Separation

2. Poly[(4,40-(Hexafluoroisopropylidene)-(4,40-(Hexafluoro-Isopropylidene)-Phthalimide] Film Blend Containing bis[(1,2-Trifluoromethyl)Ethylene-1,2-Dithiolato] Nickel(II)

A blend was prepared by mixing an 11wt% solution of bis[(1,2-trifluoromethyl)ethylene-1,2-dithiolato] nickel(II) in toluenewith theStep1product.After themixturehad been stirred for at least 20minutes, the solutionwas filtered through a 0.2-m teflonsyringe filter. The filtered solution was then dispensed on a clean level Teflon dishcovered with a casting funnel to control the rate of solvent removal. After approxi-mately 8hours filmswere isolated. Thesematerialwere further dried in avacuumovenat 100�C for at least 24 hours, and the product was isolated as a clear film.

3. Selective Solubility of C3H6/C3H8 through Poly[(4,40-(Hexafluoroisopropylidene)-(4,40-(Hexafluoro-Isopropylidene)-Phthalimide] Film Blend Containing 11% bis[(1,2-[Trifluoro-Methyl)ethylene-1,2-Dithiolato] Nickel(II)

AC3H6/C3H8mixturewas bubbled through a solution of the Step 2 product in tolueneat atmospheric prressure. In approximately 30 minutes the film turned yellowishgreen, which is indicative of complexation with propylene.

DERIVATIVES

Neutral and ionic dithiolene derivatives that were prepared and used in polyimidecomposites are provided in Tables 1 and 2, respectively.

X S

SNi

X S

S X

X

TABLE 1. Neutral dithiolene derivatives blendedin polyimide composites.

Entry X

1 CH3

2 CF33 4-C4H4OCH3

Note: Only entry 2was effective in separating propene frompropene/propane mixtures.

Derivatives 659

SM

S

X

X

A

TESTING

Results of polyimide dithiolene blends on the selective adsorption of propene frompropene/propane mixtures are provided in Table 3.

NOTES

1. Selective polyimide membranes, (I), for helium, carbon dioxide, and oxygenwere previously prepared by the author [1] by condensing 4,40-(hexafluoro-isopropylidene) diphthalic anhydride with a 3:2 ratio of 2,4,6-trimethyl-1,3-phenylene diamine and diamino benzoic acid, respectively.

TABLE 2. Ionic dithiolene derivatives used in polyimide composite blends.

Entry Aþ X M�

6 N(n-C4H9)4 CH3 Ni7 N(n-C4H9)4 CH3 Pt8 N(n-C4H9)4 CH3 Fe9 N(C2H5)4 CN Co

Note: None of the blends were effective in selectively adsorping propene from propene/propane mixtures.

TABLE 3. Results of polyimides membrane blends containing 11% dithioleneon the selective adsorption of propene from propene/propane mixtures.

EntryAbsorptionSolvent

Pre-C3H6 AdsorptionPolymer Composite

Color

Post-C3H6 AdsorptionPolymer Composite

Color

Duration ofC3H3/C3H8

Introduction (hours)

1 Toluene Dark purple Color unchanged 32 Toluene Dark with a purple tint Yellowish green 0.53 Toluene Dark forest green Color unchanged 36 Toluene Green with blue tint Color unchanged 37 Toluene light blue Color unchanged 38 DMAc light red Color unchanged 39 DMAc Yellow Color unchanged 3

Note: A polymer blend color change is indicative of propene adsorption. Only entry 2 was effective.

660 Dithiolene Functionalized Polymer Membrane for Olefin/Paraffin Separation

N

O

O

F3C CF3

N

O

O

N

O

O

F3C CF3

N

O

OCO2H

(I)

a b

2. When poly(2,20-(m-phenylene)-5,5-bibenzimidazole) having aMn of 2.0� 104

daltons was crosslinked with tetrahydrothiophene-1,1-dioxide, (II), or 1,4-phenylene, (III), by Young [2] and Jorgensen [3], respectively, each membranewas selective for hydrogen, carbon dioxide, nitrogen, and methane.

N

N

A

HN

NH

N

N

a

CH2

CH2

O2SCH2

CH2

(II)(III)

A =

a

3. Benzimidazole-containing sulfonated polyimides, (IV), prepared by Brunelle[4] were effective as proton exchange membranes for fuel cells.

O

N

O O

O O

N

O O

O

NH

N

a

b

(IV)HO3SSO3H

References

1. W.J. Koros et al., US Patent 6,755,900 (June 29, 2004)2. J.S. Young et al., US Patent 6,997,971 (February 14, 2006)3. B.S. Jorgensen et al., US Patent 6,946,015 (September 20, 2005)4. D.J. Brunelle et al., US Patent Application 2007-0112170 (May 17, 2007)

Notes 661

B. Solutions

a. Amine Separation

Title: Tethered Polymer Ligands

Author: R. F. Hammen et al., US Patent 7,220,703 (May 22, 2007)Assignee: Hammen Corporation (Missoula, MT)

SIGNIFICANCE

A method for preparing polyisobutylene-g-acrolein and then converting intopolyisobutylene-g-alkylamines is described. These polymeric agents are designedfor binding biomacromolecules and metal ions to the amine surface.

662

REACTION

Cl3Si

OO

O

Blocking groups

Blocking groups

OO

O

Blocking groups

Blocking groups O O O

OO

O

Blocking groups

Blocking groupsNHR NHR NHR

Silica

Silica

Silica

a

a

a

aa

.....

Not isolated

ii

iii

i

R= CH2(CH2)4CH2NH2

i: Trichlorosilane, chloroplatinic acid, silica gel, pyridine, bis(trichlorosilyl)ethaneii: Acrolein, 2,20-azobis(2-methylpropioniamidine) dihydrochloride, wateriii: Pentaethylene hexamine, acetic acid, ethanol, sodium borohydride

EXPERIMENTAL

1. Preparation of Polybutadiene Silica

Phenyl terminated polybutadiene (Mn� 1300 daltons, 45% vinyl) was reacted withtrichlorosilane and chloroplatinic acid and then mixed with a slurry of 105 m particlesize silica gel having a 250A

�average pore diameter in dry toluene for 24 hours. The

quantity of trichlorosilane used was 2mol per mole of polybutadiene. Pyridine wasadded to remove HCl, and the slurry was gently shaken for 18 hours at ambienttemperature. The surface of the silica was blocked by addition of 1,2-bis(trichlor-osilyl)ethane, and the mixture was treated with pyridine. After three hours of shakingthe reaction was worked up by vacuum filtration in a sintered glass funnel and washedwith toluene and methanol. The modified silica gel was dried in the filter funnel bycontinued application of vacuum to the filter funnel.

Experimental 663

2. Preparation of Polyacrolein Silica

The Step 1 product was packed into a 4.6� 100mm high-pressure liquid chromato-graphy column and treated with 1.0M acrolein and 0.025M 2,20-azobis(2-methyl-propioniamidine) dihydrochloride dissolved in water. This mixture was injected intothe column, and both ends of the column were plugged. The column was thenimmersed in a 78�C water bath for 2 hours to complete the reaction.

3. Reductive Amination of Polyacrolein Silica with Pentaethylene Hexamine

The Step 2 product was packed into an HPLC column and 1M solution pentaethylenehexamine and 0.1M acetic acid in anhydrous ethanol injected into the column. After 2hours a 0.6M sodium borohydride solution in anhydrous ethanol was injected into thecolumn. After an additional hour unreacted reagents were flushed from the column.The resulting polypentaethylene hexamine silica was able to hold about 800 mmolcopper per gram of silica gel.

NOTES

1. Additional derivatives of the current invention are provided by the author [1] inan earlier investigation.

2. In a previous investigation by the author [2] composite matrices consisting ofpolyethylene glycol microspheres containing pendant polyacrolein havingsolid spaces, interstitial spaces, and interstitial polymer networks were pre-pared and used to isolate the protein, repligen. Worms-becher [3] developedaffinity chromatographic solid compositions for selective adsorption of pro-teins from complex mixtures.

3. Solid supports consisting of oligonucletoides were prepared by Ravikumar [4]and used in the preparation of substituted pixyl alcohol and analogues.

References

1. R.F. Hammen et al., US Patent 6,689,715 (February 10, 2004)2. R.F. Hammen et al., US Patent 7,201,844 (April 10, 2007)3. R.F. Wormsbecher., US Patent 7,166,213 (January 23, 2007) and US Patent 6,998,042 (February

14, 2006)4. V. Ravikumar et al., US Patent 7,202,264 (April 10, 2007)

664 Tethered Polymer Ligands

b. Sulfones

Title: Isolatable, Water-Soluble, and HydrolyticallyStable Active Sulfones of Poly(Ethylene Glycol)and Related Polymers for Modification of Surfacesand Molecules

Author: J. H. Harris, US Patent 7,214,366 (May 8, 2007)Assignee: Nektar Therapeutics AL Corporation (Huntsville, AL)

SIGNIFICANCE

Poly(ethylene glycol) chloroethyl sulfone and -vinyl sulfone have been prepared inessentially quantitative yields, beginning with polyethylene glycol. Both productsselectively reacted with Cys-SH while remaining inert toward Lys-NH2, suggestingtheir usefulness as chromatography substrates.

REACTION

OOH

OOSO2CH3 O

SCH2CH2OH

OSO2CH2CH2Cl

67

676767i ii

iiiiv

OSO2CH=CH2

67

OSO2CH2CH2OH

67

v

i: Methanesulfonyl chloride, toluene, triethylamine, CH2Cl2ii: Mercaptoethanol, sodium hydroxide, wateriii: Hydrogen peroxide, water, tunstic acidiv: Thionyl chloridev: Sodium hydroxide, CH2Cl2

665

EXPERIMENTAL

1. Preparation of Polyethylene Glycol Mesylate

A reactionvesselwas chargedwith polyethylene glycol (25 g;Mn¼ 3400 daltons) anddried by azeotropic distillation in 150ml of toluene.The solutionwas then treatedwith40ml ofCH2Cl2 followedby cooling in an ice bath; itwas further treatedwith 1.230mlmethanesulfonyl chloride and 2.664ml of dry triethylamine. Thereafter the mixturewas stirredovernight at ambient temperature and then filtered.The solventvolumewasreduced to 20mlwhereupon the product was precipitated from solution, isolated afterfiltration, and washed with 100ml of cold diethyl ether.

2. Preparation of Poly(Ethylene Glycol) Mercaptoethanol

TheStep 1 product (25 g)was dissolved in 150ml of distilledwater and then cooled byimmersion in an ice bath and treatedwith 2.366ml ofmercaptoethanol and16.86ml of2MNaOHsolution.Themixturewas refluxed for 3hours, extracted3 timeswith25mlof CH2Cl2, and dried with MgSO4 in 25ml of CH2Cl2. The solvent volume wasreduced to 20mlwhereupon the product was precipitated from solution, isolated afterfiltration, and washed with 150ml of cold diethyl ether.

3. Preparation of Poly(Ethylene Glycol) Ethanol Sulfone

The Step 2 product (25 g)was dissolved in 30ml of 0.123M tungstic acid solution andcooled in an ice bath. The mixture was treated with 2.876ml of 30% hydrogenperoxide and stirred overnight at ambient temperature. Themixturewas then extracted3 times with 25ml of CH2Cl2, washed with dilute aqueous NaHCO3, and dried usingMgSO4. The product was isolated as described in Step 1.

4. Preparation of Poly(Ethylene Glycol) Chloroethyl Sulfone

TheStep 3product (25 g)was dissolved in 100ml of thionyl chloride and then refluxedovernight and concentrated. The residue was dissolved in 50ml apiece of toluene andCH2Cl2 and re-concentrated by distillation. The product was isolated after re-crystallization from 50ml of ethyl acetate.

1H-NMR (d6-DMSO) d PEG–SCH2CH2OH 2.57 ppm, triplet, –CH2–S–; 2.65 ppm, triplet, –S–CH2–; 3.5backbone singlet; and 4.76 ppm, triplet, –OH

1H-NMR (d6-DMSO) d PEG–SO2CH2CH2OH: 3.25 ppm, triplet, –CH2–SO2–; 3.37 ppm, triplet, –SO2–3.50 ppm, backbone; 3.77 ppm, triplet, –CH2OH; 5.04 ppm, triplet, –OH

1H-NMR (d6-DMSO) d 3.50 ppm, backbone; 3.64 ppm, triplet, –CH2SO2–; 3.80 ppm, triplet, –SO2CH2–

666 Isolatable, Water-Soluble, and Hydrolytically Stable Active Sulfones of Poly(Ethylene Glycol)

5. Preparation of Polyethylene Vinyl Sulfone

Polyethylene glycol vinyl sulfone was prepared by dissolving the Step 4 product inCH2Cl2 and treatingwith twoequivalents ofNaOHbaseThe solutionswere separated,concentrated, and the product was isolated.

DERIVATIVES


TESTING

Onlyqualitative informationwas supplied by the author concerning the selectivities ofthe Step 4 and Step 5 products with Lys-NH2 andCys-SH at pH 8 and 9.After 24 hoursat either pH neither reagent reacted with Lys-NH2; reactions with Cys-SH werecompleted within 15 minutes.

NOTES

1. In other investigations by the author [1], an additional polyethylene glycolderivative, (I), was prepared and used to modify lucifer-yellow modifiedlysozyme and bovine serum albumin.

67OO

OO

O

O

O N

O

O

O(I)

2. Isothiocyanate-terminated polyethylene glycol derivatives, (II) and (III), wereprepared by Smith [2] and Acharya [3], respectively, and were effective inselectively reacting with biomolecules including antibodies, enzymes, andproteins.

1H-NMR (d6-DMSO) d 3.50 ppm, backbone; 3.73 ppm, triplet, –CH2SO2–; 6.21 ppm, triplet, C¼CH6.97 ppm, doublet of doublets, –SO2CH–.

Notes 667

aaH3CO

OO

O NH

O

NCS

NH

O

O

OO

OCH3

(II)

OO

O NH

O

NCS

(III)

112

3. A multi-branched compound consisting of mixed polyethylene oxide seg-ments, (IV),was prepared byDavis [4] for use in diagnostics and therapeutics ofbiologically active molecules.

O

PEG4

PEG4

PEG11

PEG11

PEG11

PEG11

OPEG4

PEG4

PEG11

PEG11

PEG11

PEG11

(IV)

References

1. J.H. Harris et al., US Patent 7,214,388 (May 8, 2007), US Patent 7,166,304 (January 23, 2007) USPatent 7,030,278 (April 18, 2006), and US Patent Application 2006-0155059 (July 13, 2006)

2. P.K. Smith et al., US Patent 7,084,112 (August 1, 2006)3. S. Acharya et al., US Patent Application 2005-0159339 (July 21, 2005)4. P.D. Davis et al., US Patent Application 2006-0020134 (January 26, 2006)

668 Isolatable, Water-Soluble, and Hydrolytically Stable Active Sulfones of Poly(Ethylene Glycol)

c. Optically Active Polymaleimide Derivatives

Title: Optically Active Maleimide Derivatives, OpticallyActive Polymaleimide Derivatives, Process for TheirProduction, Separating Media Comprising the OpticallyActive Polymaleimide Derivatives, and Method ofSeparating Optically Active Compounds Using Them

Author: T. Miyata et al., US Patent 7,186,750 (March 6, 2007)Assignee: Tosoh Corporation (Yamaguchi-ken, JP)

SIGNIFICANCE

Optically active malimides have been prepared by condensing succinic anhydridewith either (1R, 2R)- or (1S,2S)-2-benzyloxycyclopentylamine and then polymeri-zing into the corresponding polysuccinimide. When used on a silica gel support in apacked chromatographic column, the polysuccinimide separated selected racemicmixtures.

REACTION

OO O

NO O

O

NO O

O

i ii

i: Benzene, (1S,2S)-2-benzyloxycyclopentylamine, zinc chloride, hexamethyl-disilazane, ethyl acetate

ii: Diethylzinc, (-)-sparteine, and toluene

669

EXPERIMENTAL

1. Preparation of N-[(1S,2S)-2-Benzyloxycyclopentyl]Maleimide

A reactor was charged with maleic anhydride dissolved in 140ml of benzene and thencooled in an ice bath to 0�C and treated dropwise with (1S,2S)-2-benzyloxycyclo-pentylamine (26.0mmol) in 80ml of benzene. The mixture was warmed to ambienttemperature and stirred for 1 hour. This mixture was treated with zinc chloride(26.0mmol), heated to 80�C, and then further treated with the dropwise addition ofhexamethyldisilazane (52.0mmol) in70mlofbenzene.Thereafter the reactionmixturewas refluxed for 5 hours. It was then cooled to ambient temperature and washed with2MhydrochloricacidandextractedwithEtOAc.Theextractwaswashedwithsaturatedaqueous NaHCO3, and the saturated brine was dried with MgSO4. The mixture wasconcentrated, the residue purified by column chromatography using n-hexane/EtOAc,9:1, respectively, and the product isolated as a pale yellow oil in 91% yield.

2. Preparation of Poly{N-[(1S,2S)-2-Benzyloxycyclopentyl]Maleimide}

A reactor was charged with diethylzinc (1.0mmol), (-)-sparteine (1.2mmol), andtoluene and then stirred for 30minutes at�10�C. Thismixturewas added to the Step 1product (10.0mmol) dissolved in 18ml of dry toluene and stirred at �10�C for 168hours. Thereafter the mixturewas poured into 200ml of methanol, and the precipitatewas collected by filtration. The reddish solid was washed with 1M hydrochloric acidand water and dried at ambient temperature under reduced pressure. The product wasisolated as a white solid in 82% yield.

3. Preparation of 10% Poly{N-[(1S,2S)-2-Benzyloxycyclopentyl]Maleimide}on a Silica Gel Support in a Packed Column

The Step 2 product (500mg) was dissolved in 10ml of CCl3H containing silica gel(4.5 g) and having an average particle size of 5 mmand average pore size of 100A

�. The

CCl3H was distilled off under reduced pressure by means of a rotary evaporator, and5 g of 10% optically active Step 2 product was loaded onto silica gel. This blend wasthen dispersed in isopropanol and packed into a stainless steel column of 4.6mm

½a�D25 ¼ þ36:6� (C¼ 1.0, THF, I¼ 10 cm)1H-NMR (CDCl3) d 7.32-7.21 (m, 5H), 6.61 (s, 2H), 4.51 4.25 (m, 4H), 2.20 1.63 (m, 6H)13C-NMR (CDCl3) d 170.39, 138.29, 133.77, 128.13, 127.34, 127.30, 81.62, 71.20, 56.66, 30.97,

27.82, 21.94MS (m/z) 272 ([MþH]+)IR (KBr, cm�1) 3099, 3065, 3031, 2962, 2874, 1768, 1705, 1595, 1496, 1454, 1404, 1203, 1176, 1140,

1027, 913, 827, 738, 696Elemental analysis: Found C 70.69; H, 6.31; N, 5.04; Calc: C, 70.83; H, 6.32; N, 5.16Mn¼ 2.05� 104 daltonsPDI¼ 7.0½a�D25 ¼ 209:6.degree. (C¼ 1.0, CHCl3)

670 Optically Active Maleimide Derivatives

ID� 150mmL by means of a high-pressure pump under a pressure of 300 kg/cm2.The theoretical plate number of the packed column was 4470.

TESTING

The effectiveness of the Step 3 optically active agent in separating selected racematesis provided in Table 1.

NOTES

1. Additional racemic mixture separations of trans 1,2- and 2,3-epoxy derivativesare provided by co-author Kagawa [1].

2. Enantioselective polyelectrolyte materials suitable for use as capillary tube andchromato-graphic packing material and consisting of polyvinyl pyridiniumsalts, (I), were prepared by Schlenoff [2] for use in analytical and membraneseparations of chiral agents.

TABLE 1. Enantionmer separation of selected compounds using the Step 2 opticallyactive agent in a GC column having a flow rate of 1.0ml/minute and using n-hexane/isopropinol, 9:1, respectively, as the mobile phase.

Entry Enantiomeric Mixture k1*1 k2*2 a*3

6 2-Methyl-1-tetralone 0.95 1.08 1.147 Benzoin 0.74 1.45 1.978 Methyl 2-chloropropionate 0.40 0.50 1.239 2-Benzoxymethyl-2,3-dihydro-4H-pyran-4-one 4.34 4.74 1.09

*1Retention coefficient of the first eluded enantiomer*2Retention coefficient of the second eluded enantiomer*3Separation factor

1H-NMR (CDCl3) d 7.35 (br, 5H), 4.50 4.02 (br, 4H), 2.04 1.74 (br, 6H).13C-NMR (CDCl3) d 176.27, 138.24, 128.28, 127.78, 127.44, 82.96, 71.38, 58.35, 43.48, 32.45, 28.13,

23.41IR (KBr, cm�1) 3063, 3031, 2960, 2876, 1773, 1686, 1496, 1454, 1395, 1212, 1152, 1095, 1028, 911, 847,

815, 738, 697, 646Elemental analysis: Found: C, 71.02; H, 6.24; N, 5.29; Calc: C, 70.83; H, 6.32; N, 5.16

Notes 671

N

*

+

(I)

Br

_

a

3. Lindsey [3] prepared phosphono-substituted porphyrin derivatives, (II), forattachment to metal oxide surfaces for use as a chromatographic columnpacking agent. Surface separation methods using 9-borabicyclo[3.3.1]nonanederivatives, (III), are described by Lindsey [4].

N

HNNH

NHP P

OR

OR

O

RO

RO

O

(II)

R = H; O-t-C4H9

672 Optically Active Maleimide Derivatives

B

N

O

N

O

(III)

References

1. T. Kagawa et al., US Patent 6,777,526 (August 17, 2004)2. J.B. Schlenoff et al., US Patent Application 2007-0037948 (February 15, 2007)3. J.S. Lindsey et al., US Patent 7,148,361 (December 12, 2006)4. J.S. Lindsey et al., US Patent 7,153,975 (December 26, 2006)

Notes 673

d. Protein Separations

Title: Polymeric Membranes and Uses Thereof

Author: D. H. Solomon et al., US Patent 7,169,847 (January 30, 2007)Assignee: Life Therapeutics, Inc. (Clarkston, GA)

SIGNIFICANCE

Electrophoresis protein separation membranes have been prepared by step-growthcondensation of water-soluble polyvinyl alcohol with selected water-soluble difunc-tional crosslinking agents. These membranes have broad pore size ranges, restrictedpore size distribution, greater resistance to hydrolysis in an alkaline medium, andimproved gel clarity when higher amounts of crosslinkers are used.

REACTION

OH OH OH OH

O

HO

HO

OOH OH OH O

HOO

OH

OO

OHO

OH

HO

O

OH OH

OH

OH

i

Note 1

a

b

c

i: Hydrochloric acid, glutaraldehyde

674

EXPERIMENTAL

1. Preparation of Polyvinyl Alcohol Membrane Crosslinkedwith Glutaraldehyde

A reaction vessel was charged with 10ml 5% of solution polyvinyl alcohol having aMwof roughly 20,000daltons ofwhich 97.5% to99.5%were hydrolyzed and0.333 mLof 6.0M hydrochloric acid and then treated with 91.5 mL of 25% solution ofglutaraldehyde. The solution was then poured across a PET support and allowed tostandat ambient temperature for30minutes.Themembraneswerewashedwith excessdistilled water to remove residual catalyst prior to use.

DERIVATIVES

A summary of membrane derivatives is provided in Table 1.

TESTING

Electrophoresis Separations

Electrophoresis separations were conducted in a membrane-based electrophoresisapparatus under electrophoretic conditions.

Protein samples used to conduct a protein transfer were bovine serum albumin(BSA, 67,000 daltons), chicken egg ovalbumin (Ovalb, 45,000 daltons), and humanserumcryo-precipitate. These agentswere obtained fromplasma containing amixtureof proteins including Fibrinogen (340,000 daltons), human serum albumin (HSA,67,000 daltons), and immunoglobulin G (IgG, 47,000–56,000 daltons). The cryo-precipitate was diluted with 20ml of buffer solution prior to separation.

A summary of selected separation conditions is provided in Table 2.

TABLE 1. Membranes prepared by reacting selected crosslinking agents with 10mlof 5% solution of polyvinyl alcohol having a Mw of roughly 20,000 daltons and 97.5%to 99.5% hydrolyzed.

Entry Crosslinker Crosslinker (mL)

3 Glutaraldehyde 9.25 Glutaraldehyde 4.510 Divinyl sulfone 31714 Polyethylene glycol diglycidyl ether 5664

Note: Very limited characterization data supplied by author.

Testing 675

NOTES

1. In an earlier investigation by the author [1] electrophoresis protein separationmembranes were prepared using triacryloyl-tris(2-aminoethyl)amine, (I), tri-methacryloyl-tris(2-aminoethyl)amine, (II), and polyethylenimine acrylates,(III). These agents were polymerized either by using ammonium persulphate orphotolytically.

RNH

NNH

RO

HN O

R

OR

NH

NNH

ROO

OR

N

O

(I) (II)

(III)

R = H, CH3

a

2. In a subsequent investigation by the author [2] hydrogels were prepared usingstyryl derivatives, (IV) and (V), with ethylene glycol diacrylate, (VI), as thecrosslinking agent. These materials had a hetero-microphase structure charac-terized by a plurality of highly crosslinked loci or cores interconnected byrelatively linear polymer chains. They were useful both as intraocular lensesand as biological separation matrices.

TABLE 2. Experimental electrophoresis protein separation conditions usingmembranes prepared by reacting polyvinyl alcohol having a Mw of roughly 20,000daltons 97.5% to 99.5% hydrolyzed and selected crosslinking agents.

Entry Crosslinker Buffer (nM) pH

3 Glutaraldehyde Tris-Borate Buffer 8.53 Glutaraldehyde Tris-Glycine Buffer 9.05 Glutaraldehyde Mes-BisTris Buffer 6.8510 Divinyl sulfone Mes-BisTris Buffer 6.85

676 Polymeric Membranes and Uses Thereof

HO

OH

O

O

OO

O

O

(IV) (V)

(VI)

3. Pathak [3] prepared polyalkoxyether hydrogels, (VII) and (VII), that absorbed asubstantial portion of water present in whole blood so that when the swollenhydrogel phase was removed a fibrinogen-rich phase was isolated.

O

O

OO

O

OO

OO O

O O

a = 280

a = 105b = 30

a

a b a

(VII)

(VIII)

4. Harris [4] prepared degradable crosslinked hydrogels with controllable half-lives using hydrolytically unstable imine linkages, (IX).

Oa

(IX)

NN

N

N

NN

N NO

N

-PEO]-...

-PEO]-...

-PEO]-...

-PEO]-...

-PEO]

...-[PEO-

...-[PEO-

b

a = 11b = 5

c

References

1. D.H. Solomon et al., US Patent 6,585,873 (July 1, 2003)2. D.H. Solomon et al., US Patent Application 2003-0027965 (February 6, 2003)3. C.P. Pathak et al., US Patent 7,057,019 (June 6, 2007)4. J.M. Harris, US Patent Application 2004-0076602 (April 22, 2004)

Notes 677

e. Polysaccharide Derivatives

Title: Separating Agent Including a PolysaccharideDerivative Having a Polycyclic Structure

Author: Y. Okamoto et al., US Patent 7,156,989 (January 2, 2007)Assignee: Daicel Chemical Industries, Ltd. (Sakai, JP)

SIGNIFICANCE

Polysaccharides containing grafted 9H-fluorenyl- or 5-indanyl-carbamates have beenprepared that are effective in the separation of aromatic racemicmixtureswhenused asfiller in gas chromatography column.

REACTION

OO

HO OH

OH OO

O O

O

HNO

HN

ONH

O

aa

i

i: Lithium chloride, dimethylacetamide, pyridine, 9H-fluorenyl isocyanateii: THF, silica gel

678

EXPERIMENTAL

1. Preparation of Cellulose-g-tris-(9H-Fluorenyl Carbamate)

Cellulose (0.30 g) and lithium chloride (0.21 g) were dried for 3 hours and thentreated with 2.0ml of dimethylacetamide and swollen at 90�C to 100�C overnight.The mixture was next treated with 6.0ml of pyridine and 9H-fluorenyl isocyanate(1.3 eq) and reacted for 6 hours. The carbamated cellulose was precipitated, filteredthrough a glass filter, and dried, and 1.16 g of cellulose product was isolated.

Fabrication of a Filler for Coating Cellulose-g-tris-(9H-Fluorenyl Carbamate)onto Silica Gel

The Step 1 product (0.75 g) was dissolved in 10ml of THF, and the solution wasperfused uniformly onto silica gel (3 g) of particle size 7 mmwith a thin-pore diameterof 1,000A

�. The solvent was then distilled off to fabricate a filler on which the Step 1

product was attached.

Fabrication of a Column Filled with Silica Gel Coated with Cellulose-g-tris(9H-Fluorenyl Carbamate

The Step 2 product (2.5 g) was pressed and filled into a stainless steel column with F0.46 cm�L25 cm by the slurry filling method and used directly for enantiomericisomer separations.

DERIVATIVES

TABLE 1. Elemental analysis of polysaccharides functionalizedwith 9H-fluorenyl- and 5-indanyl carbamates.

Elemental Analysis

Entry Isocyanate Isocyanate Equivalents C (%) H (%) N (%)

IA 9H-fluorenyl- 1.5 71.95 4.98 5.13IB 5-Indanyl- 1.5 65.49 5.75 6.23IIB 5-Indanyl- 1.6 66.19 5.76 6.44

Derivatives 679

SEPARATIONS

Results of enantiomeric isomer separations for the six compounds below using entriesIA, IB, and IIB provided in Table 2.

O

OH

OH HO

O

O CF3

N

N

(a) )c()b(

(d) (e) (f)

TABLE 2. Effectiveness of enantiomeric separations for racemates (a)–(f) usingcarbamate-functionalized polysaccharides entries IA, IB, and IIB describedin Table 1 with hexane/2-propanol, 90:10, v/v, as the mobile phase at a flow rateof 0.5ml/min at 25�C.

Racemate Entry IA*1 (a) Entry IB (a) Entry IIB (a)Comparative

Example 1*2 (a)

a 1.56 1.41 1.46 1.19b to 1 1.25 1.49 1.0c 1.26 1.78 1.30 1.47d to 1 1.12 1.41 to 1e to 1 1.5 to 1 1.0f to 1 1.57 1.21 to 1

*1The separation coefficient factor, a, is defined as a ¼ k02=k

01 where k

01 and k

02 are the holding coefficients of

the weakly and strongly held enantiomer, respectively.*2The comparative example consisted of cellulose functionalized with triphenyl carbamate.

680 Separating Agent Including a Polysaccharide Derivative Having a Polycyclic Structure

NOTES

1. Additional carbamate-modified polysaccharides, (I), were prepared byOhnishi[1] and used in separating enantiomeric racemates of both non-aromaticheterocyclics and aromatic derivatives.

OO

ROOR

OR

n R=HN

COCO

HN

;

(I)

2. Duval [2] prepared three-dimensional chromatographic polysaccharide sup-ports for use in asymmetric synthesis by crosslinking cellulose-g-(4-alloxy-phenyl-carbamate), (II), with mercaptopropyl silica, (III).

OO

O O

O

a

HNCO

O

HN

CO

O

NHOC

O

(II)

O OSilica

HS SH

(III)

3. Roussel [3] prepared chiral polysaccharide esters by grafting a-phenylpro-pionic acid, (R)-, (IV), and (S)-ibuprofen, or (R)- and (S)-naproxenonto cellulose. These agents were then used for isolating optically active acids.

Notes 681

OO

OO

O

n

O O

O

(IV)

References

1. A. Ohnishi, US Patent 7,090,775 (August 15, 2006)2. R. Duval et al., US Patent 7,067,640 (June 27, 2006)3. C. Roussel et al., US Patent 7,012,138 (March 14, 2006)

682 Separating Agent Including a Polysaccharide Derivative Having a Polycyclic Structure

f. Metal Ion Chelators

Title: Functionalized Polymers for Binding to Solutesin Aqueous Solutions

Author: B. F. Smith et al., US Patent 7,138,462 (November 21, 2006)Assignee: Los Alamos National Security, LLC (Los Alamos, NM)

SIGNIFICANCE

A method for extracting cadmium, copper, europium, and nickel metal ions fromaqueous solution using modified polyethyleneimine is described. The polymermodification consists of grafting an imide, diol, triol, carboxylic acid, or thiocar-boxylic acid function to poly(ethyleneimine), which then forms stable metal com-plexes that are readily removed from solution.

REACTION

NH N

HN

NO O

OHHO

i

aa

i: Ethanol, diethyl tartrate acid

683

EXPERIMENTAL

Preparation of Poly(Ethyleneimine-g-3,4-Dihydroxysuccinimide)

Areactorcontainingpolyethyleneimine(43.75mmol)dissolvedin150mlofethanolwastreatedwithdiethyltartrate(43.75mmol)andthenrefluxedfor15hours.Themixturewascooled to ambient temperature, filtered, and concentrated. The residuewas dissolved inwater and purified by diafiltration and 9.5 g product isolated.

DERIVATIVES

N

HN

HNR

n

TESTING

TABLE 1. Modified polyethyleneimine derivatives effective for chelating copper,zinc, nickel, cadmium, europium, and lead metal ions in aqueous solution.

Entry R Polymer Functionalization (%)

16 CH2CH(OH)CH(OH)CH2OH 3632 CH2CSSH 1%34 CH2COOH —36 CH2CH(OH)CH2OH 49

TABLE 2. Effectiveness of a 20% solution of polyethyleneimine-g-1,2-dihydroxy-prop-3-yl (Table 1, entry 36) as a metal ion chelating agent at pH¼ 7.

Metal IonInitial Solution

Concentration (ppm)Final Solution

Concentration (ppm)Metal Ions

Complexed in Resin (%)

Cdþ2 224.8 152.3 32.25Cuþ2 127.2 19.41 84.74Euþ3 304.0 114.5 62.34Niþ2 117.4 87.46 25.50

FTIR (cm�1): 1654 cm�1 indicative that the starting ester (C¼O, 1734 cm�1) consumed.

684 Functionalized Polymers for Binding to Solutes in Aqueous Solutions

NOTES

1. In an earlier investigation by the author [1] polyethyleneimine-g-1,2-dihydroxy-prop-3-yl was used to chelate boric acid as a function of tempera-ture. Results from this investigation are provided in Table 3.

2. Frecht [2] prepared Generation-0 polyhydroxyl dendrimeric monomers, (I), foruse as diagnostic agents in metal chelate-based contrast materials.

O

O

OH

OH

O

O

HO

HO O

O

OH

OH(I)

Core

3. Solid phase extraction systems containing surfaces with dicarboxylic acidtermini, (II), were prepared by Bakry [3] and used to extract biomolecules suchas viruses, proteins, antigens, and RNA and DNA complexes. A similarextraction system was prepared by Gierde [4] using polyglutarmic acid.

TABLE 3. Effectiveness of polyethyleneimine-g-1,2-dihydroxy-prop-3-yl(Table 1, entry 36) in removing boric acid from solution at varioustemperatures.

Temperature(�C)

Final SolutionConcentration*1 (ppm)

Metal Ions Complexedin Resin (%)

40 64.3 75.540 69.7 73.420 53.4 79.620 56.3 78.54 35.3 86.54 35.5 86.5

*1Reference solution 262 ppm.

Notes 685

OSi N

HO

OH

O

ON

O

O

CO2

CO2Surface

(II)

Polystyrene

4. Raymond [5] prepared salicylamide derivatives (III), that upon complexationwith lanthanide metal ions became luminescent.

N

NHO

HO

O

O

H2N

a

a = 1–3

(III)

5. Using low molecular urea-formaldehyde resins, Wright [6] selectively ex-tracted mercury from mineral ore containing platinum, gold, palladium,titanium, molybdenum, copper, uranium, chromium, and zinc.

References

1. B.F. Smith et al., US Patent Application 2005-0040109 (February 24, 2005)2. J.J. Frechet et al., US Patent 7,097,856 (August 29, 2006)3. R. Bakry et al., US Patent Application 2007-0036685 (February 15, 2007)4. D.T. Gierde et al., US Patent Application 2006-0286599 (December 21, 2006)5. K.N. Raymond et al., US Patent 2006-0286567 (December 21, 2006)6. J.T. Wright et al., US Patent Application 2007-0012630 (January 18, 2007)

686 Functionalized Polymers for Binding to Solutes in Aqueous Solutions

XXIII. THERMOSETS

A. Poly(Ethyl a-Acetoxyacrylate)

Title: Acrylic Copolymer

Author: M. Mouri et al., US Patent 7,230,062 (June 12, 2007)Assignee: Kabushiki Kaisha Toyota Chuo Kenkyusho (Aichi-gun, JP)

SIGNIFICANCE

Alkyl a-acetoxyacrylate intermediates were prepared by condensing pyruvate deri-vatives with acetic anhydride and then free radically converting them into thecorresponding homo- or copolymers. All copolymers had thermal properties thatwere superior to that of polymethyl methacrylate. In addition poly(ethyl a-acetoxy-acrylate) homopolymers were injection moldable at 250�C.

REACTION

O

OC2H5

O

O

OC2H5

O

O

iii

O

OC4H9O

OO

OC2H5O

O

a bNote 1

i: Acetic anhydride, p-toluenesulfonic acid monohydrate

ii: Butyl a-acetoxyacrylate, 2,20-azobisisobutyronitrile, xylene

EXPERIMENTAL

1. Preparation of Ethyl a-Acetoxyacrylate

A mixture consisting of ethyl pyruvate (2.7mol) and acetic anhydride (5.4mol) wastreated with p-toluenesulfonic acid monohydrate (8 g) and then heated to 120�C for


687

24 hours. The mixture was next concentrated under reduced pressure, and 250 g ofproduct were isolated after distillation at 90�C to 103�C at 35 to 40mmHg.

2. Preparation of Poly(Butyl a-Acetoxyacrylate-co-Ethyl a-Acetoxyacrylate)

The Step 1 product (60 g), butyl a-acetoxyacrylate (40 g), and 2,20-azobisisobutyro-nitrile (0.4mol%)were dissolved inxylene to forman80wt%solution and thenheatedfor 10 hours at 60�C.The reactionmixturewas next dissolved in 300ml ofCH2Cl2 andslowly precipitated into 5 liter of methanol. The precipitated material was recoveredand dried, and the product was isolated having a Mn of 80,000 daltons with a Mw of160,000 daltons.

TESTING

NOTES

1. a-Acetoxyacrylate copolymers were initially prepared by Kenyon [1] and usedas molding components.

2. Rau [2] prepared terpolymers of ethyla-acetoxyacrylate, acrylic acid, and vinylacetate that were used as bleach stabilizers in phosphate-free laundry detergentformulations.

References

1. W.O. Kenyon et al., US Patent 2,559,635 (July 10, 1951)2. I. Rau et al., US Patent 6,921,746 (July 26, 2005)

TABLE 1. Storage modulus testing of homopolymers and a-acetoxyacrylatecopolymers. Polymethyl methacrylate is provided as a reference.

Storage Modulus (Pa)

Polymer 100�C 200�C 250�C

Polymethyl methacrylate (Reference) 3.2� 106 170 (dec) —Poly(ethyl a-acetoxyacrylate) 2� 109 3.6� 107 2.2� 107

Poly(propyl a-acetoxyacrylate-co-octyla-acetoxyacrylate

2.8� 109 3.2� 106 4.5� 105

Poly(ethyl a-acetoxyacrylate-co-stearyla-acetoxyacrylate)

1.4� 109 3.1� 106 4.1� 105

688 Acrylic Copolymer

B. Polyethersulfone

Title: High-Heat Polyethersulfone Compositions

Author: D. Steiger et al., US Patent Application 2007-0117962 (May 24, 2007)Assignee: General Electric Company (Schenectady, NY)

SIGNIFICANCE

High-performance polyfluorene derivatives consisting of 9,9-bis(4-hydroxyphenyl)-fluorene and 4,40-bis((4-chlorophenyl)sulfonyl)-1,10-biphenyl have been preparedusing reagent ratios from 100:0 to 0:100. When poly(9,9-bis(4-hydroxyphenyl)-fluorene) was prepared it had a Mn of 58,000 daltons with a glass transistiontemperature greater then 300�C. When copolymers of 9,9-bis(4-hydroxyphenyl)-fluorene and 4,4-hydroxybiphenyl were prepared, however, the glass transitiontemperature was lowered by up to 30�C.

REACTION

a

HO OH O O

O2S

SO2

O

i

i: bis((4-Chlorophenyl)sulfonyl)-1,10-biphenyl, potassium carbonate, sulfolane

689

EXPERIMENTAL

Preparation of Poly(9,9-bis(4-Hydroxyphenyl)Fluorene-co-40-bis((4-Chlorophenyl)-Sulfonyl)-1,10-Biphenyl)

A N2 purged reactor was charged with 9,9-bis(4-hydroxyphenyl)fluorene (0.02854moles), 4,40-bis((4-chlorophenyl)sulfonyl)-1,10-biphenyl (0.02854moles), potassiumcarbonate (0.03256 moles), and 50ml of sulfolane. Toluene was added to the mixturethen azotropically distilled to make the final water concentration in the mixtureless than 80 ppm. The two components were then heated for 9.25 hours at 200�C andcooled to ambient temperature, and 150ml of orthodichlorobenzenewere added. Themixturewas then heated to 120�C to dissolve the polymer, which was filtered, and thefiltratewas precipitated by adding 500ml of stirringmethanol. The solid was isolated,re-dissolved in 250ml of hot chloroform, and re-precipitated in 500ml of methanol,and the productwas isolated having aMwof 54,000daltonswith a polydispersity indexof 2.9 and a Tg of 292

�C.

DERIVATIVES

NOTES

1. Polyethersulfone compositions, (I), having high heat tolerance, good impactresistance, and Tg’s greater than 235

�Cwere prepared by Brunelle [1] and usedas trays in steam autoclave sterilization units and as microwave cookware.Johnson [2] determined that the impact strength of this compositionwas greaterthan the commercially available polyethersulfone, RADEL�.

(I)

O

O2S

a

TABLE 1. The effect of sulfone/fluorene copolymer composition on the glasstransition temperature and number average molecular weight.

Entry Ratio of Sulfone/Fluorene Mn 1� 104 (daltons) Tg (�C)

1 0/100 58 3012 50/50 56 2923 75/25 52 2894 100/0 55 271

690 High-Heat Polyethersulfone Compositions

2. Hung [3] incorporated benzimidazole derivatives, (II), into sulfonated poly-ethersulfones as a method for preventing filler leaching, improvingmechanicalproperties, and decreasing methanol permeability.

NHN

HO OH

(II)

3. Crosslinked polyether sulfone membranes containing pendant sulfonic acidgroups were prepared by Michot [4] and used in electrochemical cells.

References

1. D.J Brunelle et al., US Patent Application 2006-0069236 (May 30, 2006)2. D.S. Johnson et al., US Patent Application 2006-0167216 (July 27, 2006)3. J. Hung et al., US Patent Application 2007-0100131 (May 3, 2007)4. C. Michot et al., US Patent 7,045,248 (May 16, 2006)

Notes 691

C. Polynorborene

Title: Novel (Co)polymer, Process for Producingthe Same, and Process for Producing Carboxylated(Co)polymer

Author: T. Hayakawa et al., US Patent Application 2007-0112158 (May 17, 2007)Assignee: JSR Corporation (Tokyo, JP)

SIGNIFICANCE

Thermoplastic resin compositions consisting of ethylene, propylene, 5-ethylidene-2-norborene, and trimethylsilyl 4-methyl-tetracyclo[6.2.1.13,6. 02,7]-dodec-9-ene-4-carboxylate were prepared and hydrolyzed into the corresponding carboxylic acid.These materials are useful as transparent resins in automotive components.

REACTION

CO2H CO2Si(CH3)3 CO2Si(CH3)3

a b c

i ii

CO2H

a b c

iii

i: THF, pyridine, trimethylchlorosilaneii: 5-Ethylidene-2-norbornene, ethylene, propylene, hydrogen, hexane, vanadium

(V) oxytrichloride, triethylaluminum trichloride, acetic acidiii: Toluene, hydrochloric acid

EXPERIMENTAL

1. Preparation of Trimethylsilyl 4-Methyl-Tetracyclo[6.2.1.13,6. 02,7]

Dodec-9-Ene-4-Carboxylate

A reactor was charged with 4-methyltetracyclo[6.2.1.13,6. 02,7]dodec-9-ene-4-car-

boxylic acid (68.7mmol), 100ml of THF, and pyridine (75.6mmol) and then treated

692

with the dropwise addition of trimethylchlorosilane (75.6mmol) at 0�C. Thereafterthe mixture was stirred at this temperature for 5 hours and filtered and concentrated.The residue was treated with 50ml of n-hexane and stirred for 1 hour, re-filtered, andre-concentrated. The residuewas then distilled between 129�Cand 132�Cat 3mmHg,and the product was isolated.

2. Preparation of Poly(Ethylene-co-Propylene-co-Trimethylsilyl-4-Methyl-Tetracyclo-[6.2.1.1.sup.3,6.0.sup.2,7]Dodec-9-Ene-4-Carboxylate)

A 2000-ml reactor was purged with nitrogen and charged with 1000ml of hexane and3.5ml of the 1.0Mhexane solution of the Step 1 product. Thismixturewas treatedwith2ml of 5-ethylidene-2-norbornene and a gaseousmixture of ethylene (feed rate 5.0 L/min), propylene (feed rate 4.5 L/min), and hydrogen (feed rate 0.6 L/min) wascontinuously fed to the mixture at 28�C. This reaction mixture was initially treatedwith 3.66ml of a 0.32Mhexane solution ofVOCl3 and further treatedwith 20.7ml of a0.41M hexane solution of Al2(C2H5)3Cl3. After polymerizing for 10 minutes, thereaction was quenched with 4.8ml of acetic acid. The polymer was then washed withwater, and 24.1 g of a white solid was isolated. The product consisted of ethylene67.5mol%, propylene 32.14mol%, and trimethylsilyl 4-methyltetracyclo[6.2.1.13,6.02,7] dodec-9-ene-4-carboxylate 0.33mol% having a Mw of 31.6� 104 daltons.

3. Preparation of Poly(Ethylene-co-Propylene-co-4-Methyl-Tetracyclo[6.2.1.13,6. 0

2,7]Dodec-9-Ene-4-Carboxylic Acid)

TheStep 2 productwas hydrolyzed bydissolving 20 g into 1000ml of toluene and thentreating with 40ml of hydrochloric acid and stirring for 3 hours. The reaction mixturewas washed with 500ml of water, precipitated in a copious amount of methanol, anddried, and the product was isolated.

DERIVATIVES

TABLE 1. Summary of Mw’s obtained using silyl monomers after 10 minutesof polymerization with ethylene and propylene.

Silyl Monomer Comonomer Mw� 104 (daltons)

CO2Si(CH3)3

None 31.6

CO2Si(CH3)3

5-Ethylidene-2-norborene 29.0

(continued)

Derivatives 693

NOTES

1. In conjunction with an antioxidant and colorant, Kanae [1] used the Step 3products as thermoplastic elastomers in automobile moldings. Thermoplasticelastomers having good tensile and impact strengthwere also prepared byDatta[2] by blending isotactic polypropylene with ethylene-propylene rubber.

2. In an earlier investigation by the author [3] Step 2 analogues containing2-hydroxyethyl methacrylate were prepared and used as rubber componentsin engineered plastics for automotive applications.

3. Functionalized norborenederivatives, (I) and (II),were prepared byLiaw [4] andused in preparing norborene block copolymers, (III), using RuCl2(CHC6H5)[P(C6H11)] as the polymerization catalyst.

BrBr

+

(I)

(II)

(III)

i

ba

i: RuCl2(CHC6H5)[P(C6H11)]

References

1. K. Kanae et al., US Patent 7,163,983 (January 16, 2007), US Patent 6,982,302 (January 3, 2006), andUSPatent Application 20050096437 (May 5, 2005)

2. S. Datta et al., US Patent 7,056,982 (June 6, 2006)3. T. Hayakawa et al., US Patent 6,803,423 (October 12, 2004)4. D-J. Liaw et al., US Patent 7,205,359 (April 17, 2007)


Silyl Monomer Comonomer Mw� 104 (daltons)

CO2Si(C2H5)3


CO2Si(CH3)2t-C4H9


694 Novel (Co)polymer, Process for Producing the Same and process

D. Polyformals

Title: Polyformals and Copolyformals with ReducedWater Absorption, Production, and Use Thereof

Author: H.-W. Heuer et al., US Patent 7,199,208 (April 3, 2007)Assignee: Bayer MaterialScience AG (Leverkusen, DE)

SIGNIFICANCE

Linear (co)polyformals consisting of biphenyl derivatives have been prepared havingMw’s of at least 10,000 daltons and reducedmoisture absorption. These thermosets areused in molding components and related applications where low moisture absorptionis required.

REACTION

HO OH O OO O

t-C4H9 t-C4H9i

aNote 1

i: 4-t-Butylphenol, NMP, CH2Cl2, sodium hydroxide

EXPERIMENTAL

Preparation of Poly(3,3,5-Trimethylcyclohexane Bisphenol)

A reactor was charged with CH2Cl2 (28.7 kg) and NMP (40.18 kg) and treated with3,3,5-trimethylcyclohexane bisphenol (22.55mol), sodium hydroxide (56.38mol),4-t-butylphenol (0.34mol), and 500 liter of CH2Cl2 and then refluxed for 1 hour. Themixturewas cooled to ambient temperature and dilutedwith 35 liter of CH2Cl2 and 20liter of water; it was washed with water in a separator until a neutral pH and salt freemixturewasobtained. The organic phasewas transferred to an evaporator tankwhere asolvent exchange was performed, CH2Cl2 being replaced with chlorobenzene. The

695

mixture was next extruded at 270�C with subsequent pelletization, the process beingperformed twice. After discarding the initial material, a total of 9.85 kg of crudeproduct was isolated as transparent pellets. This material was divided into two partswhere each partwas swollen overnightwith 5 liter of acetone to remove lowmolecularweight material. The purifiedmaterial was re-dissolved in chlorobenzene and then re-extruded, and 7.31 kg of product were isolated.

DERIVATIVES

NOTES

1. Additional polyformals, (I), used as protective coatings on polycarbonatesurfaces were prepared by the author [1] in a subsequent investigation.

O2S

O O O a b(I)

TABLE 1. Physical properties of polyformal derivatives prepared accordingto the present invention.

Entry StructureMw

(daltons)Mn

(daltons)Tg(�C) PDI

1

O OO O

t-C4H9 t-C4H9

a

38,345 20,138 170 1.90

3

aO O O O

39,901 19,538 89 2.04

14

aO OO O

t-C4H9 t-C4H9 10,644 7,400 158 1.44

Note: The copolyformal in Entry 3 was prepared using 30wt% of bisphenol A.

696 Polyformals and Copolyformals with Reduced Water Absorption, Production, and Use Thereof

2. In an earlier investigation by the author [2], polycarbonates, (II), were preparedthat had reduced water uptake and improved flowability.

O O

O

(II)a

3. Polyindanebisphenol, (III), thermosetting polymers were prepared byMcCarthy [3] and were characterized as having a low dielectric constant, lowmoisture absorption, and a low coefficient of expansion. These materials wereused in the production of epoxy-based laminates.

aOHHO

(III)4. Cyclic oligomeric formals, (IV), characterized by a lowered water absorption

were prepared by Wehrmann [4] and blended with polycarbonates for use inoptical data storagemedia. Copolyformals, (V), were prepared by the author [5]and also used in optical data storage media applications.

a

O O

O O

(IV)

aO O O OO O

t-C4H9 t-C4H9

(V)

Notes 697

5. Branched (co)polyformals were prepared by the author [6] that had reducedwater uptake, improved hydrolytic stability, and they were used in the prepa-ration of molded articles.

References

1. H.-W. Heuer et al., US Patent Application 2006-0251900 (November 9, 2006)2. H.-W. Heuer et al., US Patent 7,132,497 (November 7, 2006)3. T.F. McCarthy et al., US Patent 6,858,304 (February 22, 2005)4. R.Wehrmann et al., USPatentApplication 2006-0025559 (February 2, 2006) andUSPatentApplication

2006-0089483 (April 27, 2006)5. H.-W. Heuer et al., US Patent Application 2006-0100389 (March 11, 2006)6. H.-W. Heuer et al., US Patent 7,028,564 (April 24, 2006)

698 Polyformals and Copolyformals with Reduced Water Absorption, Production, and Use Thereof

E. Styrene and Zinc Diacrylate Ionomers

Title: Branched Ionomers

Author: J. Reimers et al., US Patent 7,179,873 (February 20, 2007)Assignee: Fina Technology, Inc. (Houston, TX)

SIGNIFICANCE

Ionomers were prepared that consisted of styrene and zinc diacrylate or acrylic acidneutralized by sodium-, calcium-, or aluminum bases. Homo- and copolymersdisplayed sufficient flex strength and elongation as well as enhanced melt flow indexproperties for use in microwave ovens as dishes and utensils.

REACTION

O O OO

Zn

ia b

2

i: LUPERSOL® 233, zinc dimethacrylate

EXPERIMENTAL

1. Preparation of Poly(Styrene-co-Zinc Diacrylate)

The free radical polymerization was initiated at 131�C using styrene andLUPERSOL� 233 (170 ppm). This mixture was then treated incrementally withsufficient amounts of zinc dimethacrylate dissolved in styrene monomer to preparedcopolymers having a zinc diacrylate contents of 400 ppm, 600 ppm, and 800 ppm.The results of copolymer physical testing of these experimental agents is provided inTable 1.

699

TESTING

NOTES

1. Muramoto [1] prepared the polymeric solid ionomer, (I), that had high thermaland strong physical properties andwere used in electrochemical devices such asbatteries, capacitors, and sensors.

O

O

OOO

OCH3

Li(I)

a b

2. Macrocyclic ionomers consisting of fullerenes containing grafted Nafion�

acidic termini, (II), were prepared by Wudl [2] and used in composites forconductingmembranes. Rao [3], however, used Nafion�directly in membranesin electrode assemblies in fuel cells.

TABLE 1. Properties of poly(styrene-co-zinc dimethacrylate) prepared usingLUPERSOLR233.

Parameter Copolymer IA Copolymer 1B Copolymer IC

Zinc dimethacrylate (ppm) 400 600 800Melt flow index — 3.84 3.51Flex strength — 13,808/95.2 13,377/95.2Elongation — 3.0 2.5Viscosity index — 220/104 220/104Mn (daltons) 94 95 94Mw (daltons) 249 298 315

Note: Copolymers 1B and 1C were subsequently used as microwave utensils.

700 Branched Ionomers

CF2(CH2)aSO3

CF2(CF2)aSO3

(II)

a > 3

3. Poly(ethylene terephthalate) functionalized with hyperbranched polyaminecations was prepared by Rao [3] and used to splay layered materials in a matrixin polymer-layered nanotubes.

4. Chen [4] prepared a bimodal terpolymer poly(ethylene-co-n-butylacrylate-co-methacrylic acid) thatwas converted into a sodium salt and used as a componentin gold balls.

OC4H9O OO Na(III)

cba

5. Smith [5] prepared polyurethanes ionomers, (IV), where the material remainedelastic between �20�C and 76�C by reacting isocyanate-terminated prepoly-mers with acid salt diols.

NH

O

OO

NH

O O

O

OO

Na(IV)

ba

References

1. H. Muramoto et al., US Patent Application 2007-0040145 (February 22, 2007)2. F. Wudl et al., US Patent Application 2007-0003807 (January 4, 2007)3. Y.Q. Rao et al., US Patent 7,166,657 (January 23, 2007)4. J.C. Chen., US Patent 7,037,967 (May 2, 2006)5. W.M. Smith Jr et al., US Patent 6,949,604 (September 27, 2005)

Notes 701

F. Polycyclodiene

Title: Copolymer of Conjugated Cyclodiene

Author: J. Shishiki et al., US Patent 6,995,228 (February 7, 2006)Assignee: Asahi Kasei Kabushiki Kaisha (Osaka, JP)

SIGNIFICANCE

Poly(1,3-cyclohexadiene-co-styrene) having a Mn of 63,603 daltons and containingup to 86% 1,3-cyclohexadiene has been anionically prepared using 1,3-bis(1-lithio-1,3,3-trimethyl-butyl)benzene as catalyst. When hydrogenated, the material is con-verted into a high-performance resin.

REACTION

abi

i: Cyclohexane, 1,1-dimethoxycyclohexane, 3-bis(1-lithio-1,3,3-trimethyl-butyl)ben-zene, triethylamine, styrene

EXPERIMENTAL

A N2 purged high-pressure reactor was charged with cyclohexane (2,219 g), 1,1-dimethoxycyclo-hexane (346 g), 1,3-cyclohexadiene (600 g), and 40.44ml of 0.82Mcyclohexane solution consisting of an equimolar mixture of 1,3-bis(1-lithio-1,3,3-trimethyl-butyl)benzene and triethylamine. Immediately after the polymerizationbegan, cyclohexane (45 g) containing 33% styrene was charged into the reactor; asecond additionwasmade3minutes later. Sample aliquotswere removed5, 10, 20, 30,

702

60, 120, and 240 minutes for analytical evaluation. The reaction was continued for4 hours and was then quenched with methanol (1.39 g). The polymer solution wasprecipitated inmethanol andwashedwith acetone, and theproductwas isolatedhavinga Mn of 63,600 daltons.

REACTION SCOPING

NOTES

1. Bicyclic conjugated diene polymerswere anionically prepared byWatanabe [1]using bicyclo[4.3.0]-2,9-nonadiene and bicyclo[4.3.0]-1,8-nonadiene and pro-ducts used in high-performance resins. The polymer product of dicyclopenta-diene and 1,3-cyclohexadiene was also prepared by Oshima [2] and used inoptical applications.

2. Poly(1,3-cyclohexadiene) homopolymers were previously prepared by Natori[3] using n-BuLi and tetramethylethylenediamine and had excellent thermaland mechanical properties.

3. Poly((1,3-cyclohexadiene)-g-maleic anhydride), (I), was prepared by Imaizu-mi [4] by postreacting poly(1,3-cyclohexadiene) with maleic anhydride in1,2,4-trichlorobenzene. Up to 1.4 wt% maleic anhydride was incorporatedusing this method.

OO O

(I)

a

TABLE 1. Physical properties of poly(1,3-cyclohexadiene-co-styrene) as a functionof reaction extend use of 1,3-bis(1-lithio-1,3,3-trimethyl-butyl)benzene as a catalyst.

AliquotReaction Time

(min)Amount of 1,3-

Cyclohexadiene in Copolymer (%)Mn

(daltons) PDI

1 5 67 5,507 2.872 10 75 9,092 2.703 20 76 31,673 1.634 30 82 44,085 1.655 60 85 56,595 1.736 120 86 62,065 1.767 240 86 63,603 1.81

Notes 703

4. Poly((1,3-cyclohexadiene)-co-butadiene), (II), and the hydrogenation product,poly((1,3-cyclohexadiene)-co-butane), (III), were prepared by Nakano [5].

i

(II) (III)

a a bb

i: Hydrogen, dicyclopentadienyltitanium dichloride, triisobutylaluminum

References

1. S. Watanabe et al., US Patent 7,034,095 (April 25, 2006)2. N. Oshima et al., US Patent 7,015,293 (March 21, 2006)3. I. Natori., US Patent 5,795,945 (April 18, 1998)4. K. Imaizumi et al., US Patent 5,830,965 (November 3, 1998)5. M. Nakano et al., US Patent 6,426,396 (July 30, 2002)

704 Copolymer of Conjugated Cyclodiene

G. a-Aromatic Ketones

Title: Poly(Aralkyl Ketone)s and Methodsof Preparing the Same

Author: A. Parthiban, US Patent 7,034,187 (April 25, 2006)Assignee: Agency for Science, Technology, and Research (Singapore, SG)

SIGNIFICANCE

Asingle-stepmethod for convertinga-aromatic carboxylic acids into poly(a-aromaticketones) using phosphorus pentoxide and methane sulfonic acid is described. Theseagents are useful as high-performance engineering thermo-plastics having goodchemical resistance and high temperature properties.

REACTION

OH

O Oi a

i: Phosphorus pentoxide, methane sulfonic acid

EXPERIMENTAL

Preparation of Poly(4-Benzylketone)

Phosphorus pentoxide (0.0367mol) was dissolved in 50ml of methane sulfonic acidby heating themixture to 80�C and then cooling to ambient temperature. The solutionwas next treatedwith phenyl acetic acid (0.0367mol) and stirred for 4 days at ambienttemperature. The solution was subsequently precipitated in 1000ml water, isolated,and repeatedly washed with water until a neutral pH was observed. After drying the

705

solid, it was dissolved in THF, re-precipitated in hexane, and dried, and 2 g of productwere isolated having a Mw of 5500 daltons and Mn of 2275 daltons.

DERIVATIVES

NOTES

1. Poly(ethylene-co-carbon monoxide) and poly(ethylene-co-carbon monoxide-co-vinyl acetate), (I), were prepared by Patil [1] and used as adhesive additivesand solvents.

a

OO OCH3

(I)2. Poly(propylene-co-carbon monoxide) was prepared by Queisser [2] using [Pd

(1,3-bis(diphenylphosphino)propane)(NCCH3)2](BF4)2. Fagon [3] used 1,2-bis(2,3,4,5-tetramethylphospholyl)ethane for preparing poly(ethylene-co-carbon monoxide.

3. Taniguchi [4] prepared high molecular weight poly(ethylene-co-carbon mon-oxide) using a catalytic mixture consisting of palladium acetate, 1,3-bis[di(2-methoxyphenyl)-phosphino]-propane, sulfuric acid, and 1,4-benzoquinone.

TABLE 1. Selected aromatic polyketones prepared according to the presentinvention.

Entry Structure Yield (%) Mw (daltons)

5

aS

O86.0 —

7

aO

NO O85.5 15,777

Note: Extensive FTIR characterization supplied by the author.

FTIR (KBr) cm�1: 3440(b), 3059(s), 3028(s), 1758(s), 1711(ss), 1600(ss), 1495(ss), 1444(s), 1412(w),1370(w), 1332(w), 1223(ss), 1181(w), 1113(ss), 1028(w), 755(s), 699(ss) and 521(w)

706 Poly(Aralkyl Ketone)s and Methods of Preparing the Same

4. Shigematsu [5] observed that by treating glycerin with 96% sulfuric acid andthen heating to 160�C for 15 minutes, a polymeric ketone, (II), was produced.

a

O

O

(II)

References

1. A.O. Patil et al., US Patent 6,677,279 (January 13, 2004)2. J. Queisser et al., US Patent 7,169,535 (January 30, 2007) and US Patent 6,573,226 (June 3, 2003)3. P.J. Fagan et al., US Patent 6,579,999 (June 17, 2003)4. R. Taniguchi et al., US Patent Application 2006-0135738 (June 22, 2006) and US Patent Application

2005-0075475 (April 7, 2005)5. T. Shigematsu et al., US Patent Application 2006-0252907 (November 9, 2006)

Notes 707

H. Polyimide Sulfones

Title: Polyimide Sulfones, Method and ArticlesMade Therefrom

Author: R. R. Gallucci et al., US Patent 7,041,773 (May 9, 2006)Assignee: General Electric Company (Pittsfield, MA)

SIGNIFICANCE

Apolyimide sulfone resin has been prepared having aTg of roughly 250�Cand aMn of

roughly 35,000 daltons while still remaining melt processable. When extruded andconverted into molded articles at 370�C to 390�C, the molecular weight of thepolyimide was diminished by less than 30%.

REACTION

N N

O

O

O

O

O2SN

O

O

n

O2S

H2N NH2

i

i: Bisphenol A dianhydride, phthalic anhydride, dichlorobenzene, sodium phenylphosphinate

EXPERIMENTAL

Preparation of Polyetherimide Sulfone

A vessel was charged with bisphenol A dianhydride (490 kg), diaminodiphenylsulfone (245 kg), phthalic anhydride (11.0 kg), 1,287 liters of o-dichlorobenzene,and sodium phenyl phosphinate (360 g) as the reaction catalyst. The mixture washeated to 150�C to 180�C with removal of water, and the reaction was analyzed forresidual amine and anhydride end groups. Additional bisphenol A dianhydride or

708

diaminodiphenyl sulfone was added to keep the total amine and anhydride end groupconcentrations below 20meq/kg of resin. The reaction mixture was then moved to aholding tank kept at 170�C, and the solvent was removed using two evaporators inseries to reduce o-dichlorobenzene to less than 500 ppm. The molten polymer wasextruded into strands, cooled in awater bath, and then chopped to give finished pellets.The polymer product had a Mw of 34,000 daltons, a polydispersity index of 2.3, and aTg of 248

�C.

DERIVATIVES

No additional derivatives prepared.

RESIN PROCESSING

Polyimide sulfone resins were melt processed using a single screw extruder with an80m filter, extruded into strands, cooled, and then cut into pellets. Pelletswere injectionmolded into parts at 370�C to 390�C. The resins in themolded parts showed less than a30% thermal deterioration in molecular weight.

NOTES

1. Ohno [1] prepared a polyaromatic ether containing an imide termini, (I), thathad a lower dielectric and moisture absorption properties and ease of pro-cessability than the imide-free precursor. The imide-functionalized productwas used to prepare molding.

baO OO

N

O

ON

O

O

O

(I)

2. An easily processable polyimide was prepared by Mercado [2] from thecondensation of bisphenol A dianhydride and bis[4-(4-amino-phenoxy)phe-noxy]sulfone that had a Mn of 76,300 daltons and was used in making thinfilms.

Notes 709

a

O2S

O O

O O

N

N

O

OO

O

(II)

3. Photosensitive resins consisting of pre-imidized aromatic polyamic acids, (III),having a light transmittance of 365 nm and a low residual stress after cure wereprepared by Dueber [3] and used for coating silicon wafers.

a

O2S

NH2

O2C CO2

H2N

O O

OHHO(III)

4. Cured polyimide resins, (IV), used as coatings for semiconductor devices wereprepared by Akiba [4] that had good heat resistance, improved adhesion tosubstrates, and resistance to thermal deterioration.

a

O

N

O

O

N

O

O

SiOSi

9

(IV)

5. Matsuwaki [5] prepared polyimide films, (V), having molecular orientation inthe machine direction that were used in high-density mounting of flexibleprinted circuit boards.

710 Polyimide Sulfones, Method and Articles Made Therefrom

c

O

N N

O

O

O

ON

O

ONH

a

b(V)

6. A new class of cyclic polyimides, (VI), was prepared by Ding [6] and used inelectronic applications.

aN

O

O

N

O

O

(VI)

References

1. D. Ohno et al., US Patent 7,193,030 (March 20, 2007)2. R.-M.L. Mercado et al., US Patent 7,192,999 (March 20, 2007)3. T.E. Dueber et al., US Patent Application 2007-0083016 (April 12, 2007)4. H. Akiba et al., US Patent Application 2007-0066796 (March 22, 2007)5. T. Matsuwaki et al., US Patent Application 2007-0045895 (March 1, 2007)6. J. Ding et al., US Patent Application 2007-0066734 (March 22, 2007)

Notes 711

I. Benzoxazine Resins

Title: Method for Producing Benzoxazine Resin

Author: T. Aizawa et al., US Patent 7,041,772 (May 9, 2006)Assignee: Hitachi Chemical Co., Ltd. (Tokyo, JP)

SIGNIFICANCE

A method for preparing thermosets by modifying o,p-phenol-formaldehyde resinsusing paraformaldehyde and aniline to provide N-phenyl benzoxazine having a meltviscosity between 2 and 4 poise at 125�C is described.

REACTION

OH NO

i

a a

Note 1

i: Methyl ethyl ketone, paraformaldehyde, aniline

EXPERIMENTAL

Preparation of Benzoxazine

A5-liter resinkettlewaschargedwitho,p-phenol-formaldehyde resin (1040 g)havingaMn of roughly 400 daltons dissolved in methyl ethyl ketone (560 g) and treated withparaformaldehyde (600 g). This mixture was treated with the dropwise addition of

712

aniline(931 g)andthenrefluxedfor7hours.Themixturewasconcentrated,andtheresinandisolatedhavingasofteningpointof115�Cwithameltviscosityof40poiseat150�C.

DERIVATIVES


NOTES

1. The preparation of the o,p-phenol-formaldehyde reagent is described by Hirai[1]. In this preparation oxalic acid was used as the catalyst to ensure high ortho-para methylene content.

2. Benzoxazine Step 1 analogues containing s-triazine as a crosslinker, (I), wereprepared by Johnson [2] and Gerber [3] as used as thermosets with enhancedhigh temperature properties.

NO N

NN

N

N O

O

a

b

c

(I)

References

1. Y. Hirai et al., US Patent 6,005,064 (December 21, 1999)2. C.K. Johnson et al., US Patent 5,910,521 (June 8, 1999)3. A.H. Gerber et al., US Patent 7,169,535 (July 15, 2007)

Notes 713

J. Acrylonitrile

Title: Block Copolymer

Author: R. Tsuji et al., US Patent 7,094,833 (August 22, 2006)Assignee: Kaneka Corporation (Settsu, JP)

SIGNIFICANCE

Economically produced block copolymers containing acrylonitrile or methacrylo-nitrile as the principal component have been prepared that are heat resistant, weath-erable, and oil and flame resistant. These materials were prepared using reversibleaddition-fragmentation chain transfer polymerization.

REACTION

c c

O-n-C4H9O O-n-C4H9OCN

i a b

Note 1O-n-C4H9O

HS

CN

SHa bii

i:Water, sodiumdodecyl sulfate, acrylonitrile, cumenyl thiobenzoic acid, 4,40-azobis(4-cyanovaleric acid)

ii: Toluene, ethylamine

EXPERIMENTAL

1. Preparation of Poly(Acrylonitrile-b-n-Butyl Acrylate)

A reactor was chargedwithwater (490 g), sodiumdodecyl sulfate (0.56 g), acrylonitrile(8.8 g),andcumenyl thiobenzoicacid (1.09)and thenheatedto80�Cfor20minutes.Thissolutionwas treatedwith 4,40-azobis(4-cyanovaleric acid) (0.93 g) and additionalwater(25 g) and then stirred for 30 minutes. Thereafter additional acrylonitrile (45.0 g) wasaddeddropwiseover1hour, and themixtureheatedforapproximately5hours.Asamplewastakenthat indicatedthepolymerhadaMwof13,700daltonsandMnof10,300daltonswith a polydispersity index of 1.33. The mixture was then treated with n-butyl acrylate(20.0 g), 4,40-azobis(4-cyanovaleric acid) (0.40 g), andwater (10 g) and stirred 1 hour at80�C. The mixture was further treated with n-butyl acrylate (80.0 g) over 2 hours and

714

stirred an additional 5 hours. After the mixture cooled to ambient temperature it wassaltied-out and the block copolymer isolated having a Mw of 48,600 daltons and Mn of34,500 daltons with polydispersity index of 1.41.

2. Preparation of Mercapto-Terminated Poly(Acrylonitrile-b-n-ButylAcrylate)

The Step 1 product (50 g) was dissolved in 200ml of toluene and treated withethylamine (15 g) and stirred 8 hours at 30�C. The toluene solution was washedwith water and then poured into methanol to precipitate and the product isolated.1H-NMR and FTIR analyzes confirmed that the end groups had been quantitativelyconverted into mercapto groups.

DERIVATIVES

Selected diblock polymers are provided in Table 1. Izod impact strength and flameretardancy testing are provided in Table 2. Flame retardancywasmeasured accordingto the UL-94 standard.

DERIVATIVES

TESTING

TABLE 1. Selected mercapto-terminated di- and tri-block polymers prepared usingeither cumenyl thiobenzoic acid, (I), or 1,4-bis(thiobenzoyl-thiomethyl)benzene, (II),as the polymerization regulator.

Entry Block PolymerMw

(daltons)Mn

(daltons) PDI

15 Acrylonitrile-butyl acrylate-acrylonitrile 127,000 84,500 1.5017 Acrylonitrile-vinyl chloride 71,100 49,400 1.4418 (Acrylonitrile-methyl methacrylate)-butyl acrylate 62,900 45,200 1.3921 (Acrylonitrile-methyl methacrylate)-vinyl chloride 68,200 46,200 1.48

TABLE 2. Selected Izod impact strength and flame retardancy for block polymershaving mercapto termini.

EntryIzod Impact

Strength (kJ/m2)Flame

Retardancy

Step 1 product 10.5 V-215 13.3 V-217 7.2 V-018 8.8 V-221 7.7 V-0

Note: Flame retardancy testing was measured according to the UL-94 standard.

Testing 715

NOTES

1. Polymerization regulators consisted of either cumenyl thiobenzoic acid, (I), or1,4-bis(thiobenzoyl-thiomethyl)benzene, (II).

S

SS

S

S

S

)II()I(

2. In other investigations by the author [1] curable di- and tri-block copolymerswere prepared containing an allyl terminus that had good thermal stability andweatherability properties.

3. Moisture curable n-butyl acrylate oligomers materials containing a dimethox-ymethyl hydrosilane termini were prepared by Ohshiro [2] and the author [3]that had good heat resistance, weatherability, oil resistance, and low stainingproperties.

4. Polyurethane-based materials having hot water resistance, strength, and chlo-rine and chemical resistancewere prepared by the author [4] by reacting poly(n-butyl acrylate) containing mercapto termini with 4,40-diphenylmethane diiso-cyanate and 1,4-butanediol.

5. Nakagawa [5] prepared poly(styrene-b-isobutylene) through atom transferradical polymerization that had good weatherability properties.

References

1. R. Tsuji et al., US Patent 7,081,503 (July 25, 2006), US Patent 7,009,004 (March 7, 2006), andUSPatentApplication 2006-0004171 (January 5, 2006)

2. N. Ohshiro et al., US Patent Application 2005-0004318 (January 6, 2005)3. R. Tsuji et al., US Patent 6,914,110 (January 5, 2005)4. R. Tsuji et al., US Patent 6,992,138 (January 31, 2006)5. Y. Nakagawa et al., US Patent 7,056,983 (January 6, 2006)

716 Block Copolymer

K. Polycarbonates

Title: Aliphatic Diol Polycarbonatesand Their Preparation

Author: D. Dhara et al., US Patent 7,138,479 (November 21, 2006)Assignee: General Electric Company (Schenectady, NY)

SIGNIFICANCE

Polycarbonate resins were prepared by reacting diphenyl carbonate with bisphenol Aand isosorbide. These resins had light transmissions exceeding 90% with little or nohaze. As a result of the favorable elastic modulus and hardness properties, these resinswere scratch resistant.

REACTION

O

O

HO

OH

O

O O

OO

O

OO

O

a

bi

Note 1

c

i: Bisphenol A, diphenyl carbonate, sodium hydroxide, tetramethylammoniumhydroxide

EXPERIMENTAL

Preparation of Poly[(Isosorbide-co-Bisphenol A)Carbonate)]

A glass reactor was passivated by soaking in a bath containing 1M aqueous hydro-chloric acid solution for 24 hours and then thoroughly rinsed and dried. The reactorwas charged with isosorbide, bisphenol A, and diphenyl carbonate where the numberof moles of diphenyl carbonate to the sum of number of moles of bisphenol A and

717

isosorbide was 1.12, respectively. The catalyst consisted of a combination of sodiumhydroxide and tetramethylammoniumhydroxide in amole ratio of 1:100, respectively.In all cases, however, the molar ratio of tetramethylammonium hydroxide to the totalmoles of isosorbide and bisphenol Awas 5.0� 10�4. The reactor was heated to 180�Cwith stirring at 40 to 60 revolutions per minute then further heated to 210�C at18,000 Pa. After stirring for 30 minutes, the pressure was reduced to 10,000 Pa, andstirring continued an additional 50minutes. The temperaturewas then raised to 240�Cwhile lowering the pressure to about 1500 Pa and the reaction continued for anadditional 30 minutes. Finally the reaction temperature was further raised to 260�Cwhile the pressure was lowered to 150 Pa. The mixture was then brought to atmo-spheric pressure, the reactor was cooled to ambient temperature, and the product wasisolated.


Physical properties of polycarbonates derived from diphenyl carbonate, and isosor-bide and/or bisphenol and those derived from bismethylsalicylcarbonate, (I), bi-sphenol A and/or isosorbide are provided in Tables 1 and 2, respectively.

TABLE 1. Polycarbonates prepared by reacting diphenyl carbonate with isosorbideand bisphenol A.

Entry CompositionMw

(daltons)Mn

(daltons) Tg (�C)

ElasticModulus(Gpa)

Hardness(Mpa)

YellownessIndex

1 Isosorbide,100%

16,060 8,728 151.0 4.95 311.8 10.54

3 Isosorbide,bisphenol A,

50:50

27,879 15,832 152.0 3.34 234.3 4.53


25:75

38,795 21,597 152.0 3.63 222.7 9.74


83:17

25,767 15,358 — — — —

Note: Light transmittance for all materials exceeded 90% with excellent scratch resistance.

718 Aliphatic Diol Polycarbonates and Their Preparation

NOTES

1. Optically active poly[(isosorbide-co-bisphenol A) carbonate)], (II), was alsoprepared and consisted of 90% isosorbide and 10% bisphenol Awith diphenylcarbonate and had an optical rotation of 140� with excellent scratch resistance.

O

O O

OO

O

OO

O

a

b

(II)

2. Glasgow [1] prepared a blend consisting of the reaction product of bisphenol Aand diphenyl carbonate with poly(caprolactone-b-dimethylsiloxane-b-poly-caprolactone) terpolymer that showed superior resistance to scratching andhazewhile having excellent transmittance properties. Food andmedical articlesderived from this blend were readily sterilized by steam at atmosphere pressureas taught by Chatterjee [2].

TABLE 2. Physical properties of polycarbonates obtained from the reactionof bisphenol A and isosorbide with bismethylsalicylcarbonate, (I).

O O

O

CO2CH3 CO2CH3

(I)

Entry CompositionMw

(daltons)Mn

(daltons)Tg(�C)

ElasticModulus(Gpa)

Hardness(Mpa)

YellownessIndex

2 Isosorbide,100%

20,678 10,147 152.0 4.83 313.8 0.44

4 Isosorbide,bisphenol A,50:50

28,991 15,955 152.8 3.29 232.7 0.343

6 Isosorbide,bisphenol A,25:75

33,588 17,696 151.0 3.45 219.8 0.62

Note: Light transmittance exceeded 90% for all experimental agents and had high scratch resistance.

Notes 719

3. Polycarbonates prepared by reacting phosgene and bisphenol A and cappingwith a perfluoroalcohol, (III), were prepared by Davis [3] and used as thesurface layer of molded articles in flame retardant and weatherable articles.

OO

O

O O

OO OO

O

O

O

C9H17 C9H17

(III) a

4. McCloskey [4] prepared high molecular weight polymer carbonates consistingof bis(methyl salicyl) carbonate, bisphenol A, and an oligomeric carbonate ofmethyl salicylate using the transesterification catalyst, tetrabutylphosphoniumacetate.

5. Boven [5] prepared polycarbonates consisting of dimethyl bisphenol cyclo-hexane and phosphine. Copolymers of dimethyl bisphenol cyclohexane withbisphenol and interfacial phosgene, (V), were also prepared and were used asglass panes because they exhibited enhanced scratch and molecular weightdegradation resistance.

OO

O

O

O

(IV)a

O

References

1. K. Glasgow et al., US Patent 7,135,538 (November 14, 2006)2. G. Chatterjee et al., US Patent Application 2006-0002814 (January 5, 2006)3. G.C. Davis et al., US Patent Application 2006-0135737 (June 22, 2006)4. P.J. McCloskey et al., US Patent Application 2006-0069228 (March 30, 2006)5. G. Boven et al., US Patent Application 2007-0009741 (January 11, 2007)

720 Aliphatic Diol Polycarbonates and Their Preparation

L. Poly(Silarylene-Siloxane-Acetylene)

Title: High-Temperature Elastomers from LinearPoly(Silarylene-Siloxane-Acetylene)

Author: T. M. Keller et al., RE39,428 (December 12, 2006) [formally US Patent6,362,289]

Assignee: TheUnited States ofAmerica as represented by the Secretary of theNavy(Washington, DC)

SIGNIFICANCE

Flexible and oxidatively stable thermosets were prepared by thermally curing linearpoly(silarylene-siloxane-acetylene) elastomers at up to 450�C. Thermooxidativeweight loss of 3.69% to 7.69% was observed for these crosslinked inorganic-organichybrid polymers when isothermed at 350�C under air flow.

REACTION

Cl

Cl Cl

Cl

Cl

Cl

Li Li Si Si NN

Intermediate

Si SiHO OH Si O Si Si O HSiHOIntermediate

i ii

iii

Si O Si Si O HSiOSi Si3

3iv

CuringPostcuringvvi

Notes 1,2

O

O

i: THF, butyl lithium

ii: Dimethylaminodimethylchlorosilane

iii: Bis(dimethylamino)dimethylsilane, toluene

iv: Toluene, diethyl ether, 1,4-bis(dimethylaminodimethylsilyl)butadiyne

721

EXPERIMENTAL

1. Preparation of Di-lithium 1,4-Butadiyne

A 250-ml Schlenk flask containing 20ml of THFand 20ml of 2.4M n-butyl lithiumwas cooled to �78�C and then treated dropwise with hexachlorobutadiene(12.0mmol) over 10 minutes. After the addition was completed, the mixture stirred3 hours at ambient temperature and used directly without purification.

2. Preparation of 1,4-bis(Dimethylaminodimethylsilyl)Butadiyne

The entire Step 1productwas re-cooled to�78�Cand treated dropwisewith dimethyl-aminodimethylchlorosilane (24 mmol) and stirred 16 hours at ambient temperature.The mixture was concentrated, and the residue was dissolved in a small amount ofpentane, filtered, and re-concentrated. The product was isolated in 96% yield.

3. Preparation of Hydroxyl Terminated Silarylene-Siloxane Prepolymer

A mixture consisting of 1,4-bis(hydroxydimethylsilyl)benzene (11.7mmol) and10ml of toluene was treated with bis(dimethylamino)dimethylsilane (8.81mmol)and then refluxed until there was no evidence of dimethylamine evolution asdetermined usingmoist red litmus paper. Themixturewas then refluxed an additionalhour and used without further purification.

4. Preparation of High-Temperature Elastomer Precursor, LinearPoly(Silarylene-Siloxane-Acetylene)

The entire Step 3 product was treated with a 4.0ml of aliquot consisting of 5.0ml oftoluene containing the Step 2 product (3.28mmol) and then refluxed for 1 to 2 hours.The mixture was next treated with 50 to 100 ml of toluene containing 1,4-bis(dimethylaminodimethylsilyl)butadiyne every 15 to 30 minutes until the viscosityof the solution visibly increased and dimethylamine evolution ceased. The mixturewas concentrated, treatedwith excess diethyl ether, andwashed twicewith 100ml of asaturated solution of NH4Cl; and the ethereal solution was dried using Na2SO4.Diethyl ether was vacuum removed, and the product was isolated in 67% yield.

5. Thermal Curing

A platinum thermogravimetric analyzer pan containing 28.7410mg of the Step 4productwas heated under nitrogen at 150, 200, 350, and450�Cfor 60, 60, 120, and120minutes, respectively. After completion of the isothermal curing experiment, thesample was void free and exhibited the characteristics of an elastomeric material.

IR (cm�1) 2074 (w), (–C.ident.C–C.ident.C–), 1052 (vs, broad), (Si–O)1H NMR (CDCl3) d 7.50 (s), (C6H4), 0.35 (s), 0.30 (s), 0.28 (s), 0.22 (s), 0.02 (s), (Si(CH3)2)13C NMR (CDCl3) d 140.7, 140.2, 132.2, (C6H4) 86.9, 85.3, (–C.ident.C–C.ident.C–), 2.11, 1.40, 0.96,0.77,), (Si(CH3)2)

722 High-Temperature Elastomers from Linear Poly(Silarylene-Siloxane-Acetylene)

6. Postcure Thermo-Oxidative Stability

Following the isothermal curing cycle in Step 5 the sample was cooled to ambienttemperature and then further isothermed on a thermogravimetric analyzer for 120minutes at 200, 250, 300, and 350�C in an air atmospherewith a 50 cc/min flow rate. Inthis experiment theplastic sample exhibitedonlya3.69%weight loss as determinedbyTGA.

DERIVATIVES


TESTING RESULTS

a bSiO O Si Si O HSiOSi Si

NOTES

1. Additional fexible and oxidatively high-temperature stable elastomers wereprepared by the author [1,2] by thermal curing modified linear poly(silar-ylene-siloxane-acetylene) prepolymers, (I), and (II), respectively.

OSi Si Si OSiOSi Si

(I)

a = 0 – 3

OSi Si Si O SiSiOSi Si

a = 0 – 4

Si O

(II)

a

b

b

a

TABLE 1. Physical and oxidative stability of poly(silarylene-siloxane-acetylene)elastomers after isothermal curing.

n Postcured PropertiesOxidative Stability(% weight loss)

0 Solid plastic material 0.171 Soft and flexible 3.262 Soft and flexible 7.693 Soft and flexible 3.96

Notes 723

2. In earlier investigations by the author [3,4] high-temperature oxidatively stableeastomers containing 1,7-dodecacarboranyl (carborane), (III), or borate-termi-nated derivatives, (IV), respectively, were prepared that could be thermallycrosslinked to a cured polymer or pyrolyzed to a ceramic surface.

aa

ba a

Si O Si Si O Si

(IV)

OB

HO

Si O Si Si O Si Carborane Si O Si Carborane

(III) a, b = 0, 1c = 1– 10

a > 0

c

3. Rantala [5] prepared hybrid organic-inorganic polymers by condensingpentafluorophenyl-vinyl-dichlorosilane, (V), and pentafluorotrichlorosilane,(V), with water and then free radically initiating the mixture.

SiCl3SiCl2

F5 F5

(VI)(V)

References

1. T. M. Keller et al., RE39,332 (October 16, 2006)2. T.M. Keller et al., US Patent 6,787,615 (September 7, 2004) andUS Patent 6,784,259 (August 31, 2004)3. T. M. Keller et al., US Patent 6,967,233 (November 22, 2005)4. T. M. Keller et al., US Patent 6,784,270 (August 31, 2004)5. J. Rantala et al., US Patent 7,144,827 (December 5, 2006)

724 High-Temperature Elastomers from Linear Poly(Silarylene-Siloxane-Acetylene)

CONTRIBUTORS

Academic Contributors

Board of Regents, The University of Texas System (Austin, TX)Board of Trustees of the University of Illinois (Urbana, IL)Changchun Institute of Applied Chemistry Chinese Academy of Science

(Changchun, CN)California Institute of Technology (Pasadena, CA)Centre National de la Recherche Scientifique (FR)Cornell Research Foundation, Inc. (Ithaca, NY)Ecole Polytechnique Federale de Lausanne (Lausanne, CH)Emory University (Atlanta, GA)Industrial Technology Research Institute (Hsinchu, TW)Korea Advanced Institute of Science and Technology (Daejeon, KR)Korea Institute of Science and Technology (Seoul, KR)Ministero dell ‘Universita’e della Ricerca Scientifica e Technologica (Rome, IT)National Institute of Advanced Industrial Science and Technology (Tokyo, JP)Ohio State University (Columbus, OH)Rensselaer Polytechnic Institute (Troy, NY)Research Foundation of State University of New York (Albany, NY)Rice University (Houston, TX)Seoul National University Industry Foundation (Seoul, KR)Simon Fraser University (Burnaby, CA)Societe de Conseils de Recherches et d’Applications Scientifiques (Paris, FR)University of Dayton (Dayton, OH)University of Florida Research Foundation, Inc. (Gainesville, FL)University of Hull (North Humberside, GB)University of Iowa Research Foundation (Iowa City, IA)University of Pittsburgh (Pittsburgh, PA)University of Southern Mississippi (Hattiesburg, MS)Virginia Tech Intellectual Properties, Inc. (Blacksburg, VA)

Government Contributors

Agency for Defense of Korea (Daejeon, KR)Agency for Science, Technology, and Research (Singapore, SG)Commissariat a L’Energie Atomique (Paris, FR)Japan Science and Technology Agency (Kawaguchi-shi, JP)


725

Laboratories d’Hygiene et de Dietetique (Chenove, FR)Los Alamos National Security, LLC (Los Alamos, NM)Secretary of State for Defense DSTL (Salisbury, GB)United States of America as Represented by the Secretary of the Air Force

(Washington, DC)United States of America as Represented by the Secretary of the Navy

(Washington, DC)

Industrial Contributors

Aerojet-General Corporation (Sacramento, CA)Agfa-Gevaert (Mortsel, BE)Akzo Nobel N.V. (Arnhem, NL)Alliant Techsystems, Inc. (Edina, MN)A.P. Pharma, Inc. (Redwood City, CA)Aquero Company (Eugene, OR)Arkema, Inc. (Philadelphia, PA)Arkema, Inc. (Puteaux, FR)Asahi Denka Company, Ltd. (Tokyo, JP)Asahi Kasei Kabushiki Kaisha (Osaka, JP)Baker Hughes, Inc. (Houston, TX)BASF Aktiengesellschaft (Ludwigshafen, DE)Bausch and Lomb, Inc. (Rochester, NY)Bayer MaterialScience AG (Leverkusen, DE)Biosphere Medical, Inc. (Rockland, MA)Borealis Technology Oy (Porvoo, FI)BP Chemicals, Ltd. (London, GB)Bridgestone Corporation (Tokyo, JP)Cambridge Display Technology, Ltd. (Cambridge, GB)Canon Kabushiki Kaisha (Tokyo, JP)Central Glass Co., Ltd. (Ube, JP)Chartered Semiconductor Manufacturing, Ltd. (Singapore, SG)Cheil Industries, Inc. (Kyeonggi-do, KR)Ciba Specialty Chemicals Corporation (Tarrytown, NY)Construction Research and Technology, GmbH (Trostberg, DE)Cyclics Corporation (Schenectady, NY)Daicel Chemical Industries, Ltd. (Sakai, JP)Daikin Industries, Ltd. (Osaka, JP)Dainippon Ink and Chemicals, Inc. (Tokyo, JP)Denki Kagaku Kogyo Kabushiki Kaisha (Tokyo, JP)Dow Global Technologies, Inc. (Midland, MI)DuPont de Nemours and Company (Wilmington, DE)Dupont Performance Elastomers, LLC (Wilmington, DE)Elsicon, Inc. (Newark, DE)Ethicon, Inc. (Somerville, NJ)

726 Contributors

ExxonMobil Chemical, Inc. (Houston, TX)Fidia Advanced Biopolymers s.r.l. (Abano Terme, IT)Fina Technology, Inc. (Houston, TX)Fujifilm Imaging Colorants Limited (Manchester, GB)Fuji Photo Film Company, Ltd. (Tokyo, JP)General Electric Company (Niskayuna, NY)General Electric Company (Pittsfield, MA)General Electric Company (Schenectady, NY)Goodyear Tire and Rubber Company (Akron, OH)Hammen Corporation (Missoula, MT)Hammersmith Imanet, Ltd. (London, GB)Hercules, Inc. (Wilmington, DE)Hitachi Chemical Company, Ltd. (Tokyo, JP)Hoffmann-La Roche, Inc. (Nutley, NJ)Honda Giken Kogyo Kabushiki Kaisha (Tokyo, JP)Honeywell International, Inc. (Morristown, NJ)Hyperion Catalysis International, Inc. (Cambridge, MA)Hynix Semiconductor, Inc. (Kyungki-do, KR)IM&T Research, Inc. (Denver, CO)Infineon Technologies AG (Munich, DE)International Business Machines Corporation (Armonk, NY)Invista North America S.a.r.l. (Wilmington, DE)Ivoclar Vivadent AG (Schaan, LI)Japan Science and Technology Corporation (Saitama, JP)Johnson and Johnson Vision Care, Inc. (Jacksonville, FL)JSR Corporation (Tokyo, JP)Kabushiki Kaisha Toyota Chuo Kenkyusho (Aichi-gun, JP)Kaneka Corporation (Settsu, JP)Kimberly-Clark Worldwide, Inc. (Neenah, WI)Korea Kumho Petrochemical Company, Ltd. (Chongno-gu, Seoul, KR)Landec Corporation (Menlo Park, CA)Life Therapeutics, Inc. (Clarkston, GA)Lumera Corporation (Bothell, WA)3M Innovative Properties Company (St. Paul, MN)Matsushita Electric Industrial Company, Ltd. (Kadoma, JP)Merck Patent Gesellschaft (Darmstadt, DE)Michelin Recherche et Technique S.A. (Granges-Paccot, CH)Mitsui Chemicals, Inc. (Tokyo, JP)National Starch and Chemical Company Bridgewater, NJ)NEC Corporation (Tokyo, JP)Nektar Therapeutics (San Carlos, CA)Nektar Therapeutics AL Corporation (Hunstville, AL)Nissan Chemical Industries, Ltd. (Tokyo, JP)Nitto Denko Corporation (Osaka, JP)Nova Molecular Technologies, Inc. (Janesville, WI)

Contributors 727

Noveon, Inc. (Cleveland, OH)Ocutec, Ltd. (Glasgow, GB)Organic Vision, Inc. (Brossard, CA)Organon, Inc. (Oss, NL)Promerus LLC (Brecksville, OH)Rhodia Chimie (Aubervilliers, FR)Rhodia, Inc. (Cranbury, NJ)Samsung Electro-Mechanics Company, Ltd. (Suwon, KR)Sartomer Technology, Inc. (Wilmington, DE)Sekisvi Chemical Company, Ltd. (Osaka, JP)Shin-Etsu Chemical Company, Ltd. (Tokyo, JP)Shin-Etsu Chemical Company, Ltd. (Annaka-shi, JP)Shipley Company, LLC (Marlborough, MA)Sigma Laboratories of Arizona, LLC (Tucson, AZ)SmithKline Beecham Corporation (Philadephia, PA)Solvay Advanced Polymers, LLC (Alpharetta, GA)Solvay Solexis, S.p.A. (Milan, IT)South African Nuclear Energy Corporation, Ltd. (ZA)Sumitomo Chemical Company, Ltd. (Osaka, JP)Sun Bio, Inc. (Orinda, CA)SurfaTech Corporation (Dacula, GA)SurModics, Inc. (Eden Prairie, MN)Tosoh Corporation (Yamaguchi-ken, JP)Unimatec Company, Ltd. (Tokyo, JP)Xerox Corporation (Stamford, CT)Zyvex Corporation (Richardson, TX)

728 Contributors

INDEX

AdhesivesBiochips

Poly[(lactide-g-butene)-g-poly(ethyleneglycol)] as a hydrophilic and biodegradableadhesive, 69

Biocompatible adhesivesa-Cyanoacrylate adhesives, 15, 19

Computer chipsPolybenzoxazoles, 20, 21

Pressure sensitive adhesivesPolymetharylate block terpolymers, 11

AutomotiveTire hysteresis

Covalently bound rubber additives bis-[2-(2-Thiazolyl)-phenyl]disulfide, 8

Methyl-N-phenylnitrone, 64-(2-Oxazolyl)-phenylnitrone, 6

Thermoplastic resins useful as transparent resinsin automotive components

Polynorborene terpolymers containingethylene and propylene, 692

Vulcanization methodsPoly(styrene-co-butadiene) initiated with athioacetal initiator and terminated with

a vulcanization agent, 474

BatteryCathode for lithium secondary batteries

Condensation product of N,N0-1,4-phenylene-bis-thiourea with phenylene-1,4-diisothiocyanate, 169

ElectrodesPoly(3-hexyl)thiophene with high head-to-tailregioregularity, 158

Self-doped polyaniline graft copolymers, 93Bioabsorbables polymers

ConjugatesPoly(ethylene oxide-co-glycidol-butyric acidconjugated with Grob-t and di-stearoylphosphatidyl-ethanolamine, 48–49

Poly(ethylene oxide)-succinimidylester conjugated with AZT, T-20polypeptide, and human erythropoietin, 52

Poly(ethylene oxide-co-propylenesulfide-co-ethylene oxide) conjugatedwith cysteine containingpeptides, 76

Polymethoxypolyethylene oxidealkylaldehydes conjugated with IFNs-a, b,and �, factors VII, VIII, and IX, insulin, orerythropoietin, 65

Diminished cytotoxicityMethoxypolypropylene glycol aldehyde drug

delivery systems, 84Poly(ethylene glycol-b-(lactide-co-

glycolide)) implants, 55Drug deliveryAmphiphilic poly(ethylene glycol-b-

valerolactone) derivatives for delivery ofwater insoluble drugs, 44

Injectable thermosensitive biodegradable drugdelivering system, 278

125I-Polyacetals, 31Polylactones for delivering Lanreotide�, 35Poly(ortho esters) with bioerodible

matrices for the sustained release ofmedicaments, 61

ImplantsCoumarin end-capped absorbable polymers as

in vivo implants, 72High molecular weight poly(lactide-co-

glycolide), 557Injectable implants, 55Injectable thermosensitive biodegradable drug

delivering systems, 278Staples consisting of mercaptoethylamine-

modified poly(monooleoyl glyceride-co-maleic anhydride), 29

Polymer modificationFree radical functionalization of

polycaprolactone with poly(lactic-co-glycolic acid), 80

Biocompatible materialsBone regeneration materialsPolypyrrole films prepared using hyaluronic

acid, 161


729

Biocompatible materials (continued)Contact lenses

Fumarate- and fumaramide-containinghydrogels, 265

High tensile strength poly(dimethylsiloxane-urea-propylene oxide), 25, 26, 27

Poly(2-hydroxethyl methacrylate) modifiedwith methacrylate acid and glycerolmethacrylate, 40

HemocompatibleThromboresistant heparinized surfaces, 89

Bullet proof vestsHeterocyclic rigid-rod polymers

Benzobisthiazole-naphthalic fibers, 224Polybenzazole fibers, 227

CatalystsAcyclic diene metathesis catalyst

1,3-Dimesityl-4,5-dihydroimidazol-2-ylidene)benzylidene ruthenium(II)dichloride, 481

Ethylene polymerization catalystsMerrifield resin containing grafted carboranetrianion, 566

Nickel(II) dibromide salts, 546Siloxy/zirconium derivatives, 523Zirconium metallocene derivatives, 542

Macromolecular depolymerization-repolymerization catalysts

1,3-Diacetoxy-1,1,3,3-tetra-butyldistannoxane, 517

Tetraphenoxyl titanates, 520a-Olefin polymerization

2,6-Di-(1,3,5-trimethyl-4-pyrazolyl)ethanimidoyl pyridine iron chlorideprocatalyst, 553

Merrifield resin containing grafted carboranetrianion, 566

Norbornene polymerizationMixture comprising palladium acetate,tricyclohexylphosphine, dimethyl zinc,and hexafluoroisopropanol, 569

Transesterification method for preparingpolybranched polyesters

Tin(di(chlorodimethylsiloxy)-tinchlorodimethylsilane), 406

Ziegler–Natta catalysisPreparation of high cis poly(1,4-butadiene)using neodymium versatate as the co-catalyst, 539, 540

Charge transport materialsDonor acceptor polymeric complexes

1,3-Dinitrobenzeneandpoly(9-hydroxymethyl-9-fluorene carboxylic acid), 156

Liquid crystal displaysLow molecular weight [2,3-b]-thienothiophene derivatives, 196

Chain transfer polymerization agentsAcrylic acid, butadiene, and styrene

terpolymerization1-Benzyl-2,5-cyclohexadiene-1-carboxylicacid, 577

AcrylonitrileCumenyl thiobenzoic acid, 714

ChloropreneDithiocarbamic esters, 492

N,N-dimethylacrylamideN,N-Dimethyl-S-thiobenzoylthiopropionamide, 588

2-EthylhexylacrylateS,S0-bis-(a,a0-dimethyl-a00-acetic acid)-trithiocarbonate, 584

2-Hydroxyethyl methacrylate1,1-Diphenylethylene, 575, 595

Methacrylic acid1,4-Dimercaptobutane-2,3-diol, 581

Reactivation of polymethyl methacrylatepolymerization

bis(Ethoxythiocarbonyl)disulfane, 511Tetrafluoroethylene

Chloroform, 238Ethane, 237

Crosslinking agentsDegradable

N,N0-(Dimethacryloyloxy)glutarylamide andderivatives, 274

Superabsorbent swellable hydrogelsCrosslinked polyethers capped with acrylicacid, 262

DispersionAqueous

Oligomeric ethylene oxide phosphonic acidderivatives, 105

Non-aqueous nanotube dispersantNoncovalent dispersion of nanotubes usingelectron donor/electron interactionsacceptor characteristics of the polymerbackbone, 351

Dental cementsPre-cured cement paste

Low shear viscosity UV curable dentalcomposite containing of 1,3,5-oxadiazine-2,4-dione trimethacrylate, 133

Visible light curable diacrylate derivativeswhich have small polymerizationshrinkage and high X-ray contrastproperties, 138

730 Index

Dielectric constant materialsLow dielectric constant polymeric agents

Poly1,3-butadiynyl derivatives, 150

ElastomersPerfluoro elastomers containing hydroxyl cure

sitesBasic hydrolysis of poly(tetrafluorene-co-perfluoro(methylvinyl ether)-co-vinylacetate), 241–242

Very low surface energy elastomersOxetanes containing 2,2,2-trifluoroethoxy-methyl substituents, 244

ElectroconductiveBattery electrodes

Poly(3-hexyl)thiophene with high head-to-tailregioregularity, 158

Electrically conducting artificial musclesDibenzodiazocine polymers, 164

Electroconductive layer in a light-emitting diode3,4-Alkylenedioxy-thiophene copolymers,177

Film conductivityPolyaniline dopedwith di(butoxyethoxyethyl)ester of sulphosuccinic acid, 172

ElectroluminescencePhotovoltaic device

Polyether containing polyaromatics andpolyheteroaromatic, 185

Polyethylene-g-2-(7-benzothiazolyl-9,90-dioctylfluorene), 180

Electroluminescent materialsHole transport and electroluminescent agents

Isotactic and syndiotactic poly(9-fluorenylmethacrylate), 147

Poly(methyl methacrylate-co-naphthylcarbamate) and pyrene polyamides, 144,145

Emulsifing agentPolymeric

Kraton G-1901� esterified withmethoxypolyethylene glycol, 497

EmulsionInverse emulsion

Mixture consisting of paraffin oil, sorbitanmonooleate, and poly(ethyleneoxide) fattyacid esters, 501

Energetic polymersPropellant binder and explosive

Elastomers containing polyoxiraneand polyoxetane blocks withazides, 220

Stable energetic binderPoly(glycidyl dinitropropyl formal), 217

FibersHydrophobic/oleophobicVapor deposition of perfluoroacrylate onto

nonwoven fabrics, 121Heterocyclic rigid-rod polymers comprising

ballistic vestsBenzobisthiazole-naphthalic fibers, 224Polybenzazole fibers, 227

Vapor-grown carbon nanofibersDispersion of vapor-grown nanoscale tubes

using 4-(2,4,6-trimethylphenoxy)benzoicacid, 339

FluorineVery low surface energy polymersPolyoxetanes containing 2,2,2-trifluor-

oethoxymethyl substituents, 244

Gas chromatography columnsBinding of biomacromolecules and metal ionsSilica-g-polybutadiene-g-(polyamine), 663

Functionalized polymers for binding metal ionsin aqueous solutions

Poly(ethyleneimine-g-3,4-dihydroxysucci-nimide) and related derivatives, 684

Selective binding of cysteine while remaininginert to lysine

Poly(ethylene glycol) chloroethyl sulfone and-vinyl sulfone, 665

Separation of racemic mixturesOptically active malimides prepared by

condensing succinic anhydride with either(1R, 2R)- or (1S,2S)-2-benzyloxycyclopentylamine, 669

Polysaccharides containing grafted 9H-fluorenyl- or 5-indanyl-carbamates, 678

GelsCosmeticHairspray consisting of crosslinked C6-, C12-,

C14-, and C16-polyacrylates, 99Polyethylene oxide urethane/urea hairspray

containing casein, 129Electrochemical processesFerrocene amide polyethers, 255

ImplantsThermosensitive implants, 55Photogelation of coumarin ester end-capped

polylactones, 72Graft copolymers

AnticorrosiveSelf-doped polyaniline graft

copolymers, 93Polyamide graft copolymersPoly(4-amino-benzoic acid-co-(cysteine-g-

poly(n-butyl acrylate)), 59

Index 731

High-performance polymersEngineered thermoplastic with chemical

resistance and favorable high temperatureproperties

Poly(a-aromatic ketones), 705High-performance resin with high heat

resistance and high transparencyHydrogenated poly(1,3-cyclohexadiene-co-styrene), 702

High temperature stable flexible thermosetsPoly(silarylene-siloxane-acetylene)elastomers stable to 450�C with nominalweight loss, 721

High temperature injection moldable polymersModerate molecular weight polyimidesulfones, 708

Poly(ethyl a-acetoxyacrylate) homo- andalkyl a-acetoxyacrylate copolymers, 687–688

Ionomer resins with enhanced flex strength,elongation, and low melt flow indexproperties

Styrene and zinc diacrylate copolymers, 699Moderate molecular weight materials having

very high glass transition temperaturesPolyfluorene, polysulfonyl, and poly(fluorene-co-sulfonyl) copolymers, 689

Resins with enhanced light transmissionsexceeding 90% with little or no haze

Polycarbonates containing bisphenol A andisosorbide, 717

Resins with reduced water absorption used asmolding components

Polyformals and copolyformals thermosets,695

Thermoplastic resins useful as transparent resinsin automotive components

Polynorborene terpolymers containingethylene and propylene, 692

Thermoset ResinsBenzoxazines prepared usingo,p-Novolak resins, formaldehyde,and aniline, 712

HydrogelsDegradable crosslinked hydrogels

N,N0-(Dimethacryloyloxy)glutarylamidecrosslinking agents and derivatives for 2-hydroxyethyl acrylate, 272

Moderate strength copolymer hydrogelLinear urea-urethane block copolymer, 259

Oxygen permeableFumarate- and fumaramide-containinghydrogels, 265

Superabsorbent swellable hydrogelsCrosslinked polyethers capped with acrylicacid, 262

a,b-Poly aspartate sodium salt, 273

Ink jet printingFixing agents

Chain-extended thermoplastic guanidiniumpolymers, 289

Light emittingLight-emitting diodes

3,4-Alkylenedioxy-thiophene copolymers,177

Crosslinkable perfluorinated bisphenol Apolymeric derivatives, 190

Liquid crystalsBiaxial liquid crystals

Oligomeric phenylacetylene liquid crystallinederivatives, 307

Liquid crystal alignersPolyimides spin-coated withg-butyrolactone and N-methylpyrrolidone,293

Polyimides containing pendant 2-butenylsubstituents, 299

Nematic liquid crystal materialsPerfluoroalloxy aromatic derivatives, 316

Photo-inducable birefringencePolymethacrylates containing azosubstituents, 303

Processable, high tensile strength, and low meltviscosity

Polynaphthyl esters, 318

MacromonomersS-(Poly(n-butyl acrylate)-cysteine, 58

Polyethylene-methylmethacrylate, 59Magnetic resonanceImaging contrast-enhancing agents

Polypeptide imaging agents containinggadolinium(III) diethylenetriaminepentaacetic acid, 283

Mechanical strengthAdhesives and membranes

High tensile strength poly(dimethylsiloxane-urea-propyleneoxide), 26, 27

Enhancing polyolefin strengthIncorporation of 0.02 mol%norbornene-2,3-dicarboxylic acidanhydride, 560

732 Index

High strength fluorinated terpolymerTerpolymers consisting of tetrafluoroethylene,perfluoro(ethyl vinyl ether), and perfluoro(propyl vinyl ether), 234

Moderate strength copolymer hydrogelLinear urea-urethane block copolymer, 259

MembranesHydrophobic

Poly(dimethyl ketone) as industrial packagingfor water-containing foods, 117

Membrane blend of dithiolene and perfluoropolyphthalimide

Selective removal of propene from propene/propane streams, 531

Membranes having broad pore size ranges andrestricted pore size distribution

Polyvinyl alcohol membrane crosslinked withglutaraldehyde for use in separatingproteins, 675

NanofibersInorganic

Spiral shaped hollow silicon oxidenanofibers, 347

Vapor-grown carbon nanofibersDispersion of vapor-grown nanoscale tubesusing 4-(2,4,6-trimethylphenoxy)benzoicacid, 339

NanoparticlesCatalytic agents

Nanotubes functionalized with Wilkinson0scomplex, 333

Drug deliveryNanoparticles derived from poly(ethyleneglycol-b-valerolactone) derivatives, 44

Inorganic nanotubesPyrolysis of 1-(ferrocenylethynyl)-3-(phenylethynyl)benzene thermosets as amethod

for preparing iron nanoparticles, 344Nanotubes

DispersantsCarbon nanotubes electrochemicallyderivatized with diazonium4-alkylaromatics, 329

Noncovalent dispersion of nanotubes usingelectron donor/ acceptor interactions

characteristic of the polymerbackbone, 351

Enhanced mobilities and transconductanceproperties

Nanotubes functionalized with Wilkinson0scomplex, 333

Enhanced water solubilityMulti-walled nanotube amidated with

guanidine containing polystyrene-g-dibenzo-18-crown-6-ether, 325

Oxidation reactionsIntroduction of carboxylic acids on nanotubes

using ammonium persulfate and sulfuricacid, 336

Nonlinear optical chromophoresLight-emitting diodesCrosslinkable perfluorinated bisphenol A

polymeric derivatives, 192Method of improving photorefractive efficienciesComposition consisting of C60 fullerene-

terminated polymethacrylate derivative,plasticizer, and a nonlinearchromophore, 458

WaveguidesPolystyrene containing pendant thiophenes,

419

Oxidative stabilityAtomic oxygen-resistant materials for use in

space explorationPolydiamantane derivatives containing

phosphine oxide, 119Fire resistant materialsPolybenzazole derivatives, 227Polymeric benzobisthiazole-naphthalic

derivatives, 224High temperature stable flexible thermosetsLinear poly(silarylene-siloxane-acetylene)

elastomers cured 450�C with around 7weight loss, 721

Paint additivesLatex paintTerblock methacrylate as viscosity index

improver, 1Marine paintNontoxic polyacrylates containing pendant

semifluorinated substituents, 108Photoactive materials

Curing agentsBenzophenone s-triazine derivatives, 112Photoactive coumarin end-capped polymers,

72Photo-inducable birefringencePolymethacrylates containing azo

substituents, 304Photoluminscence

Blue and blue-green spectral emission materialsFluorene copolymers containing pyrrole, 432

Index 733

Photoluminscence (continued)High efficiency

Biphenyl copolymers containing a cyclicbidentate iridium substituent, 427

Lower power consumption with higherbrightness and ease of material processing

Poly(thiophene-co-fluorene) derivatives, 437Solvent-soluble light-emitting agents

Conjugated fluorene block, co-, andterpolymers, 448

Conjugated poly(fluorene-oxadiazole)polymers, 453

PhotorefractionMethod of improving photorefractive efficiency

Composition consisting of C60 fullerene-terminated polymethacrylate derivative,plasticizer,andanonlinearchromophore,458

PhotoresistsAnti-reflective coating and photoresist pattern

Crosslinked product of polysuccinic anhydrideand polyvinyl dimethylacetal, 125

Chemical amplification type resist compositionPerfluoroacetal or perfluoroketalpolymethacrylates containing norbornenesubstituents, 611

Photoresist compositions effective in the 193 and157 nm useful in photolithography andhaving enhanced etch resistance

Norborene lactones and sultonescopolymers, 632

Photoresists useful in multilayer resist systemsthat provide contrast upon exposure tophotogenerated acid

Norborene silsesquioxanes copolymers, 636Photoresist compositions that are transparent to

irradiation at 160 nm or lessPolymerizable perfluoro norbornene, 623

Positive and negative tone photoresistcompositions activated at 193 nm

Solvent-soluble fluoroacrylatescopolymers, 627

Positive photosensitive composition effective at200 nm or less

Diamantane acrylate terpolymers containinglactones and diadamantane, 651

Positive resists sensitive to electron beams ordeep UV radiation

Adamantane methacrylates terpolymershaving lactone substituents, 642

Adamantane 4-hydroxyphenyl methacrylatescopolymers, 647

Resist compositions and patterning processsuitable for deep UV lithography

Fluoro vinylsulfones terpolymers, 616

Polymer fractionalizationPoly(2-hydroxethyl methacrylate-co-methacrylic acid) using ethanol andn-hexane, 41

Polymerization methodsAnionic

Anionic polymerisation of oxiraneswithout the use of crown ethers orcryptands, 463

Amido-organoborate initiator systems, 465Polyisocyanates end-capped with acylchlorides, 478

Preparation of high molecular weighpoly(a)-methylstyrene using sec-butyllithium, 472

Atom transfer radical polymerizationPolymerization of styrene using ethyl 2-bromo-isobutyrate, 596

CationicPolymerizing of liquefied isobutylene using1,2-bis(9-bora-1,2,3,4,5,6,7,8-octafluorofluorenyl)-3,4,5,6-tetrafluorobenzene, 487

Terpolymerization of THF, 3-ethyl-tetrahydrofuran, and ethylene oxide usingNAFION� NR-50 acidic resin, 489

Critical polymerizationPolymerization of vinylidene fluoride aboveits critical density and temperature, 231

Free radicalDithiocarbamic-5-oxo-4,5-dihydro-oxazolederivatives, 606

Macromolecular photoinitiators containingpolyisobutylene, 507

Polymerization of perfluoromonomers usingperfluorodiacylperoxides, 504

Nitric oxide mediatedN-Alkoxy-4,4-dioxy-polyalkyl-piperidines,600

t-Butyl 1-diethylphosphono-2,2-dimethylpropyl nitroxide, 1

Nitric oxide, 595Phenyl-t-butylnitrone, 595Spiro-ketal nitroxide, 592

Photolytically mediatedPolymerization using diethanolamine withmethylene blue, 605

Reactivatable polymerizationReactivatable polymethyl methacrylate usingbis(ethoxythiocarbonyl)disulfane as thechain transfer agent, 511

Reactivatable poly(styrene-co-maleicanhydride) with 2,2,6,6-tetramethyl-1-piperidinyloxy, 514

734 Index

Reversible addition–fragmentation chaintransfer

Block copolymers of acrylonitrile and butylacrylate using cumenyl thiobenzoic acid,714

Low molecular weight polystyrene usingdibenzyl trithiocarbonate, 596

Preparation of low polydispersity poly(N,N-dimethylacrylamide) using N,N-dimethyl-S-thiobenzoylthiopropionamide, 588

Ring-opening metathesis polymerizationCatalyst comprising bis(tricyclohexylpho-sphine)benzylidine ruthenium(IV)dichloride, 529

Use of ruthenium salts in preparing high A,B-alternating copolymers, 533

SemiconductorsEnhanced mobilities and transconductance

propertiesNanotubes functionalized with Wilkinson0scomplex, 333

Film transistorsPolythiophenes, 205Poly(fluorene-co-thiophene), 209

Insulator filmsPolyarylene ethers, 201

Liquid crystal displaysLow molecular weight [2,3-b]-thienothiophene derivatives, 196

Silicon FluidsWater and oil repellency with weather, solvent,

and chemical resistanceCyclic siloxane compounds containing anunsaturated substituent, 247

SurfacesBiological

Thromboresistant heparinized surfaces, 89Cosmetic

Hair sprays consisting of crosslinked C6-, C12-,C14-, and C16-polyacrylates, 99

Polyethylene oxide urethane/urea derivativescontaining casein, 129

MechanicalOxyfluorination for improving shear bondstrength, 97

Very low surface energyAcrylate fluorocyclic silanes furniture polishadditives, 102

Polyoxetanes containing 2,2,2-trifluor-oethoxymethyl substituents, 244

SurfactantsVery low surface tensionPerfluoro organosilicons, 251

Synthetic methodsAniline formaldehyde oligomers, 384Biodegradable aliphatic polyesters by

deglycolation, 371Cysteine graft copolymers containing S-poly

(n-butylacrylate), 395N,N0-Dialkylpolyvinylamines using poly(N-

vinylformamide), 409Guerbet polymers, high molecular

weight, 398Hydroaminomethylation of polyolefins, 373Method for preparing high trans content poly

(styrene-co-butadiene) using barium salt oftri(ethyleneglycol)ethyl ether, 469

Method for preparing vinyl-richpolybutadiene rubber using ironisooctanoate, 467

Multistar polystyrene containing 34 arms, 417Natural and unnatural oligonucleotide

preparation, 413Nonsymmetrical peroxides, 367Perdeuterated polyiimides, 376Permutational synthesis of new heterocyclic

amines, 362Poly(aniline-co-thiophene), 381Polybutadiene (meth)acrylates, 379Polyether maleimides, 386Poly(9-fluroenone), 389Poly(1,4-phenylene vinylene) derivatives, 401Polypropylene containing high graft levels of

succinic anhydride without viscosityincrease, 392

Preparation of high cis-1,4-polyisoprene usingneodymium tris(bis(2-ethylhexyl)-phosphate), 550

Preparation of polypropylene-g-perfluoroacrylate by vapor deposition ofperfluoroacrylate monomer, 122

S-Poly(n-butylacrylate)cysteinemacromonomer, 395

Solid state synthesis of 18F-fluorobromomethane, 357

Suzuki method for polymerization of aromaticmonomers, 444

Index 735

advances in-polymer-chemistry-and-methods-reported-in-recent-us-patents

Education