Polymer Synthesis: Theory and Practice

Springer-Verlag Berlin Heidelberg GmbH

D. Braun . H. Cherdron . H. Ritter

Polymer Synthesis:Theory and Practice

Fundamentals, Methods, Experiments

Third Edition

With 33 Figures and 31 Tables

, Springer

Professor Dr. Dr. h.c. Dietrich BraunDeutsches Kunststoff-InstitutSchlossgartenstrasse 664289 Darmstadt, Germany

Professor Dr. Harald CherdronEichenweg 4065207 Wiesbaden, Germany

Professor Dr. Helmut RitterIohannes-Gutenberg-UniversitatInstitute of Organic ChemistryDuesbergweg 10-1455099 Mainz, Germany

Library of Congress Cataloging-in -Publication DataBraun, Dietrich, 1930- Polymer synthesis : theory and practice: fundamentals, methods,experiments 1D. Braun, H. Cherdron, H. Ritter. p. cm. Includes bibliographical references and index.

QD281.P6 B6852001 547'.28-dc21

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Preface

This book is an English translation of"Praktikum der Makromolekularen Stoffe"published in 1999 and based on three previous editions of "Praktikum derMakromolekularen Organ ischen Chemie" (1966/1971/1979).

The basic concept of the book has remained unchanged: We did not aim tocompile a comprehensive collection of recipes for the synthesis of a host of poly­mers. Instead, emphasis was put on a broader description of the general methodsand processes for the synthesis, modification, and characterization of macromol­ecules. These more fundamental chapters are supplemented by 110 selected anddetailed experiments and by sufficient theoretical treatment. Thus, an additionaltextbook is not necessarily needed in order to understand the experiments.

In addition to the preparative aspects we have also tried to give the reader animpression of the relation of chemical structure and morphology of polymers totheir properties.

Some experiments in the previous edition were deleted and several of the re­maining ones were technically updated. Newly added are: Polymerization withsupported catalysts and with metallocene catalysts; photopolymerization (pho­tolithography); liquid crystalline polymers; polyoxazolines and poly(aryleneether)s. Chapter 5 "Modification of Polymers" is also new. It contains chemicalconversions of macromolecules, addition of stabilizers, fillers and reinforcingfibers as well as polymer blends and polymer foams.

The target groups of this book are students in organic and polymer chemistryas well as chemists in industry who want to acquaint themselves with this inter­disciplinary field. Of course, it can also give guidance for already established ornew practical courses.

During the preparation of the English edition we were assisted by a highly mo­tivated team of the Organic Chemistry Department of the University of Mainz(Germany) . We wish to express our sincerest appreciation to H.W. Schnecko, Ms.M. Tabatabai, P.Casper, M. Heinenberg, L.M. Mejias-Llanos, M. Roth, J. Storsberg,and A. Theis. Finally, we thank the Chemistry Editorial and the DeskeditingChemistry of Springer-Verlag for an optimal cooperation.

Spring 2001 Dietrich Braun, DarmstadtHarald Cherdron, WiesbadenHelmut Ritter, Mainz

Contents

Introduction. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

1.1 Definitions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

1.2

1.31.3.1

1.3.21.3.3

1.3.3.11.3.3.2

1.3.3.31.3.4

1.41.4.11.4.2

1.4.31.4.4

1.4.5

1.5

1.6

1.7

2

2.1

2.2

2.2.1

2.2.22.2.2.1

2.2.2.2

2.2.3

Structure and Nomenclature of Macromolecular Substances

Properties of Macromolecular Substances .Macromolecules in Solution . . . . .

Macromolecules in the Molten State . . .Macromolecules in the Solid State.....Macromolecules in the Amorphous State.

Macromolecules in the Crystalline State ..Macromolecules in the Elastomeric State..Liquid Crystal Polymers (LCP) .

General Literature on Macromolecules. . . . . . . . . . . . . . . . . . . . .

Textbooks .Monographs and Handbooks . . . . . . . .Laboratory Manuals .

Nomenclature . . . . . . . . . . .Journals and Periodicals . . . . . . . . ...

List of General Abbreviations . . . . . . . . . . . . . . . . . . . . . . . . . .

Abbreviations for Technically Important Polymers . .. . .

Relevant SI Units and Conversions . . . . . . . . . . . . . .

Methods and Techniques for Synthesis, Characterization, Processing,

and Modification of Polymers. . . . . . . . . . . . . . . . . . . . . . . .

Methods for Synthesis of Macromolecules. . . . . . . . . . . . . . . . .

Processes for Manufacturing Macromolecular Materials . . . . . . . . .

Particularities in the Preparation of Polymers .

Polyreactions in Bulk . . . . . . . . . . . . . . . . . . . . . .

Homogeneous Polyreactions in Bulk. . . . .

Heterogeneous Polyreactions in Bulk .

Polyreactions in Solution. . . . . . . . . . . . . . . . . . . . . . . .

2

10

111214

14152021

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25

29

30

32

35

35

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47

494950

50

VIII Contents

2.2.4

2.2.4.1

2.2.4.2

2.2.5

2.2.5.1

2.2.5.2

2.2.5.3

2.2.5.4

2.2.5.5

2.2.5.6

2.2.5.7

2.3

2.3.1

2.3.2

2.3.2.1

2.3.2.2

2.3.3

2.3.3.1

2.3.3.2

2.3.4

2.3.4.1

2.3.4.2

2.3.4.3

2.3.5

2.3.6

2.3.7

2.3.8

2.3.8.1

2.3.8.2

2.3.9

2.3.10

2.3.11

2.3.12

2.3.12.1

2.3.12.2

2.3.12.3

2.3.12.4

2,4

2,4.1

2,4.2

2.4.2.1

Polyreactions in Dispersion . . . . . . . . .Polyreactions in Suspension . . . . . . . . .

Polyreactions in Emulsion . . . . . . . . . . .General Techniques for Preparation of Macromolecular Substances inthe Laboratory. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

Safety in the Laboratory . . . . . . . . . . . . . . . . . . . . . . . . . .Working with Exclusion of Oxygen and Moisture. ..... ...

Purification and Storage of Monomers . . . . . . . . . . . . . . .Reaction Vesselsfor Polymerization Reactions . . . . .

Control and Termination of Polymerization Reactions . . . . .

Isolation of Polymers . . . . . . . . . . . . .Purification and Drying of Polymers ...

Characterization of Macromolecules . . .Solvents and Solubility .Determination of Molecular Weight of Polymers . . .

Determination of Solution Viscosity of Polymers. . .Determination of the End Groups of Polymers . . . . . . . . ..Fractionation of Polymers . . . . . . . . . . . . . . .. .

Analysis of Fractionation Data. . . . . . . . . . . . .. . .Fractionation According to the Chemical Composition . . . . . . . . . . .

Determination of Glass Transition Temperature, Softening Point, MeltingRange, and Crystallite Melting Point . . . . . . . . . ...Determination of the Glass Transition Temperature . . . . . . . . . . . . .

Determination of the Softening Point . . . . . . . . . . . . . . . . . . . . . .Determination of the Melting Range and the Crystallite Melting Point. . .Determination of the Melt Viscosity (Melt Index) of Polymers .Determination of the Crystallinity of Polymers . . . . . . . . . . . . . . . .Determination of the Density of Polymers. . . . . . . . . . . . . . . . . . .Degradation of Polymers. . . . . . . . . . . . . . . . . . . . . . . . . . . . .Thermal Degradation of Polymers . . . . .Chemical Degradation of Polymers . . . . .

Optical Investigations on Polymers. . . . .

Determination of Important Groups and Elements.

Characterization of Copolymers. . . . . . . . . . . .

Mechanical Measurements on Polymers. .

Stress-Strain Measurements . . . . . . .. ..

Dynamic-Mechanical Measurements. .. . .

Determination of Impact Strength and Notched Impact Strength . . . . .

Determination of Hardness . . . . . . . . . . . . . . . . . . . . . . . . . . .

Processing of Polymers .Size Reduction of Polymers . . . . . . . . .Melt Processing of Polymers. . . . . . . . .

Preparation of Polymer Films from the Melt . . . .

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53

57

57

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58

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64

65

6667

71

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84

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95

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97

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98

100102

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105

105

106

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107

Contents IX

2.4.2.22.4.32.4.3.12.4.3.22.4.4

2.5

3

3.13.1.1

Melt-Spinning .Processing of Polymers from Solution .Preparation of Films from Solution. . .Solution-Spinning .Processing of Aqueous Polymer Dispersions. . . . . . . . .

References for Chapter 2 . . . . . . . . . . . . . . . . . .

Synthesis of Macromolecular Substances by Addition Polymerization . .

Radical Homopolymerization . . . . . . . . . . . . . . . .Polymerization with Peroxo Compounds as Initiators . .

107

108108109109

110

III

112

119

Example 3-1

• Example 3-2

Example 3-3

Example 3-4

Example 3-5

Example 3-6

Example 3-7

ThermalPolymerization of Styrene in Bulk(Effect ofTemperature) .

Emulsion Polymerization of Styrene with PotassiumPeroxodisulfate. . . . . . . . . . . . . . . . . . . . .

Bulk PolymerizationofVinyl Acetate with DibenzoylPeroxide .

Polymerization ofVinyl Acetate with AmmoniumPeroxodisulfatein Emulsion. . . . . . . . . . .. . .. . . .

Polymerization of Acrylonitrile with AmmoniumPeroxodisulfatein OrganicSolution .

BeadPolymerization ofVinyl Acetate .

Polymerization of MethacrylicAcid with PotassiumPeroxodisulfate in AqueousSolution .

121

121

122

122

123

124

124

3.1.2 Polymerization with Azo Compounds as Initiator . . . . . . . . . 125

Example 3-8 Bulk Polymerization of Styrene with 2,2'-Azo-bisisobutyronitrile (Effect of InitiatorConcentration) 126

Example 3-9 Bulk Polymerization of Styrene with 2,2'-Azo-bisisobutyronitrile in a Dilatometer. . . . . . . . . . . . . . . 126

Example 3-10 Polymerizationof Styrene with 2,2'-Azobisisobutyronitrilein Solution. . . . . . . . . . . . . . . . . . . . . . . . . . . . . 128

Example 3-11 Bulk Polymerization of Methyl Methacrylatewith 2,2'-Azo­bisisobutyronitrile . . . . . . . . . . . . . . .. . . . . . . 129

3.1.3 Polymerization with Redox Systems as Initiators. . . . . . . 130

Example 3-12 Polymerization of Acrylamide with aRedoxSysteminAqueousSolution. . . . . . . . . . . . . . . . . . . . 131

• Example 3-13 Fractionation of Polyacrylamide byGelPermeationChromatography inWater. . . . . . . . . . . . . . . 132

Example 3-14 Polymerization of Acrylonitrilewith a Redox SysteminAqueousSolution(Precipitation Polymerization) . . . . . . . 133

x Contents

Example 3-15 Emulsion Polymerizat ion of Isoprene with a Redox System.. 134

Example 3-16 Polymerization of Styrene with Redox Systems in an Organic

Solvent. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 135

3.1.4

3.1.5

3.2

3.2.1

3.2.1.1

Polymerization Using Photolabile Compounds as Initiators . . . . . . . . .

• Example 3-17 Photopolymerization of Hexamethylene Bisacrylate .

Polymerization of Cyclodextrin Host-Guest Complexes in Water .

• Example 3-18 Free Radical Polymerization of Cyclodextrin Host-GuestComplexes of Butyl Acrylate from Homogeneous AqueousSolution (Precipitation Polymerization). . . . . .

Ionic Homopolymerization. . . . . . . . . . . . . . .

Ionic Polymerization via C=C Bonds. . . . . . . . . . . . . . . . . . .

Cationic Polymerization with Lewis Acids as Initiators. . . . . . . . . .

• Example 3-19 Cationic Polymerization of Isobutylene with Gaseous BF3

at LowTemperatures .

Example 3-20 Cationic Polymerization of Isobutyl Vinyl Ether withBF3-Etherate at LowTemperatures . . . . . . . .

Example 3-21 Cationic Polymerization of a-Methylstyrene in Solution .

136

136

137

138

138

139

143

145

145

146

3.2.1.2 Anionic Polymerization with Organometallic Compounds as Initiators. . 147

Example 3-22 Anionic Polymerization of a-Methylstyrene with Sodium

Naphthalene in Solution ("Living Polymerization") . . . . . .. 147

Example 3-23 Stereospecific Polymerization of Styrene with Pentylsodium . 150

Example 3-24 Preparation of Isotactic and Syndiotactic Poly(methylMethacrylate) with Butyllithium in Solution . . . . . . . . .. 152

• Example 3-25 Stereospecific Polymerization of Isoprene with Butyllithium.. 153

Ionic Polymerization via C=O Bonds. . . . .

Example 3-26 Anionic Polymerization of Formaldehyde in Solution(precipitation Polymerization) . . . . . . . . . .

Ring-Opening Polymerization. . . . . . . . . . . . . . . . . . .

Ring-Opening Polymerization of Cyclic Ethers . . . . . . . . . . . . . . . .

• Example 3-27 BulkPolymerization ofTHF with Antimony Pentachloride •.•

3.2.2

3.2.3

3.2.3.1

3.2.3.2

3.2.3.3

3.2.3.4

Ring -Opening Polymerization of Cyclic Acetals. . . . . . . . . . . . . . . .

Example 3-28 Polymerization ofTrioxane with BFrEtherate

as Initiator. . . . . . . . . . . . . . . . . . . .

Ring-Opening Polymerization of Cyclic Esters (Lactones) .

Example 3-29 Ring-Opening Polymerization of Dilactide with Cationic

Initiators in Solution . . . . . . . . . . . . . . . . . . . . . . .

Ring-Opening Polymerization of Cyclic Amides (Lactams) .

Example 3-30 BulkPolymerization of e-Caprolactarn with Anionic Initiators(Flash Polymerization) . . . . . . . . . . . . . . . . . . . . . .

156

157

158

158

159

160

162

163

164

164

166

Contents XI

3.2.3.5 Ring-Opening Polymerization of Oxazolines . . . . . . . . . . . . . . . . . 166

• Example 3-31 Synthesis of a Linear,N-Acylated PolyethylenimineThrough Cationic Polymerization of an Oxazoline Preparedfrom Octanoic Acid and 2-Aminoethanol. . . . . . . . . . . 167

3.3.1.1

3.3

3.3.1

3.3.2

3.4

3.4.1

Metal Catalyzed Polymerization. . . . . . . . .

Polymerization with Ziegler-Natta Catalysts .

• Example 3-32 Polymerization of Ethylene with Ziegler-Natta-Catalysts .

• Example 3-33 Polymerization of Ethylene on a Supported Catalyst

Example 3-34 Stereospecific Polymerization of Propylene withZiegler-Natta-Catalysts. . . . . . . . . . . . .. .

Example 3-35 Stereospecific Polymerization of Styrene withZiegler-Natta-Catalysts .

Example 3-36 Stereospecific Polymerization of Butadiene with Ziegler­Natta-Catalysts: Preparation of cis-l A-Polybutadiene . . . . .

Metathesis Polymerization. . . . . . . . . . . . . . . . . . . . . . . . . . . .

Example 3-37 Poly(l-Pentenylene) by Metathesis Polymerization

of Cyclopentene with a Ziegler-Natta-Catalyst in Solution . .

Polymerization with Metallocene Catalysts . . . . . . . . .

Example 3-38 Metallocene-Catalyzed Polymerization of Propylene toHighly Isotactic Polypropylene . . . . . . . . . . . . . . . ..

Copolymerization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

Random and Alternating Copolymerization . . . . . . . . . . . . . . . . . .

Example 3-39 Radical Copolymerization of Methacrylic Acid with n-Butyl

Acrylate in Emulsion . . . . . . . . . . . . . . . . . . . . . . .

• Example 3-40 Copolymerization of Styrene with Methyl Methacrylate.. .

• Example 3-41 Radical Copolymerization of Styrene with 4-Chlorostyrene(Determinat ion of the Reactivity Ratios) . . . . . .

Example 3-42 Cationic Copolymerization of Styrene with 4-Chlorostyrene(Determination of the Reactivity Ratios) . . . . . . . . .

Example 3-43 Radical Copolymerization of Styrene with Acrylonitrile(Determination of the Reactivity Ratios) . . . . . .

Example 3-44 Radical Copolymerization of Styrene with Butadiene inEmulsion .

Example 3-45 Radical Copolymerization of Butadiene with Acrylonitrile in

Emulsion .

168

169

171

173

174

175

176

178

179

180

181

182

182

191

192

194

194

196

197

198

Example 3-46 Radical Copolymerization of VinylChloride with VinylAcetate

(Internal Plasticization) . . . . . . . . . . . . . . . . . 198

• Example 3-47 Copolymerization of Styrene with Methyl Acrylate(Internal Plasticization) . . . . . . . . . . . . . . . . . 200

Example 3-48 Preparation of a Styrene/Butyl Acrylate Copolymer

Dispersion. . . . . . . . . . . . . . . . . . . . . . . . . . . . . 201

XII Contents

Example 3-49 Radical Copolymerization of Styrene with 1,4-Divinylbenzenein Aqueous Suspension (Crosslinking Copolymerization) . .. 202

• Example 3-50 Cationic Copolymerization of 1,3,5-Trioxane with1,3-Dioxolane (Ring-Opening Copolymerization) . . . . . . . 202

Example 3-51 Radical Copolymerization of Styrene with Maleic Anhydride(Alternating Copolymerization) . . . . . . . . . . . . . . . . . 203

• Example 3-52 Radical Copolymerization of Cyclohexene with Sulfur Dioxide(Alternating Copolymerization) . . . . . . . . . . . . . . . . . 203

3.4.2 Block and Graft Copolymerization . . . . . . . . . . . . . . . . . . . . . . . 204

Example 3-53 Preparation of a BlockCopolymer of 4-Vinylpyridine and

Styrene by Anionic Polymerization . . . . . . . . . . . . . .. 207

• Example 3-54 Preparation of a Butadiene-Styrene BlockCopolymer. . . .. 208

Example 3-55 Graft Copolymerization of Styrene on Polyethylene. . . . .. 209

3.5 References for Chapter 3 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 210

4 Synthesis of Macromolecular Substances by Condensation

Polymerization and Stepwise Addition Polymerization . . . . . . . . . .. 212

4.1 Condensation Polymerization (Polycondensation) . . . . . . . . . . . . .. 212

4.1.1 Polyesters..... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 217

4.1.1.1 Polyesters from Hydroxycarboxylic Acids . . . . . . . . . . . . . . . . . .. 219

4.1.1.2 Polyesters from Diols and Dicarboxylic Acids . . . . . . . . . . . . . . . . . 219

• Example 4-1 Preparation of a Low Molecular Weight Branched Polyesterfrom a Dioland a Dicarboxylic Acid by Melt Condensation.. 219

Example 4-2 Preparation of a High MolecularWeight Linear Polyester

from a Diol and a Dicarboxylic Acid by Condensationin Solution. . . . . . . . . . . . . . . . . . . . . . . . . . . . . 221

4.1.1.3 Polyesters from Diols and Dicarboxylic Acid Derivatives. . . . . . . . . .. 222

Example 4-3 Preparation of a Polyester from Ethylene Glycoland Dimethyl

Terephthalate by Melt Condensation. . . . . . . . . . . . .. 223

Example 4-4 Preparation of a Polycarbonate from 4,4'-lsopropylidene-

diphenol (Bisphenol A) and Diphenyl Carbonate by

Transesterification in the Melt. . . . . . . . . . . . . . . . . . 223

Example 4-5 Preparation of a Thermotropic, Main-Chain Liquid Crystalline

(LC) Polymer by Interfacial Polycondensation . . . . . . . . . 225

Example 4-6 Preparation of a Liquid Crystalline (LC), Aromatic Main-Chain

Polyester by Polycondensation in the Melt. . . . . . . . . .. 226

• Example 4-7 Preparation and Crosslinking (Curing) of UnsaturatedPolyesters . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 227

Example 4-8 Preparation and Crosslinking (Curing) of Alkyd Resins. . . . . 230

Contents XIII

4.1.2.3

4.1.2

4.1.2.1

4.1.3

4.1.3.1

4.1.2.2

Polyamides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

Polyamides from w-Aminocarboxylic Acids .

Example 4-9 Preparation of an Aliphatic Polyamide by Polycondensation

of E-Aminocaproic Acid in the Melt . . . . . . . . . . . . . . .

Polyamides from Diamines and Dicarboxylic Acids . . . . . . . .

Example 4-10 Preparation of Nylon-6,6 from Hexamethylenediammonium

Adipate (AH Salt) by Condensation in the Melt. . . . . . . . .

Polyamides from Diamines and Dicarboxylic Acid Derivatives . . . . . . .

Example 4-11 Preparation of Polyamide 6,10 from Hexamethylenediamineand Sebacoyl Dichloride in Solution and by InterfacialPolycondensation .

Example 4-12 Microencapsulation of a Dyestuff by Interfacial

Polycondensation. . . . . . . . . . . . . . . . . . . . . . . . .

• Example 4-13 Synthesis of a Lyotropic Liquid Crystalline AromaticPolyamide from Terephthalic Acid Dichloride and Silylated2-Chloro-1A-phenylenediamine by Polycondensation in

Solut ion .

Phenol-Formaldehyde Resins .

Acid-Catalyzed Phenol-Formaldehye Condensation (Novolaks) .

Example 4-14 Acid-Catalyzed Phenol-Formaldehyde Condensation .

232

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234

235

235

236

237

238

240

243

244

245

4.1.3.2 Base-Catalyzed Phenol-Formaldehyde Condensation (Resols) . . . . . . . 245

Example 4-15 Base-Catalyzed Phenol-Formaldehyde Condensation. . . . . 246

4.1.4

4.1.4.1

Urea- and Melamine-Formaldehyde Condensation Products .

Urea-Formaldehyde Resins .

Example 4-16 Urea-Formaldehyde Condensation . . . . . . . . . . .

247

247

248

4.1.4.2 Melamine-Formaldehyde Resins. . . . . . . . . . . . . . . . . . . . . . . . . 249

Example 4-17 Melamine -Formaldehyde Condensation . . . . . . . . . . . . 250

4.1.5

4.1.6

4.1.6.1

4.1.6.2

4.1.6.3

Poly(alkylene Sulfide)s .

Example 4-18 Preparation of a Poly(alkene Sulfide) from1,2-Dichloroethane and Sodium Tetrasulfide .

Poly(arylene Ether)s .

Poly(phenylene Ether)s .

Example 4-19 Preparation of Poly(2,6-dimethylphenylene Ether) .

Aromatic Polysulfides [Poly(arylene Sulfide)s] .

Poly(arylene Ether Sulfone)s .

Example 4-20 Synthesis of Poly(arylene Ether Sulfone) from Bisphenol A

and 4A'-Dichlorodiphenyl Sulfone .

251

252

253

254

255

256

257

258

XIV Contents

4.1.6.4

4.1.7.2

4.1.8

4.1.7

4.1.7.1

4.2

4.2.1

4.2.1.1

Poly(arylene Ether Ketone)s .

Example 4-21 Preparation of a Substituted Poly(ether Ether Ketone) from4,4-Bis(4-hydoxyphenyl)pentanoic Acid and

4,4'-Difluorobenzophenone . . . . . . . . . . . . .

Polymers with Heterocydic Rings in the Main Chain. . . . . . . . . . . . .

Polyimides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

Example 4-22 Preparation of a Polyimide from Pyromellitic Dianhydrideand 4,4'-Oxydianiline by Polycyclocondensation .

Poly(benzimidazole)s .

Polysiloxanes. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

• Example 4-23 Ring-Opening Polymerization of a CyclicOligosiloxane to aLinear,High Molecular Weight Polysiloxane with Hydroxy EndGroups; Curing ofthe Polymer . . . . . . . . . . . . . . . . ..

Example 4-24 Equilibration of a Silicone Elastomer to a Silicone Oilwith

Trimethylsilyl End Groups . . . . . . . . . . . . . . . . . . . .

Stepwise Addition Polymerizations . . . . . . . . . . . . . . . . . . . . . . .

Polyurethanes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

Linear Polyurethanes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

Example 4-25 Preparation of a Linear Polyurethane from l,4-Butanediol

and Hexamethylene Diisocyanate in the Melt . . . . . . . . .

Example 4-26 Preparation of a Linear Polyurethane from 1A-Butanediol

and Hexamethylene Diisocyanate in Solution .

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4.2.1.2 Branched and Crosslinked Polyurethanes . . . . . . . . . . . . . . . . . .. 271

4.2.2 Epoxy Resins. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 273

• Example 4-27 Preparation of Epoxy Resins from Bisphenol AandEpichlorohydrin. . . . . . . . . . . . . . . . . . . . . . . . .. 275

4.3 References for Chapter 4 . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 277

5 Modification of Macromolecular Substances . . . . . . . . . . . . . . . .. 279

5.1 Chemical Conversion of Macromolecular Substances . . . . . . . . . . .. 279

Example 5-1 Poly(vinylAlcohol) by Transesterification of Poly(vinyl

acetate); Reacetylation of Poly(vinyl Alcohol). . . . . . . . . . 287

Example 5-2 Preparation of Poly(vinylbutyral) . . . . . . . . . . . . . . .. 288

• Example 5-3 Saponification of a Copolymer of Styrene and MaleicAnhydride. . . . . . . . . . . . . . . . . . . . . . . . . . . . . 289

Example 5-4 Preparation of Linear Poly(ethylenimine) by Saponification of

Polyoxazoline . . . . . . . . . . . . . . . . . . . . . . . . . .. 289

Example 5-5 Acetylation of Cellulose . . . . . . . . . . . . . . . . . . . . . 290

Example 5-6 Preparation ofTrimethylcellulose . . . . . . . . . . . . . . .. 291

Contents

Example 5-7

Example 5-8

Example 5-9

Preparation of Sodium Carboxymethylcellulose. . .

Esterification of Cellulose with p-Toluenesulfonyl Chloride . .

Acetylation of the Semi-Acetal End Groups of

Poly(oxymethylene) with Acetic Anhydride . . . . . . . . . .

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5.2 Crosslinking of Macromolecular Substances. . . . . . . . . . . . . . . . .. 294

Example 5-10 Crosslinking of Chlorinated Nylon-6.6 by Irradiation. . . . . . 295

Example 5-11 Vulcanization of a Butadiene-Styrene Copolymer (SBR) . . . . 297

Example 5-12 Preparation of a Cation Exchanger by Sulfonation of

Crosslinked Polystyrene . . . . . . . . . . . . . . . . . . . . . 300

Example 5-13 Preparation of a Cation Exchanger by Sulfonation of a

Phenol-Formaldehyde Condensation Polymer. . . . . . . .. 301

Example 5-14 Preparation of an Anion Exchanger from CrosslinkedPolystyrene by Chloromethylation and Amination. . . . . .. 301

5.3 Degradation of Macromolecular Substances. . . . . . . . . . . . . . . . .. 302

Example 5-15 Thermal Depolymerization of Poly(a-methylstyrene) and of

Poly(methyl Methacrylate) . . . . . . . . . . . . . . . . . . . . 305

Example 5-16 Thermal Depolymerization of Poly(oxymethylene) . . . . . . 305

Example 5-17 Oxidat ive Degradation of Poly(vinylAlcohol) with Periodic

Acid. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 306

• Example 5-18 Hydrolytic Degradation of an Aliphatic Polyester . . . . . . . 307

Example 5-19 Hydrolytic Degradation of Cellulose and Separation of the

Hydrolysis Products by Chromatography. . . . . . . . . . . . 308

5.4 Modification of Polymers by Additives. . . . . . . . . . . . . . . . . . . . . 308

5.4.1 Addition of Stabilizers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 309

Example 5-20 Suppression of the Thermo-Oxidative Crosslinking of

Polyisoprene by Addition of an Antioxidant. . . . . . . . .. 310

Example 5-21 Suppression of the Thermal Dehydrochlorination ofPoly(vinyl Chloride) by Addition of Stabilizers . . . . . . . . . 311

5.4.2

5.4.3

5.5

5.5.1

5.5.2

5.5.2.1

Addition of Plasticizers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

• Example 5-22 Polymerization of Styrene in Presence of Paraffin Oil (ExternalPlasticization) . . . . . . . . . . . . . . . . . . . . . . . . . . .

Add ition of Fillers and Reinforcing Materials . . . . . . . . . . . . . . . . .

Example 5-23 Preparation of a Composite Material from an Unsaturated

Polyester Resin and Glass Fibers. . . . . . . . . . . . . .

Mixtures of Polymers (Polymer Blends) . . . . . . . . . . . . . . . .

Properties of Polymer Blends . . . . . . . . . . . . . . . . . . . . . . . . . .

Preparation of Polymer Blends . . . . . . . . . . . . . . . . . . . . . . . . .

Concerted Precipitation from Solution. . . . . . . . . . . . . . . . . . . . .

Example 5-24 Preparation of Polymer Blends from Solution .

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XVI Contents

5.5.2.2 Coprecipitation of Polymer Latices . . . . . . . . . . . . . . . . . . . . . . . 3205.5.2.3 Mixing of Polymer Melts . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 320

Example 5-25 Preparation of Polymer Blends from the Melt. . . . . . • . •• 320

5.5.2.4 Polymerization of Monomers Containing Other Dissolved Polymers . .. 321

5.6 Stretching and Foaming of Polymers . . . . . . . . . . . . . . . . . . . . .. 322

• Example 5-26 Preparation of Foamable Polystyrene and of Polystyrene

Foam. . • . . . . . • . . . . . . . . . . . . . . • . . . . . • .. 323

• Example 5-27 Preparation of a Urea/Formaldehyde Foam. . . . . • • • • •• 325

5.6.1 Preparation of Polyurethane Foams . . . . . . . . . . . . . . . . . . . . . . . 326

• Example 5-28 Preparation of a Flexible Polyurethane Foam. . • • • • • • . • 327

Example 5-29 Preparation of a Rigid Polyurethane Foam • • • • • . . . • . • 327

5.7 References for Chapter 5 . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 327

Subject Index. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 329