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REAL TIME MANAGEMENT OF POLYMERIZATION REACTIONS

PL-PMC Polymerization Monitoring and Control

VARIAN, INC.

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IntroductionThe PL-PMC is a complete system for online polymerization monitoring

and control from Polymer Laboratories, now a part of Varian, Inc.

Founded in 1976, to develop novel techniques and instrumentation

for the characterization of polymer systems and to develop

high technology polymer-based products for chromatographic,

pharmaceutical and diagnostic applications, Polymer Laboratories has

over 30 years of expertise in Polymer Characterization.

The system allows the monitoring of key reaction parameters in near

real time and is designed for use in polymer research and development,

production monitoring and process control. The PL-PMC system

enables direct investigation of important aspects of polymerization

processes, including the reactor conditions and design, the effect of

initiator selection and importantly the monomer consumption and

polymer formation kinetics.

The PL-PMC system is particularly valuable in supporting polymer

R&D in industry and academia at the laboratory scale. The system

couples continuous sampling direct from the reactor with two

analysis philosophies. Rapid chromatographic analysis (gel permeation

chromatography (GPC), flow injection analysis (FIA) and hydrodynamic

chromatography (HDC)) and Automatic Continuous Monitoring of

Polymerization (ACOMP*) generate information on parameters such as

polymer molecular weight averages, monomer % conversions, solution

viscosity, polymer polydispersity, polymer % composition and particle

size as a function of reaction time.

These two analysis philosophies can be integrated individually, or

coupled to provide information rich detection (IRD) solutions for the

most complex of laboratory needs. Information Rich Detectors such

as NMR, MS and FT-IR, have the ability to provide multi-dimensional

layers of data (IRD instruments go beyond the mere detection of a

compound by producing highly detailed structural and compositional

molecular information).

* Manufactured by Polymer Laboratories under license from Tulane University, New Orleans

PL-PMC Instrumentation

Introducing the PL-PMCVARIAN, INC.

Key Benefits:

• Allows analysis of polymerization reactions continuously from initiation to completion in one shot, generating much more information than can be obtained from single offline or bulk property measurements.

• Obtains near real time data minimizing time lags.

• Eliminates batch failure to save time and money, and improve product yields and quality.

• Allows totally automated and unsupervised operation to maximize staff efficiency.

• Minimizes reactor downtime - rugged construction provides reliable operation.

• Promotes proactive control – move the lab to the sample.

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Real Time Management of Polymerization Reactions Polymerization reactions are controlled by several closely related

factors such as the reaction mechanism, the thermodynamics and the

kinetics of the process. These parameters vary during the reaction as

monomer is depleted and polymer formed. Obtaining concentration,

kinetic and molecular weight information during polymerization is

critical to understanding and ultimately controlling these processes.

Traditionally, this requires the analysis of products of multiple reactions

in which key parameters are systematically varied. Such investigations

are time consuming and tedious and only describe the final product, by

which time it is too late to change the reaction conditions to improve

the outcome.

The fast, efficient and routine monitoring of polymerization processes

has long been a goal for polymer chemists. Now, using the PL-PMC

system, you can access information on these changes of state during

the polymerization reaction. This allows rapid monitoring of processes

and fast and efficient control of reaction conditions, moving towards

proactive control by taking the lab to the sample, rather than assessing

the finished product.

Polymerization, monitoring and control (PMC) is key to real time

management of polymer development.

PL-PMC Schematic

** Manufactured by Polymer Laboratories under licence from Symyx Technologies, Inc.

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PL-PMC Schematic The PL-PMC operates through the careful integration of multiple components to provide seamless operation and consistent results.

Each of these system components is described below.

PL-PMC Instrumentation DesignVARIAN, INC.

ExtractionA small continuous stream of polymerization solution is

accurately removed from the reactor and delivered through a

precision flow-controlling unit to the dilution module.

ACOMP MonitoringIn this system the dilute reactor contents are continuously streamed

through an array of detectors, providing instantaneous information

relating to polymer concentration, molecular weight and composition.

DilutionDual dilution stages dilute the polymerization solution to

concentrations sufficient for all detection methods. The first dilution

is a low-pressure dilution stage performed via a temperature

controlled mixing chamber. This is followed by a secondary high-

pressure dilution and mixing stage that delivers the reactor contents

to the detection modules at sufficiently low concentration for

required measurements.

Chromatographic MonitoringIn this system the dilute reactor contents are continuously

delivered to rapid chromatography apparatus via integrated

injection modules. Rapid injections into the chromatography

system are performed with run times as low as �.5 minutes to

generate chromatography data.

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PL-GPC 50 Plus Integrated GPC System

PL-GPC ��0 Integrated GPC System

SoftwareA fully integrated custom suite of software controls the full PL-PMC

experiment, from the extraction of reactor contents through to

accurate, instantaneous processing of data throughout the course of

the polymerization.

Deriving polymerization data involves a four-stage process:

Polymer Sampling Automatic and continuous extraction from the reaction vessel

Dilution and Sample Preparation Controlled dilution of the extracted sample to a known concentration

ACOMP Measurement Continuous measurements with ‘absolute’ detectors (static light scattering or viscometry) and/or concentration detectors (ultra violet, refractive index, evaporative light scattering, etc.)

Chromatography Measurement Discrete, rapid chromatographic or flow injection analysis via gel permeation chromatography or hydrodynamic chromatography

Data Monitoring Calculation of molecular weight distributions, molecular weight averages and reaction conversion rates provides data for rapid and comprehensive characterization and management of the polymerization process

Advanced GPC InstrumentationIn addition to the PL-PMC, Varian Polymer Laboratories design,

manufacture and supply a range of sophisticated, versatile

instrumentation for polymer and materials characterization. The

advanced GPC instruments offer integrated, triple detection to ensure

excellent chromatographic performance from ambient to ��0 ˚C,

whatever the application.

PL-XT ��0 Rapid Analysis GPC System

As an ISO 9001:�000 Standard Quality Assessed Company,

Varian Polymer Laboratories assures the customer of the quality and

reliability of both the products and services provided. In addition,

a comprehensive and sophisticated range of technical support is

offered across the full product portfolio, from reference papers to

technical bulletins.

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ChromatographyPL-PMC systems specifically designed for rapid chromatography

significantly reduce FIA, GPC and HDC analysis times to as a little as

�.5 minutes. This allows these traditional chromatographic techniques

to be used in an online environment. Using these systems, molecular

weight averages, conversion data and particle size can be obtained in

near real time.

The PL-PMC system can be equipped for the following chromatographic

techniques:

GPCGPC provides information on molecular weight distribution (MWD)

and averages and polymer content above/below the MW limits of

interest. In addition, selected detector options can enhance the analysis

and provide key information on parameters such as sample viscosity,

copolymer composition and radius of gyration.

• Detector options – The PL-PMC can include refractive index, UV,

viscometry, dual angle light scattering, Fourier transform infrared

spectroscopy and photodiode array detectors for rapid GPC analysis.

• What can be calculated – important parameters such as molecular

weight averages, conversion, % incorporation, radius of gyration,

intrinsic viscosity and the degree of branching can be determined.

ACOMPACOMP is a non-chromatographic method that relies on a continuous

stream of reactor contents passing through a series of detectors

selected according to the requirements of the analysis. In a typical

ACOMP setup, continuous light scattering, viscometric, spectroscopic

and other measurements can be made on the diluted stream of reactor

contents. The data obtained can be manipulated to show the state of

the reactor contents in near real time, and can be further analyzed to

give calculations of conversions, molecular weight averages, solution

viscosities and other key reaction parameters.

• Detector options – PL-PMC can include refractive index, ultraviolet

(UV), viscometry, 7-angle light scattering, Fourier transform infrared

spectroscopy and a photodiode array for ACOMP analysis.

• What can be calculated – important parameters such as molecular

weight averages, conversion, reduced viscosity, % composition and

radius of gyration can be determined.

Analysis Options for Polymerization Monitoring

Representative ACOMP raw data obtained from a free-radical terpolymerization of styrene, MMA and butyl acrylate, showing the clear evolution of copolymeric material throughout the course of the reaction. (Data courtesy of Prof. Wayne Reed, Tulane University, New Orleans)

Representative raw data chromatograms from a free radical feed copolymerization of acrylic acid and butyl acrylate, highlighting the evolution of both polymer concentration and molecular weight every �.5 minutes throughout a full polymerization profile.

VARIAN, INC.

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Analysis Options for Polymerization Monitoring

FIAFIA is a technique that provides single point determinations of polymer

parameters extremely rapidly, providing a robust and reproducible

platform for the online measurement of polymer conversion and bulk

molecular weights.

• Detection options – The PL-PMC can include refractive index,

UV, viscometry, dual angle light scattering, and Fourier transform

infrared spectroscopy in FIA mode.

• What can be calculated – conversion, bulk MW and intrinsic viscosity

can be determined by FIA.

HDCHDC separates particles suspended in solution on the basis of their size,

providing a fast and convenient technique to establish information on

particle size distributions (PSD) and averages irrespective of particle

chemistry or density.

• Detection options – UV is the detector of choice for HDC.

• What can be calculated – particle size distributions and averages can

be determined simply and quickly by HDC.

Application NotesThe following application notes describe the use of the PL-PMC for monitoring a series of well-known commercial reactions, illustrating the

performance of the instrumentation.

Representative raw data chromatogram obtained from flow injection analysis of a free radical polymerization of methyl methacrylate, showing the RI trace from which concentration and conversion calculations are performed and the LS trace from which bulk molecular weight calculations are preformed.

Representative calculated particle size distribution from a free radical emulsion polymerization of styrene, showing the growth in particle size throughout the reaction.

Chromatography Titles1. Reproducible Online Monitoring of Molecular Weight Distributions and Monomer

Conversion in a Free Radical Polymerization Reaction using PL-PMC Instrumentation�. Online Monitoring of Molecular Weight and Monomer Conversion during a

Metallocene Catalyzed Polymerization of 1-Hexene using PL-PMC Instrumentation3. Simultaneous Online Monitoring of Molecular Weight and Particle Size Distributions in

a Free Radical Emulsion Polymerization Reaction using PL-PMC Instrumentation�. Online Flow Injection Analysis Monitoring of Molecular Weight and Monomer

Conversion in a Transition Metal Mediated Living Radical Polymerization Reaction using PL-PMC Instrumentation

5. Online Monitoring of Single Electron Transfer Polymerizations using PL-PMC Instrumentation

6. Online Monitoring of Molecular Weight Distributions and Monomer Conversion in a Free Radical Feed Copolymerization Reaction using PL-PMC Instrumentation

ACOMP Titles7. Online Analysis of Monomer Inhibitor Activity via PL-PMC ACOMP Instrumentation8. Online Analysis of Free Radical Acrylamide Homopolymerization via PL-PMC ACOMP

Instrumentation9. Online Analysis of Free Radical Methacrylate Homopolymerization via PL-PMC ACOMP

Instrumentation10. Online Analysis of Conversion, Molecular Weight and Comonomer Incorporation in

Free Radical Copolymerization via PL-PMC ACOMP Instrumentation11. Online Analysis of Reversible Addition–Fragmentation Chain Transfer (RAFT)

Polymerization via PL-PMC ACOMP Instrumentation1�. Online Characterization of Typical Reaction Pertubations via PL-PMC ACOMP Detection

Please visit www.varianinc.com or www.polymerlabs.com for details on how to request these and other application notes and technical papers.

SI-0980/A/01.08 Printed in the UK

GC • LC • MS • GPC/SEC • AA • ICP • ICP-MS • UV-Vis-NIR • FT-IR • Fluorescence • Dissolution • NMR • MRI • FTMS • Consumables • Data Systems

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Varian, Inc. – Supporting Customers WorldwideAll products are eligible for on-demand support from a worldwide network of specialists who can assist with any need. Varian, Inc. offers:

• Comprehensive programs that include a full range of services – from minor repairs, to complex applications development and training.

• Factory-qualified Field Support Representatives and Specialists, specifically chosen for each installation.

• Global support teams strategically located around the world.

To learn more about Varian’s industry-leading customer support, visit our Web site at www.varianinc.com/support

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REAL TIME MANAGEMENT OF POLYMERIZATION REACTIONS

PL-PMC Polymerization Monitoring and Control

VARIAN, INC.

Polymer Laboratories, the Polymer Laboratories logo, Varian and the Varian logo are trademarks or registered trademarks of Varian, Inc. in the U.S. and other countries.© �008 Varian, Inc.