Table Of ContentControlled/Living
Radical Polymerization
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ACS SYMPOSIUM S E R I E S 768
Controlled/Living Radical
Polymerization
Progress in ATRP, NMP, and RAFT
Krzysztof Matyjaszewski, EDITOR
Carnegie Mellon University
American Chemical Society, Washington, DC
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ACS Symposium Series; American Chemical Society: Washington, DC, 2000.
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Library of Congress Cataloging-in-Publication Data
Controlled/living radical polymerization : progress in ATRP, NMP, and RAFT / Krzysztof
Matyjaszewski, editor.
p. cm.—(ACS symposium series, ISSN 0097-6156 ; 768)
Includes bibliographical references and index.
ISBN 0-8412-3707-7
1. Polymerization—Congresses. 2. Free radical reactions—Congresses.
I. Matyjaszewski, K. (Krzysztof), 1950- . II. Series.
QD281.P656 2000
547'.28—dc21 0-3254
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Foreword
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In Controlled/Living Radical Polymerization; Matyjaszewski, K.;
ACS Symposium Series; American Chemical Society: Washington, DC, 2000.
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Preface
Radical polymerization has again become one of the hottest areas of
research. This originates with the old advantages of a radical process including a
large number of monomers that can be copolymerized to form a nearly infinite
number of different polymers under relatively undemanding conditions but also in
the new opportunities provided by controlled/living systems. Although termin
ation reactions cannot be fully suppressed, their proportion is strongly limited,
enabling preparation of polymers with precisely controlled molecular weights, low
polydispersities, novel architectures, compositions, and functionalities.
This book comprises both topical reviews and specialists' contributions
presented at the American Chemical Society (ACS) Symposium on "Controlled
Radical Polymerization" held in New Orleans, August 22-24, 1999. It was a
sequel to the previous A C S Symposium held in San Francisco in 1997, which was
summarized in the A C S Symposium Volume 685, Controlled Radical Polymer-
ization. The first seven chapters of the present volume provide a general intro
duction to conventional and controlled radical polymerizations and describe
approaches toward stereocontrolled systems. The next four chapters are focused
on recent advances in nitroxide-mediated polymerization (NMP). Atom transfer
radical polymerization (ATRP) is described in the following eight chapters. The
next three chapters refer to the application of reversible (degenerative) transfer
systems, with the most notable examples being reversible addition fragmentation
chain transfer (RAFT) and catalytic chain transfer (CCC) systems. A l l of these
techniques provide access to new materials that may lead to new commercial
applications, as discussed in the remaining eight chapters.
Papers published in this book demonstrate that radical polymerization is
becoming a preferred method for making well-defined polymers, both in academic
and industrial laboratories. Many new controlled radical systems have been
discovered; substantial progress has been achieved in the understanding of these
reactions and in quantitative measurements of the rates, equilibria, and
concentrations of the involved species. Comprehensive studies of controlled/living
radical polymerization involve a wide range of scientific disciplines, including
theoretical-computational chemistry, kinetics, physical organic chemistry, organic
synthesis, and organometallic-coordination chemistry, as well as polymer
synthesis and characterization, materials science, and so on. The facile synthesis
of many new polymeric materials calls for their precise characterization. This
should lead to the comprehensive structure-property relationship which may lead
to a foundation for new materials for specific applications.
This book is addressed to chemists interested in radical processes and
especially in controlled/living radical polymerization. It provides an introduction
to the field and summarizes the most recent progress in ATRP, N M P , and R A F T
systems.
xi
In Controlled/Living Radical Polymerization; Matyjaszewski, K.;
ACS Symposium Series; American Chemical Society: Washington, DC, 2000.
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The financial support for the symposium from the following organizations
is gratefully acknowledged: A C S Division of Polymer Chemistry, Inc., A C S
Petroleum Research Foundation, Aristech, BASF, Bayer, B F Goodrich, DuPont,
Eastman Chemicals, W. R. Gore, ICI, Lubrizol, Mitsui Chemicals, National Starch,
Polaroid, PPG Industries, Procter & Gamble, Rohm and Haas, and Solvay.
KRZYSZTOF MATYJASZEWSKI
Department of Chemistry
Carnegie Mellon University
4400 Fifth Avenue
Pittsburgh, P A 15213
xii
In Controlled/Living Radical Polymerization; Matyjaszewski, K.;
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Chapter 1
Comparison and Classification
of Controlled/Living Radical Polymerizations
Krzysztof Matyjaszewski
Department of Chemistry, Carnegie Mellon University,
4400 Fifth Avenue, Pittsburgh, PA 15213
Controlled/living radical polymerization employs the principle of
equilibration between growing free radicals and various types of
dormant species. There are several approaches to achieve good
control over molecular weights, polydispersities and end
functionalities in these systems. They can be classified depending
on the mechanism and chemistry of the equilibration/exchange
process, as well as on the structure of the dormant species. Some of
them are catalyzed and some are not, some of them exhibit the
persistent radical effect and some do not. Currently three methods
appear to be most efficient and may lead to commercial
applications: nitroxide mediated polymerization, atom transfer
radical polymerization and degenerative transfer processes. Their
relative advantages and limitations are compared herein.
INTRODUCTION
There are several approaches to controlling free radical polymerization by
suppressing the contribution of chain breaking reactions and assuring quantitative
initiation.^ A l l of these approaches employ dynamic equilibration between growing
free radicals and various types of dormant species. These reactions are described as
controlled radical polymerizations (CRP) or controlled/living radical polymerizations
2 © 2000 American Chemical Society
In Controlled/Living Radical Polymerization; Matyjaszewski, K.;
ACS Symposium Series; American Chemical Society: Washington, DC, 2000.
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3
rather than as true living radical polymerizations, due to the presence of unavoidable
termination, which is intrinsically incompatible with the concept of living
polyrnerizations.0 It is feasible to imagine that in the future a real living radical
polymerization will be invented in which tennination will be absent or at least the
termination rate coefficients wil l be strongly reduced in comparison with conventional
free radical polymerization. This could be accomplished by selective complexation of
the free radical or by carrying out the reaction in a confined space.
The exchange process is at the very core of the CRP methods and can be
approached in several ways depending on the structure of the dormant and
deactivating species, the presence of the catalyst and the particular chemistry and
mechanism of the exchange. Currently, three methods appear to be most efficient and
can be successfully applied to a large number of monomers: stable free radical
polymerization (SFRP), best represented by nitroxide mediated polymerization
(NMP), metal catalyzed atom transfer radical polymerization (ATRP), and reversible
addition-fragmentation chain transfer (RAFT) along with other degenerative transfer
processes. Their relative advantages and limitations wil l also be discussed.
CLASSIFICATION OF CRPS
Operationally, all CRPs employ the principle of dynamic equilibration between
dormant and active species. The position and dynamics of this equilibrium define the
observed rates as well as affect molecular weights and polydispersities of the formed
polymers. It is possible to group CRPs into several categories, depending on the
chemistry of exchange and structure of the dormant species. Although it may be
simpler to divide CRPs based on the structure of the dormant species, the mechanistic
classification may be more appropriate, since it enables better correlation of the rates,
molecular weights and polydispersities of the obtained polymers with the
concentration of the involved reagents. Thus, mechanistically, CRPs can be classified
into four different cases:
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