Controlled Radical Polymerization

482 Pages·1998·39.59 MB·English

by  Krzysztof Matyjaszewski (Eds.)

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In Controlled Radical Polymerization; Matyjaszewski, K.;
ACS Symposium Series; American Chemical Society: Washington, DC, 1998.
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In Controlled Radical Polymerization; Matyjaszewski, K.;
ACS Symposium Series; American Chemical Society: Washington, DC, 1998.
ACS SYMPOSIUM SERIES 685
Controlled Radical
Polymerization
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21/ Krzysztof Matyjaszewski, EDITOR
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0. Carnegie Mellon University
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e: Developed from a symposium sponsored by the Division
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n of Polymer Chemistry, Inc., at the 213th National Meeting
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April 13-17, 1997
American Chemical Society, Washington, DC
In Controlled Radical Polymerization; Matyjaszewski, K.;
ACS Symposium Series; American Chemical Society: Washington, DC, 1998.
Library of Congress Cataloging-in-Publication Data
Controlled radical polymerization / Krzysztof Matyjaszewski, editor.
p. cm.—(ACS symposium series, ISSN 0097-6156; 685)
"Developed from a symposium sponsored by the Division of Polymer
Chemistry at the 213th National Meeting of the American Chemical Society,
San Francisco, CA, April 6-11, 1997."
Includes bibliographical references and indexes.
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w ISBN 0-8412-3545-7
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6 1. Polymerization—Congresses. 2. Free radical reactions—Congresses
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99 I. Matyjaszewski, K. (Krzysztof), 1950- . II. American Chemical Society.
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k- Division of Polymer Chemistry. III. American Chemical Society. Meeting
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1/ (213th: 1997: San Francisco, Calif.) IV. Series.
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0.1 QD281.P6C66 1998
doi: 1 547'.28—dc21 97-437C3IP1
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8, This book is printed on acid-free, recycled paper.
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In Controlled Radical Polymerization; Matyjaszewski, K.;
ACS Symposium Series; American Chemical Society: Washington, DC, 1998.
Advisory Board
ACS Symposium Series
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ChemEdit Company AT&T Bell Laboratories
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University of Wisconsin at Madison Purdue University
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In Controlled Radical Polymerization; Matyjaszewski, K.;
ACS Symposium Series; American Chemical Society: Washington, DC, 1998.
Foreword
IHE ACS SYMPOSIUM SERIES was first published in 1974 to provide
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In Controlled Radical Polymerization; Matyjaszewski, K.;
ACS Symposium Series; American Chemical Society: Washington, DC, 1998.
Preface
UNTIL RECENTLY, RADICAL POLYMERIZATION has been considered
as one of the most mature areas of polymer synthesis. Many commercial
polymers and copolymers are prepared by radical polymerization because of its
1 undemanding conditions, the large number of available monomers, and the
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pr0 facileness of (co)polymerization. However, the main deficiency of conventional
85. radical polymerization is a lack of macromolecular control and the difficulty of
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19 After several years of relatively slow progress in controlled radical
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b polymerization, the field began to undergo nearly exponential development in
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02 1993, after the first disclosures of styrene radical polymerization mediated by
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0. nitroxide and several organometallic derivatives. Most recently, reports of
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19 The recent emergence of controlled radical polymerization in both academic
y 8, and industrial laboratories is expected to be converted to commercial practice in
uar the near future. It is stimulating to be part of the current growth of this diverse
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at specialists at a symposium presented at the 213th National Meeting of the
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n American Chemical Society, titled "Advances in Free Radical Polymerization",
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ubli California, April 13-17, 1997. The first five chapters provide a general
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introduction to radical reactions and controlled radical polymerization. The next
four chapters are focused on recent advances in the kinetics of conventional
radical (co)polymerization in homogeneous and heterogeneous media and on
direct measurements of concentrations of growing species. Topics related to
controlled radical polymerization are summarized in the remaining 18 chapters
and are separated into four sections covering nitroxide-mediated polymerization,
metal-mediated polymerization, and other systems, and the application of
controlled radical polymerization to the synthesis of new well-defined materials.
The articles in this book give strong evidence that radical polymerization
has entered a renaissance. Many new controlled radical systems have been
discovered, and substantial progress has been achieved in understanding these
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In Controlled Radical Polymerization; Matyjaszewski, K.;
ACS Symposium Series; American Chemical Society: Washington, DC, 1998.
reactions and in quantitative measurement of the rates, equilibria, and
concentrations of the species involved. It seems that a thorough understanding of
the reactions involved in controlled radical polymerization, especially those
carried out in the presence of organometallic derivatives, requires a concerted
effort in various areas of chemistry, including theoretical and computational
chemistry; kinetics; physical organic chemistry; organic and bioorganic
synthesis; and organometallic and coordination chemistry.
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 accomplishments in controlled
radical systems.
Acknowledgements
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0 Financial support for the symposium from the following organizations is
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5. gratefully acknowledged: ACS Polymer Division, Inc., ACS Petroleum
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0 Research Fund, Amoco, Bayer, Aristech, BFGoodrich, Ciba-Geigy, Eastman
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99 Chemicals, Eastman Kodak, Elf Atochem, Exxon, Hoechst Celanese, ICI,
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k- Kaneka, Loctite, Mitsui Chemicals, National Starch, Procter & Gamble,
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xii
In Controlled Radical Polymerization; Matyjaszewski, K.;
ACS Symposium Series; American Chemical Society: Washington, DC, 1998.
Chapter 1
Overview: Fundamentals of Controlled/Living
Radical Polymerization
Krzysztof Matyjaszewski
Department of Chemisty, Carnegie Mellon University, 4400 Fifth Avenue,
Pittsburgh, PA 15213
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8-0 The fundamentals of controlled/"living" polymerization are discussed and the
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8 | d controlled radical polymerization is reviewed. Developments of several basic
99 concepts in this field are summarized. Potential prospects for controlled
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reaction conditions, requiring the absence of oxygen but tolerant to water, and large
temperature ranges (-20 to 200 °C).(1) In addition, many monomers can easily
copolymerize radically leading to an infinite number of copolymers with properties
dependent on the proportions of the comonomers. The only disadvantage to conventional
radical polymerization is the poor control of macromolecular structures including degrees of
polymerization, polydispersities, end functionalities, chain architectures and compositions.
Thus, it is desirable to prepare, by radical polymerization, new well-defined block and graft
copolymers, stars, combs and networks that have not been previously prepared using ionic
2 © 1998 American Chemical Society
In Controlled Radical Polymerization; Matyjaszewski, K.;
ACS Symposium Series; American Chemical Society: Washington, DC, 1998.
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living polymerizations.(2) Therefore, controlledTliving" radical polymerizations allow for
the synthesis of new well-defined and functional materials from a larger range of
monomers under simpler reaction conditions than are appropriate for ionic processes.
This overview Chapter describes the fundamentals of controlledTliving" radical
polymerization, discusses historical developments of several concepts in this field and
attempts to show potential prospects for controlled radical reactions.
Requirements for Controlled /"Living" Polymerizations
Living polymerization was first defined by Szwarc (3) as a chain growth process
1 without chain breaking reactions (transfer and termination). Such a polymerization
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68 monomer addition. However, it does not necessarily provide for molecular weight control
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ary Recently, many new "living" polymerization systems, such as carbocationic, ring-
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named controlled rather than living. Since many researchers are used to the term living,
the term controlled/"living" may also describe the essence of these systems.(9)
Ideally, controlled/"living" systems lead to polymers with degrees of polymerization
predetermined by the ratio of the concentrations of consumed monomer to the introduced
initiator DP=A[M]/[I], polydispersities close to Poisson distribution (DP/DP=l +
n 0 w n
l/DP), and with all chains end-functionalized. Experimentally, the best way to evaluate
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such systems is to follow the kinetics of polymerization and the evolution of molecular
weights, polydispersities and functionalities with conversion. Well-controlled systems
should provide:
In Controlled Radical Polymerization; Matyjaszewski, K.;
ACS Symposium Series; American Chemical Society: Washington, DC, 1998.