Table Of ContentControlled/Living Radical
Polymerization
In Controlled/Living Radical Polymerization; Matyjaszewski, K.;
ACS Symposium Series; American Chemical Society: Washington, DC, 2006.
August 11, 2012 | http://pubs.acs.org
Publication Date: September 7, 2006 | doi: 10.1021/bk-2006-0944.fw001
In Controlled/Living Radical Polymerization; Matyjaszewski, K.;
ACS Symposium Series; American Chemical Society: Washington, DC, 2006.
August 11, 2012 | http://pubs.acs.org
Publication Date: September 7, 2006 | doi: 10.1021/bk-2006-0944.fw001
ACS SYMPOSIUM SERIES 944
Controlled/Living Radical
Polymerization
From Synthesis
to Materials
Krzysztof Matyjaszewski, EDITOR
Carnegie Mellon University
Sponsored by the
ACS Division of Polymer Chemistry, Inc.
American Chemical Society, Washington, D C
In Controlled/Living Radical Polymerization; Matyjaszewski, K.;
ACS Symposium Series; American Chemical Society: Washington, DC, 2006.
August 11, 2012 | http://pubs.acs.org
Publication Date: September 7, 2006 | doi: 10.1021/bk-2006-0944.fw001
Library of Congress Cataloging-in-Publication Data
Controlled/living polymerization :f roms ynthesis to materials / Krzysztof
Matyjasjzewski, editor.
p. cm.—(ACS symposium series ISSN 0097-6156 ; 944)
Includes bibliographical references and index.
ISBN 13: 978-0-8412-3991-3 (alk. paper)
ISBN 10: 0-8412-3991-6 (alk. paper)
1. Polymerization—Congresses. 2. Free radical reactions—Congresses.
I. Matyzasjewski, K. (Krzysztof) II. Series.
QD281.P64.C655 2006
547'.28—dc2 206045178
The paper used in this publication meets the minimum requirements of American
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Materials, ANSI Z39.48-1984.
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In Controlled/Living Radical Polymerization; Matyjaszewski, K.;
ACS Symposium Series; American Chemical Society: Washington, DC, 2006.
August 11, 2012 | http://pubs.acs.org
Publication Date: September 7, 2006 | doi: 10.1021/bk-2006-0944.fw001
Foreword
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In Controlled/Living Radical Polymerization; Matyjaszewski, K.;
ACS Symposium Series; American Chemical Society: Washington, DC, 2006.
August 11, 2012 | http://pubs.acs.org
Publication Date: September 7, 2006 | doi: 10.1021/bk-2006-0944.fw001
Preface
This book is addressed to chemists who are interested in radical
processes and especially in controlled/living radical polymerization. It
summarizes the most recent accomplishments in the field.
This volume comprises the topical reviews and specialists'
contributions presented at the American Chemical Society (ACS)
Symposium entitled Advances in Controlled/Living Radical Polymer-
ization that was held in Washington, D.C., August 28-September 1,
2005. The Washington, D.C. Meeting was a sequel to the previous ACS
Symposia held in San Francisco, California, in 1997, in New Orleans,
Louisiana in 1999, and in Boston, Massachusetts, in 2002. They were
summarized in the ACS Symposium Series Volume 685, Controlled
Radical Polymerization, Volume 768, Controlled/Living Radical Poly-
merization: Progress in ATRP, NMP and RAFT and Volume 854
Advances in Controlled/Living Radical Polymerization. The Wash
ington, D.C. Meeting was very successful with 77 lectures and 119
posters presented, which illustrates a continuous growth in comparison
with the San Francisco Meeting (32 lectures and 35 posters), with the
New Orleans (50 lectures and 50 posters), and with the Boston Meeting
(80 lectures and 79 posters).
The first chapter provides an overview of the current status of
controlled/living radical polymerization (CRP) systems. Twenty chapters
in this book cover atom transfer radical polymerization (ATRP) and
include m echanistic f eatures a nd m aterials m ade b y A TRP. Chemistry
and materials made by nitroxide and other stable free radical polymer
izations (SFRP) are presented in six chapters. Systems based on
degenerative transfer such as reversible-addition fragmentation transfer
(RAFT) are summarized in fourteen chapters.
Chapters published in this book show that controlled/living
radical polymerization has made a significant progress within the last
decade. New systems have been discovered; substantial progress has
been achieved in understanding the reactions involved in ATRP, SFRP,
and RAFT. The rate and equilibrium constants as well as concentrations
of the involved species were quantitatively measured for some systems
but a more detailed structure-reactivity relationship for all CRP systems
xiii
In Controlled/Living Radical Polymerization; Matyjaszewski, K.;
ACS Symposium Series; American Chemical Society: Washington, DC, 2006.
August 11, 2012 | http://pubs.acs.org
Publication Date: September 7, 2006 | doi: 10.1021/bk-2006-0944.pr001
is needed. Some effects of structural variation on properties were
reported but a comprehensive and precise relationship between
molecular structure and macroscopicp ropertiesi s n o ty e ta v ailable.I tw ill be a lso i mportant t ο u nderstand t he e ffect ο f ρ olydispersities a nd
other imperfections on materials properties in order to optimize a cost-
performance ratio. Several new commercial applications of CRP were
already announced at the Washington, D.C. Meeting and it is anticipated
that many new products will be soon on the market.
The financial support for the symposium from the following
organizations is acknowledged: ACS Division of Polymer Chemistry,
Inc., ACS Petroleum Research Foundation, Arkema, Atofina, Bayer,
Bausch & Lomb, Boston Scientific, BYK, Cabot, Ciba Vision, Dionex,
EFKA, Firmenich, Kaneka, Mitsubishi Chemicals, Mitsui Chemicals,
Rohmax, and Rohm & Haas. The editorial assistance from Joyce Von
Vreckin is gratefully acknowledged.
Krzysztof Matyjaszewski
Department of Chemistry
Carnegie Mellon University
4400 Fifth Avenue
Pittsburgh, PA 15213
xiv
In Controlled/Living Radical Polymerization; Matyjaszewski, K.;
ACS Symposium Series; American Chemical Society: Washington, DC, 2006.
August 11, 2012 | http://pubs.acs.org
Publication Date: September 7, 2006 | doi: 10.1021/bk-2006-0944.pr001
Controlled/Living Radical
Polymerization
In Controlled/Living Radical Polymerization; Matyjaszewski, K.;
ACS Symposium Series; American Chemical Society: Washington, DC, 2006.
August 11, 2012 | http://pubs.acs.org
Publication Date: September 7, 2006 | doi: 10.1021/bk-2006-0944.pr001
Chapter 1
Controlled/Living Radical Polymerization: State
of the Art in 2005
Krzysztof Matyjaszewski
Center for Macromolecular Engineering, Department of Chemistry,
Carnegie Mellon University, 4400 Fifth Avenue, Pittsburgh, PA 15213
Recent progress and future challenges in Controlled/Living
Radical Polymerization (CRP) are discussed. Stable free
radical polymerization (SFRP), atom transfer radical
polymerization (ATRP), and degenerate transfer processes,
including reversible additionf ragmentationt ransfer (RAFT)
are the most successful CRP techniques. They enable
preparation of new materials from readily available monomers
under undemanding conditions. Future developments require
better understanding structure-reactivity relationship and
deeper insight into the reactive intermediates by spectroscopic
and computational techniques. The precise relationship
between the structure and properties of materials prepared by
CRP is also needed. This study should include the effect of
higher polydispersities and other imperfections to optimize
cost-performance ratio. Fast growth of areas related to hybrids
and bioconjugate materials is anticipated.
2 © 2006 American Chemical Society
In Controlled/Living Radical Polymerization; Matyjaszewski, K.;
ACS Symposium Series; American Chemical Society: Washington, DC, 2006.
August 11, 2012 | http://pubs.acs.org
Publication Date: September 7, 2006 | doi: 10.1021/bk-2006-0944.ch001
3
Controlled/living radical polymerization (CRP) is among the most rapidly
1 4
developing areas of chemistry and polymer science. " During the last decade,
5
many novel previously inaccessible materials have been prepared using CRP.
They include macromolecules with precisely controlled composition and
architecture but also many new hybrids in which well-defined organic polymers
6 12
are covalently attached to inorganic materials or to natural products. *
The last decade has witnessed an explosive increase in the number of
publications on CRP, a dramatic increase in the number of patent applications
and several symposia devoted partially, or entirely, to CRP.
1000
<0
- Β CRP&LRP
• ATRP only
c
ο -
SFRP&NMP
CO
ο _ • RAFT&DT&CCT
= 600
SX
3
CL
«*-
Ο
400
Ε
3
200
CO ^ Ι Ο
ο ο ο
ο ο ο
CM CM CM
Year
Figure 1. Results of SciFinder Search on various CRP systems as of February 5,
2006. Detailed explanation of terms is provided in the text.
Figure 1 illustrates results of a recent SciFinder Scholar search using the
following terms: controlled radical polymn or living radical polymn
("CRP&LRP" in Figure 1), ATRP or atom transfer (radical) polymn ("ATRP
In Controlled/Living Radical Polymerization; Matyjaszewski, K.;
ACS Symposium Series; American Chemical Society: Washington, DC, 2006.
August 11, 2012 | http://pubs.acs.org
Publication Date: September 7, 2006 | doi: 10.1021/bk-2006-0944.ch001
