Controlled/Living Radical Polymerization: Progress in RAFT, DT, NMP & OMRP

386 Pages·2009·13.77 MB·English

by  Krzysztof Matyjaszewski (Eds.)

Controlled/Living Radical
Polymerization: Progress in
RAFT, DT, NMP & OMRP

In Controlled/Living Radical Polymerization: Progress in RAFT, DT, NMP & OMRP; Matyjaszewski, K.;
ACS Symposium Series; American Chemical Society: Washington, DC, 2009.
Downloaded by 89.163.34.136 on June 25, 2012 | http://pubs.acs.org
Publication Date: August 13, 2009 | doi: 10.1021/bk-2009-1024.fw001
In Controlled/Living Radical Polymerization: Progress in RAFT, DT, NMP & OMRP; Matyjaszewski, K.;
ACS Symposium Series; American Chemical Society: Washington, DC, 2009.
Downloaded by 89.163.34.136 on June 25, 2012 | http://pubs.acs.org
Publication Date: August 13, 2009 | doi: 10.1021/bk-2009-1024.fw001
ACS SYMPOSIUM SERIES 1024
Controlled/Living Radical
Polymerization: Progress in
RAFT, DT, NMP & OMRP

Krzysztof Matyjaszewski, Editor
Carnegie Mellon University

Sponsored by the
ACS Division of Polymer Chemistry, Inc.
ACS Petroleum Research Foundation
Arkena, Bayer, Boston Scientific, Ciba, CIP, Dionex, DSM,
Elsevier, Evonik, General Electric, JSR, Lion,
Mitsui Chemicals, National Starch, PPG and Sumitomo

American Chemical Society, Washington DC

In Controlled/Living Radical Polymerization: Progress in RAFT, DT, NMP & OMRP; Matyjaszewski, K.;
ACS Symposium Series; American Chemical Society: Washington, DC, 2009.
Downloaded by 89.163.34.136 on June 25, 2012 | http://pubs.acs.org
Publication Date: August 13, 2009 | doi: 10.1021/bk-2009-1024.fw001
Library of Congress Cataloging-in-Publication Data

Controlled/living radical polymerization : progress in RAFT, DT, NMP &
OMRP / Krzysztof Matyjaszewski, editor.
p. cm.
Includes bibliographical references and index.
ISBN 978-0-8412-6996-5
1. Polymerization--Congresses. 2. Free radical reactions--Congresses. I.
Matyjaszewski, K. (Krzysztof)
QD281.P6C6557 2009
547'.28--dc22
2009020533

The paper used in this publication meets the minimum requirements of
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for Printed Library Materials, ANSI Z39.48n1984.

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In Controlled/Living Radical Polymerization: Progress in RAFT, DT, NMP & OMRP; Matyjaszewski, K.;
ACS Symposium Series; American Chemical Society: Washington, DC, 2009.
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Publication Date: August 13, 2009 | doi: 10.1021/bk-2009-1024.fw001
Foreword

The ACS Symposium Series was first published in 1974 to provide a
mechanism for publishing symposia quickly in book form. The purpose of the
series is to publish timely, comprehensive books developed from the ACS
sponsored symposia based on current scientific research. Occasionally, books
are developed from symposia sponsored by other organizations when the topic is
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Before agreeing to publish a book, the proposed table of contents is
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In Controlled/Living Radical Polymerization: Progress in RAFT, DT, NMP & OMRP; Matyjaszewski, K.;
ACS Symposium Series; American Chemical Society: Washington, DC, 2009.
Downloaded by 89.163.34.136 on June 25, 2012 | http://pubs.acs.org
Publication Date: August 13, 2009 | doi: 10.1021/bk-2009-1024.fw001
Preface
This book and an accompanying volume are addressed to
chemists who are interested in radical processes and especially in
controlled/living radical polymerization. They summarize the most
recent accomplishments in the field.
The two volumes comprise the topical reviews and specialists'
contributions presented at the American Chemical Society
Symposium entitled Controlled/Living Radical Polymerization that
was held in Philadelphia, Pennsylvania, August 17-21, 2008. The
Philadelphia Meeting was a sequel to the previous ACS Symposia
held in San Francisco, California, in 1997, in New Orleans,
Louisiana, in 1999, in Boston, Massachusetts, in 2002 and in
Washington, DC, in 2005. They were summarized in the ACS
Symposium Series Volume 685, Controlled Radical
Polymerization, Volume 768, Controlled/Living Radical
Polymerization: Progress in ATRP, NMP and RAFT, Volume 854
Advances in Controlled/Living Radical Polymerization and
Volume 944, Controlled/Living Radical Polymerization: From
Synthesis to Materials. The Philadelphia Meeting was very
successful with 90 lectures and 123 posters presented. This
illustrates a continuous growth in comparison with the San
Francisco Meeting (32 lectures and 35 posters), the New Orleans
(50 lectures and 50 posters), the Boston Meeting (80 lectures and
79 posters) and with the Washington Meeting (77 lectures and 119
posters).
The fifty chapters submitted for publication in the ACS
Symposium series could not fit into one volume and therefore we
decided to split them into two volumes. In order to balance the size
of each volume we did not divide the chapters into volumes related
to mechanisms and materials but rather to those related to atom
transfer radical polymerization (ATRP) and to other
controlled/living radical polymerization methods: reversible-
addition fragmentation transfer (RAFT) and other degenerative
transfer techniques, as well as stable free radical polymerizations
(SFRP) including nitroxide mediated polymerization (NMP) and
organometallic mediated radical polymerization (OMRP).
xi

In Controlled/Living Radical Polymerization: Progress in RAFT, DT, NMP & OMRP; Matyjaszewski, K.;
ACS Symposium Series; American Chemical Society: Washington, DC, 2009.
Downloaded by 89.163.34.136 on June 25, 2012 | http://pubs.acs.org
Publication Date: August 13, 2009 | doi: 10.1021/bk-2009-1024.pr001
This volume contains 10 chapters on mechanisms and kinetics
of RAFT, other degenerative transfer processes, NMP and OMRP.
They are followed by six chapters devoted to molecular
architecture accessible by these techniques. Various materials
aspects of the resulting polymers are covered in six chapters. The
last two chapters present commercial application of polymers
prepared by NMP and RAFT (or MADIX).
The first chapter in the preceding volume provides an overview
of the current status of controlled/living radical polymerization
(CRP) systems. The following three chapters discuss important
issues relevant to all radical polymerization methods. The
mechanistic and kinetic topics of ATRP are covered in eight
chapters. The macromolecular architecture, various hybrids and
bio-related polymers prepared by ATRP are discussed in the next
six chapters, Characterization and materials aspects of ATRP
polymers are covered in six chapters, whereas the last four
chapters discuss industrial applications of ATRP.
Fifty chapters published in two volumes show that CRP has
made a significant progress within the last decade. New systems
have been discovered; substantial progress has been achieved in
understanding the mechanism and kinetics of reactions involved in
all CRP systems. Significant progress has been made towards a
comprehensive relationship between molecular structure and
macroscopic properties. Some commercial applications of CRP
were announced at the Philadelphia 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, Bayer, Boston Scientific, Ciba, CIP, Dionex, DSM,
Elsevier, Evonik, General Electric, JSR, Lion, Mitsui Chemicals,
National Starch, PPG and Sumitomo. The excellent editorial
assistance from Joyce Von Vreckin is gratefully acknowledged.
Krzysztof Matyjaszewski
Department of Chemistry
Carnegie Mellon University
4400 Fifth Avenue
Pittsburgh, PA 15213
xii
In Controlled/Living Radical Polymerization: Progress in RAFT, DT, NMP & OMRP; Matyjaszewski, K.;
ACS Symposium Series; American Chemical Society: Washington, DC, 2009.
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Publication Date: August 13, 2009 | doi: 10.1021/bk-2009-1024.pr001
Chapter 1
New Features of the Mechanism of RAFT
Polymerization
Graeme Moad,* Y.K. Chong, Roger Mulder, Ezio Rizzardo, San H.
Thang,
CSIRO Molecular and Health Technologies, Bag 10, Clayton South,
Victoria 3169, Australia
RAFT polymerizations of styrene with azobis(isobutyronitrile-
13
α- C) as initiator and various RAFT agents (cumyl
dithiobenzoate (5), cyanoisopropyl dithiobenzoate (6), benzyl
13
dithiobenzoate-thiocarbonyl- C (7) or cyanoisopropyl
13
dodecyl trithiocarbonate (8)) were followed by real time C
NMR. While the rate of AIBN decomposition and the initial
fate of the initiator-derived radicals (the initiator efficiency)
were not substantially affected by the RAFT agent, the rate of
polymerization was strongly dependent on both the type and
concentration of RAFT agent. Polymerizations with the more
active dithiobenzoate (5,6) RAFT agents and trithiocarbonate
8 display formation of a single unit styrene chain prior to any
substantial formation of higher oligomers. An unexpected
13
finding is the observation of C CIDNP for the ketenimine
formed by cage recombination of AIBN-derived
cyanoisopropyl radicals. With benzyl dithiobenzoate (7),
consumption of the initial RAFT agent is slow. By-products
from intermediate radical termination are also observed.
© 2009 American Chemical Society 3

In Controlled/Living Radical Polymerization: Progress in RAFT, DT, NMP & OMRP; Matyjaszewski, K.;
ACS Symposium Series; American Chemical Society: Washington, DC, 2009.
Downloaded by 89.163.34.136 on June 25, 2012 | http://pubs.acs.org
Publication Date: August 13, 2009 | doi: 10.1021/bk-2009-1024.ch001
4
Introduction
The RAFT process is a versatile method for conferring living characteristics
on radical polymerizations which provides unprecedented control over
1-
molecular weight, molecular weight distribution, composition and architecture.
5
It is suitable for most monomers polymerizable by radical polymerization and
is robust under a wide range of reaction conditions. RAFT polymerizations of
styrene were described in the first communication of RAFT polymerization in
6
1998 and have been the subject of many subsequent papers. The mechanism of
the RAFT process is shown in Scheme 1. Ideally, since radicals are neither
formed nor destroyed as a consequence of the RAFT equilibria, they should not
directly affect the rate of polymerization. RAFT agents can behave as ideal
7-9
chain transfer agents.

Scheme 1 Mechanism of RAFT polymerization

1 2 3

3 4 3

1
However, retardation has been observed in some circumstances. In 2000,
we reported that RAFT polymerizations of styrene, BA and MMA were subject
to retardation when high concentrations of RAFT agent were used and that the
extent, mechanism and particular manifestation of retardation were dependent
on the specific RAFT agent-monomer combination used. Much has now been
published on retardation in RAFT polymerization and the possible causes of a
7
slower rate of polymerization. The situation with respect to control of radical
polymerization with dithiobenzoate RAFT agents has been summarized by an
10
IUPAC task group in a ‘dilemma’ paper. Factors that may influence the
polymerization kinetics include (a) slow fragmentation of the intermediated
In Controlled/Living Radical Polymerization: Progress in RAFT, DT, NMP & OMRP; Matyjaszewski, K.;
ACS Symposium Series; American Chemical Society: Washington, DC, 2009.
Downloaded by 89.163.34.136 on June 25, 2012 | http://pubs.acs.org
Publication Date: August 13, 2009 | doi: 10.1021/bk-2009-1024.ch001