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Progress in Controlled
Radical Polymerization:
Mechanisms and Techniques
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Publication Date (Web): March 20, 2012 | doi: 10.1021/bk-2012-1100.fw001
In Progress in Controlled Radical Polymerization: Mechanisms and Techniques; Matyjaszewski, K., et al.;
ACS Symposium Series; American Chemical Society: Washington, DC, 2012.
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In Progress in Controlled Radical Polymerization: Mechanisms and Techniques; Matyjaszewski, K., et al.;
ACS Symposium Series; American Chemical Society: Washington, DC, 2012.
ACS SYMPOSIUM SERIES 1100
Progress in Controlled
Radical Polymerization:
Mechanisms and Techniques
Krzysztof Matyjaszewski, Editor
Carnegie Mellon University
Pittsburgh, Pennsylvania
Brent S. Sumerlin, Editor
Southern Methodist University
Dallas, Texas
Nicolay V. Tsarevsky, Editor
Southern Methodist University
Dallas, Texas
Sponsored by the
ACS Division of Polymer Chemistry, Inc.
American Chemical Society, Washington, DC
Distributed in print by Oxford University Press, Inc.
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In Progress in Controlled Radical Polymerization: Mechanisms and Techniques; Matyjaszewski, K., et al.;
ACS Symposium Series; American Chemical Society: Washington, DC, 2012.
Library of Congress Cataloging-in-Publication Data
Progress in controlled radical polymerization : mechanisms and techniques /
Krzysztof Matyjaszewski, Brent S. Sumerlin, Nicolay V. Tsarevsky, editor[s] ; sponsored
by the ACS Division of Polymer Chemistry, Inc.
p. cm. (ACS symposium series ; 1100)
Includes bibliographical references and index.
ISBN 978-0-8412-2699-9
1. Addition polymerization. 2. Radicals (Chemistry) I. Matyjaszewski, K. (Krzysztof)
II. Sumerlin, Brent S. III. Tsarevsky, Nicolay V. IV. American Chemical Society.
Division of Polymer Chemistry, Inc.
TP156.P6P76 2012
541′.224 dc23
2012005349
The paper used in this publication meets the minimum requirements of American National
Standard for Information Sciences—Permanence of Paper for Printed Library Materials,
ANSI Z39.48n1984.
Copyright © 2012 American Chemical Society
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In Progress in Controlled Radical Polymerization: Mechanisms and Techniques; Matyjaszewski, K., et al.;
ACS Symposium Series; American Chemical Society: Washington, DC, 2012.
Foreword
The ACS Symposium Series was rst 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 scientic research. Occasionally, books are
developed from symposia sponsored by other organizations when the topic is of
keen interest to the chemistry audience.
Before agreeing to publish a book, the proposed table of contents is reviewed
for appropriate and comprehensive coverage and for interest to the audience. Some
papers may be excluded to better focus the book; others may be added to provide
comprehensiveness. When appropriate, overview or introductory chapters are
added. Drafts of chapters are peer-reviewed prior to nal acceptance or rejection,
and manuscripts are prepared in camera-ready format.
As a rule, only original research papers and original review papers are
included in the volumes. Verbatim reproductions of previous published papers
are not accepted.
ACS Books Department
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In Progress in Controlled Radical Polymerization: Mechanisms and Techniques; Matyjaszewski, K., et al.;
ACS Symposium Series; American Chemical Society: Washington, DC, 2012.
Editors' Biographies
Krzysztof Matyjaszewski
Krzysztof Matyjaszewski is the J.C. Warner University Professor of
Natural Sciences and Director of the Center for Macromolecular Engineering at
Carnegie Mellon University. He developed atom transfer radical polymerization,
commercialized in the U.S., Europe, and Japan. He has co-authored 700
publications (cited ca. 50,000 times, h-index 114), co-edited 14 books, and holds
40 U.S. and 120 international patents. Matyjaszewski received the 2011 Wolf
Prize in Chemistry, 2009 Presidential Green Chemistry Challenge Award, and
from the American Chemical Society: 2011 Hermann Mark Award, 2011 Award
in Applied Polymer Science, 2002 Polymer Chemistry Award, and 1995 Creative
Polymer Chemistry Award. He is a member of the USA National Academy of
Engineering, Polish Academy of Sciences, and Russian Academy of Sciences.
Brent S. Sumerlin
Brent S. Sumerlin graduated with a B.S. from North Carolina State University
(1998) and a Ph.D. from the University of Southern Mississippi (2003) under the
direction of Charles McCormick. After serving as a Visiting Assistant Professor
at Carnegie Mellon University under the direction of Krzysztof Matyjaszewski
(2003-2005), he joined the Department of Chemistry at Southern Methodist
University (Dallas, Texas, USA) as an assistant professor in 2005 and was
promoted to associate professor in 2009. In 2012, Prof. Sumerlin joined the
Department of Chemistry at the University of Florida. Prof. Sumerlin has
received several awards, including a NSF CAREER Award and an Alfred P. Sloan
Research Fellowship.
Nicolay V. (Nick) Tsarevsky
Nicolay V. (Nick) Tsarevsky obtained a M.S. in theoretical chemistry and
chemical physics from the University of Soa, Bulgaria (1999) and a Ph.D.
in chemistry from Carnegie Mellon University (CMU, 2005, under Krzysztof
Matyjaszewski). He was visiting assistant professor at the CMU Department of
Chemistry (2005-2006), associate director of the CRP Consortium (2006-2007),
and CSO of ATRP Solutions, Inc. (2007-2010). He joined the Department
of Chemistry at Southern Methodist University in 2010. Research interests
include polymerization techniques, functional materials, coordination chemistry,
catalysis, and the chemistry of hypervalent compounds. He is the (co)author of
over 65 peer-reviewed papers or book chapters, a textbook, and several patents.
© 2012 American Chemical Society
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In Progress in Controlled Radical Polymerization: Mechanisms and Techniques; Matyjaszewski, K., et al.;
ACS Symposium Series; American Chemical Society: Washington, DC, 2012.
Preface
This book and a following 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 eld.
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 Denver, Colorado, August
29 - September 1, 2011. The Denver 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, in Washington, DC,
in 2005 and in Philadelphia, in 2008. 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, Volume
944: Controlled/Living Radical Polymerization: From Synthesis to Materials,
Volume 1023: Controlled/Living Radical Polymerization: Progress in ATRP, and
Volume 1024: Controlled/Living Radical Polymerization: Progress in RAFT,
DT, NMP and OMRP. The Denver Meeting was very successful with 96 lectures
and 83 posters presented. This illustrates a continuous growth in comparison to
the San Francisco Meeting (32 lectures), the New Orleans Meeting (50 lectures),
the Boston Meeting (80 lectures), the Washington Meeting (77 lectures), and the
Philadelphia Meeting (90 lectures).
The 41 chapters submitted for publication in the ACS Symposium series could
not t into one volume, and therefore we were asked by ACS to split them into two
volumes. We decided to divide the chapters into volumes related to mechanisms
and techniques (21 chapters) and materials (20 chapters).
The rst chapter in this 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 seven chapters, and
the next two are related to commercial aspects of ATRP. Two chapters discuss
organometallic radical polymerization, and the last six present recent progress in
reversible addition-fragmentation chain transfer polymerization and in reversible
iodine transfer polymerization.
The accompanying volume contains seven chapters on macromolecular
architecture, two chapters on materials for electronic applications, eight on hybrid
materials and four on bio-related materials.
Forty-one chapters published in two volumes show that CRP has made
signicant progress within the last 15 years. New systems have been discovered;
xi
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Publication Date (Web): March 20, 2012 | doi: 10.1021/bk-2012-1100.pr001
In Progress in Controlled Radical Polymerization: Mechanisms and Techniques; Matyjaszewski, K., et al.;
ACS Symposium Series; American Chemical Society: Washington, DC, 2012.
substantial progress has been achieved in understanding the mechanism and
kinetics of reactions involved in all CRP systems. Signicant progress has been
made towards a comprehensive relationship between molecular structure and
macroscopic properties. Some commercial applications of CRP were announced
at the Denver Meeting, and it is anticipated that new products made by CRP will
be soon on the market.
The nancial support for the symposium from the following organizations
is acknowledged: ACS Division of Polymer Chemistry, Inc., Boston Scientic,
CSIRO, DSM, Evonik, General Electric, Lubrizol, the National Science
Foundation, PPG, Royal Chemical Society and Wiley-VCH.
Krzysztof Matyjaszewski
Department of Chemistry
Carnegie Mellon University
4400 Fifth Avenue
Pittsburgh, Pennsylvania 15213
Brent Sumerlin
Department of Chemistry
Southern Methodist University
3215 Daniel Avenue
Dallas, Texas 75275
Nicolay V. Tsarevsky
Department of Chemistry
Southern Methodist University
3215 Daniel Avenue
Dallas, Texas 75275
xii
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In Progress in Controlled Radical Polymerization: Mechanisms and Techniques; Matyjaszewski, K., et al.;
ACS Symposium Series; American Chemical Society: Washington, DC, 2012.
Chapter 1
Controlled Radical Polymerization:
State-of-the-Art in 2011
Krzysztof Matyjaszewski
*
Center for Macromolecular Engineering, Department of
Chemistry, Carnegie Mellon University, 4400 Fifth Avenue,
Pittsburgh, Pennsylvania 15213, USA
*
E-mail: km3b@andrew.cmu.edu
The state-of-the-art of controlled radical polymerization (CRP)
in 2011 is presented. Atom transfer radical polymerization,
stable radical mediated polymerization, and degenerate transfer
processes, including reversible addition fragmentation chain
transfer are the most often used CRP procedures. CRP opens
new avenues to novel materials from a large range of monomers.
Detailed structure-reactivity relationships and mechanistic
understanding not only helps attain a better controlled
polymerization but enables preparation of polymers with
complex architectures. Correlation of macromolecular structure
with nal properties of prepared materials is a prerequisite for
creation of new applications and commercialization of various
CRP products.
© 2012 American Chemical Society
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In Progress in Controlled Radical Polymerization: Mechanisms and Techniques; Matyjaszewski, K., et al.;
ACS Symposium Series; American Chemical Society: Washington, DC, 2012.
Controlled/living radical polymerization (CRP) is among the most rapidly
expanding areas of chemistry and polymer science (1–5).
The advent of controlled radical polymerization (CRP) (IUPAC recommends
the term reversible-deactivation radical polymerization (RDRP), or controlled
reversible-deactivation radical polymerization and discourages using “living
radical polymerization”) (6) has opened new avenues to various advanced
materials with precisely controlled molecular architecture.
The dynamic equilibria required in RDRP systems can be reached in two ways
(7). One approach employs reversible deactivation of propagating radicals to form
dormant species that can be intermittently re-activated either in the presence of a
catalyst, as in atom transfer radical polymerization, ATRP (8), or spontaneously,
as in stable radical mediated polymerization, SRMP (with aminoxyl radicals or
organometallic species) (9). The kinetics of SRMP and ATRP generally follow a
particular persistent radical effect (10).
The second approach employs degenerate transfer between propagating
radicals and dormant species. Typical examples of degenerate-transfer radical
polymerization, DTRP, include reversible-addition-fragmentation chain-transfer
polymerization, RAFT or iodine transfer radical polymerization (11). Generally,
for DTRP, an external source of radicals is necessary but dormant species can
also be activated by Cu-based catalyst, without generation of new chains (12,
13). RAFT kinetics is similar to conventional RP but may sometimes depend on
the nature of radicals and initiators/transfer agents and can be accompanied by
retardation.
RDRP is among the most rapidly developing areas of polymer science. They
provide a versatile synthetic tool that enables preparation of new (co)polymers
with controlled architecture and materials with properties that can be targeted for
various advanced technologies and biomedicine. Figure 1 presents the cumulative
number of papers published on ATRP, SMRP and RAFT, as well as overall
RDRP (using terms living or controlled radical polymerization) during the last 16
years. The growth in the number of publications in all areas of RDRP reects the
increasing level of interest in this eld, although currently many papers do not
use terms related to RDRP in titles, abstract or keywords, as they have become
well-known “classic” terms in polymer science. Nevertheless, a continuous
increase in the number of publications on CRP can be noted. This is accompanied
by an increase in the number of patent applications and symposia partially or
entirely devoted to CRP (14–19).
Figure 1 illustrates the results of a recent SciFinder Scholar search using the
following terms: controlled radical polymn or living radical polymn (“SUM CRP”
in Figure 1); ATRP or atom transfer (radical) polymn (“SUM ATRP”, this search
does not include terms such as metal mediated or metal catalyzed (living) radical
polymerization); NMP or SFRP or nitroxide mediated polymn or stable free polymn
(“SUM SFRP”) and RAFT (“SUM RAFT”). The latter two terms were rened
with terms radical polymn and polymer or polymn, respectively, since the search
coincides with other common chemical terms such as N-methylpyrrolidone or raft-
associated proteins. In summary, over 18,000 papers have been published on
various CRP systems since 1995 and more than 11,000 on ATRP. Figure 1 also
2
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In Progress in Controlled Radical Polymerization: Mechanisms and Techniques; Matyjaszewski, K., et al.;
ACS Symposium Series; American Chemical Society: Washington, DC, 2012.
[...]... stereo- and chemoselectivities of radicals originate in the sp2 hybridization and low polarity of radicals Nevertheless, the addition of Lewis acids and other complexing or templating agents help enhance control of polymer tacticity and sequence distribution (33–35) One could also prepare dimeric or trimeric species and incorporate 6 In Progress in Controlled Radical Polymerization: Mechanisms and Techniques; ... developments in the previously discussed areas originate in understanding the mechanism and kinetics of radical processes (42–44) Profound structure-reactivity correlation for monomers, radicals, dormant species and mediating agents using computational and experimental techniques helps develop an understanding of the systems and also selection of efficient initiators, mediating agents and design the... different reaction conditions affect chain end functionality in a CRP Assuming, in the first approximation, a constant value of the rate coefficient of termination, predominant termination by disproportionation, and efficient initiation, one can derive a simple correlation between dead chain fraction (DCF), 3 In Progress in Controlled Radical Polymerization: Mechanisms and Techniques; Matyjaszewski, K., et... CRP), corresponds to the same radical concentration and to essentially the same number (concentration) of terminated chains Typically, the fraction of terminated chains is between 1 and 10% The remaining chains are in the dormant state, capable of reactivation, functionalization, chain extension to form block copolymers, etc Since the proportion of terminated chains in the final product is small, they... bioconjugates based on water soluble components and especially stimuli responsive organic polymers could find applications in drug delivery systems and tissue engineering (50–55) CRP provides access to a large variety of (co)polymers with controlled MW, MWD, topology, composition and functionality However, a 7 In Progress in Controlled Radical Polymerization: Mechanisms and Techniques; Matyjaszewski, K., et al.;... weakly influences the terminal radical, primarily because of the planarity of the propagating radical and the relatively early position of the transition state However, a number of exceptions have been documented in the experimental literature, 16 In Progress in Controlled Radical Polymerization: Mechanisms and Techniques; Matyjaszewski, K., et al.; ACS Symposium Series; American Chemical Society: Washington,... Washington, DC, 2003 17 Matyjaszewski, K., Ed.; Controlled/ Living Radical Polymerization: From Synthesis to Materials; ACS Symposium Series 944; American Chemical Society: Washington, DC, 2006 18 Matyjaszewski, K., Ed.; Controlled/ Living Radical Polymerization: Progress in ATRP; ACS Symposium Series 1023; American Chemical Society: Washington, DC, 2009 19 Matyjaszewski, K., Ed.; Controlled/ Living Radical. .. cross-propagation and block copolymer formation On the other hand, due to continuous termination, polymers may loose functionality but still have low dispersity (especially if termination occurs at high conversion by disproportionation) Thus, the correlation between dispersity and functionality in CRP may be relatively weak 5 In Progress in Controlled Radical Polymerization: Mechanisms and Techniques; Matyjaszewski,... significant inadequacy of radical based techniques is the lack of stereochemical control in common radical polymerizations Controlling the tacticity (stereochemistry) of a polymer is highly desirable because it influences its physical properties such as the melting point, solubility, density, crystallinity and mechanical strength (1, 2) For instance, the melting points of isotactic, syndiotactic and atactic... entries show the effect of DPT for 500 and 100 values for PMA at 90% conversion The former requires 4 minutes but the latter less than 1 minute Finally, green (bold underlined) entries show that the same DCF = 10% for PSt and DPT = 100 requires 3.5 days at 90% conversion but only 0.6 days at 60% conversion 4 In Progress in Controlled Radical Polymerization: Mechanisms and Techniques; Matyjaszewski, K., et . 1023: Controlled/ Living Radical Polymerization: Progress in ATRP, and
Volume 1024: Controlled/ Living Radical Polymerization: Progress in RAFT,
DT, NMP and. Polymerization: Progress in ATRP, NMP and RAFT,
Volume 854: Advances in Controlled/ Living Radical Polymerization, Volume
944: Controlled/ Living Radical Polymerization:
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