Progress in Controlled Radical Polymerization: Mechanisms and Techniques Downloaded by UNIV OF CALIFORNIA BERKELEY on April 8, 2012 | http://pubs.acs.org 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. Downloaded by UNIV OF CALIFORNIA BERKELEY on April 8, 2012 | http://pubs.acs.org 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. 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. Downloaded by UNIV OF CALIFORNIA BERKELEY on April 8, 2012 | http://pubs.acs.org 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. 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 Distributed in print by Oxford University Press, Inc. All Rights Reserved. Reprographic copying beyond that permitted by Sections 107 or 108 of the U.S. Copyright Act is allowed for internal use only, provided that a per-chapter fee of $40.25 plus $0.75 per page is paid to the Copyright Clearance Center, Inc., 222 Rosewood Drive, Danvers, MA 01923, USA. Republication or reproduction for sale of pages in this book is permitted only under license from ACS. Direct these and other permission requests to ACS Copyright Ofce, Publications Division, 1155 16th Street, N.W., Washington, DC 20036. 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PRINTED IN THE UNITED STATES OF AMERICA Downloaded by UNIV OF CALIFORNIA BERKELEY on April 8, 2012 | http://pubs.acs.org 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. 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 scientic 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 Downloaded by UNIV OF CALIFORNIA BERKELEY on April 8, 2012 | http://pubs.acs.org 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. 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 Soa, 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 Downloaded by UNIV OF CALIFORNIA BERKELEY on April 8, 2012 | http://pubs.acs.org Publication Date (Web): March 20, 2012 | doi: 10.1021/bk-2012-1100.ot001 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 signicant progress within the last 15 years. New systems have been discovered; xi Downloaded by UNIV OF CALIFORNIA BERKELEY on April 8, 2012 | http://pubs.acs.org 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. Signicant 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 Scientic, 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 Downloaded by UNIV OF CALIFORNIA BERKELEY on April 8, 2012 | http://pubs.acs.org 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. 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 Downloaded by UNIV OF CALIFORNIA BERKELEY on April 8, 2012 | http://pubs.acs.org Publication Date (Web): March 20, 2012 | doi: 10.1021/bk-2012-1100.ch001 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 reects 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 rened 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 Downloaded by UNIV OF CALIFORNIA BERKELEY on April 8, 2012 | http://pubs.acs.org Publication Date (Web): March 20, 2012 | doi: 10.1021/bk-2012-1100.ch001 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: