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Controlled Radical Polymerization PDF

482 Pages·1998·39.59 MB·English
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1 0 0 w 5.f Controlled Radical Polymerization 8 6 0 8- 9 9 1 k- b 1/ 2 0 1 0. 1 oi: d 8 | 9 9 1 8, y ar u n a J e: at D n o ati c bli u P In Controlled Radical Polymerization; Matyjaszewski, K.; ACS Symposium Series; American Chemical Society: Washington, DC, 1998. 1 0 0 w 5.f 8 6 0 8- 9 9 1 k- b 1/ 2 0 1 0. 1 oi: d 8 | 9 9 1 8, y ar u n a J e: at D n o ati c bli u P In Controlled Radical Polymerization; Matyjaszewski, K.; ACS Symposium Series; American Chemical Society: Washington, DC, 1998. ACS SYMPOSIUM SERIES 685 Controlled Radical Polymerization 1 0 0 w 5.f 8 6 0 8- 9 9 1 k- b 21/ Krzysztof Matyjaszewski, EDITOR 0 1 0. Carnegie Mellon University 1 oi: d 8 | 9 9 1 8, y ar u n a J e: Developed from a symposium sponsored by the Division at D n of Polymer Chemistry, Inc., at the 213th National Meeting o ati of the American Chemical Society, c ubli San Francisco, CA, P 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. 1 0 0 w ISBN 0-8412-3545-7 5.f 8 6 1. Polymerization—Congresses. 2. Free radical reactions—Congresses 0 8- 99 I. Matyjaszewski, K. (Krzysztof), 1950- . II. American Chemical Society. 1 k- Division of Polymer Chemistry. III. American Chemical Society. Meeting b 1/ (213th: 1997: San Francisco, Calif.) IV. Series. 2 0 0.1 QD281.P6C66 1998 doi: 1 547'.28—dc21 97-437C3IP1 8 | 9 9 1 8, This book is printed on acid-free, recycled paper. y ar u n Ja Copyright © 1998 American Chemical Society e: at D All Rights Reserved. Reprographic copying beyond that permitted by Sections 107 or 108 of the U.S. on Copyright Act is allowed for internal use only, provided that a per-chapter fee of $20.00 plus $0.25 per ati page is paid to the Copyright Clearance Center, Inc., 222 Rosewood Drive, Danvers, MA 01923, USA. c bli Republication or reproduction for sale of pages in this book is permitted only under license fromA CS. Pu Direct these and other permissions requests to ACS Copyright Office, Publications Division, 1155 16th Street, N.W., Washington, DC 20036. The citation of trade names and/or names of manufacturers in this publication is not to be construed as an endorsement or as approval by ACS of the commercial products or services referenced herein; nor should the mere reference herein to any drawing, specification, chemical process, or other data be regarded as a license or as a conveyance of any right or permission to the holder, reader, or any other person or corporation, to manufacture, reproduce, use, or sell any patented invention or copyrighted work that may in any way be related thereto. Registered names, trademarks, etc., used in this publication, even without specific indication thereof, are not to be considered unprotected by law. PRINTED IN THE UNITED STATES OF AMERICA In Controlled Radical Polymerization; Matyjaszewski, K.; ACS Symposium Series; American Chemical Society: Washington, DC, 1998. Advisory Board ACS Symposium Series Mary E. Castellion Omkaram Nalamasu ChemEdit Company AT&T Bell Laboratories Arthur Β. Ellis Kinam Park University of Wisconsin at Madison Purdue University 001 Jeffrey S. Gaffney Katherine R. Porter 5.fw Argonne National Laboratory Duke University 8 998-06 GUnuivnedrasi tIy. oGf Keoanrgsa s TDhoeu DgAlaSs G Aro.u pS, mInict.h 1 k- b Lawrence P. Klemann 1/ Martin R. Tant 2 Nabisco Foods Group 10 Eastman Chemical Co. 0. doi: 1 RUnicivhearsridty Nof. MLisosoeuprpi ky Michael D. Taylor 8 | Parke-Davis Pharmaceutical 9 Research 9 Cynthia A. Maryanoff 1 8, R. W. Johnson Pharmaceutical ary Research Institute Leroy Β. Townsend u University of Michigan n a ate: J RUnoigveerrs itAy .o fM Ililinneoaisr William C. Walker n D at Urbana-Champaign DuPont Company o ati c bli u P 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 a mechanism for publishing symposia quickly in book form. The purpose of this series is to publish comprehensive books developed from symposia, which are usually "snapshots in time" of the current research being done on a topic, plus some review material on the topic. For this reason, it is necessary that the papers be published as quickly as possible. 1 Before a symposium-based book is put under contract, the 0 w0 proposed table of contents is reviewed for appropriateness to the topic 5.f and for comprehensiveness of the collection. Some papers are 8 06 excluded at this point, and others are added to round out the scope of 8- 9 the volume. In addition, a draft of each paper is peer-reviewed prior to 9 1 k- final acceptance or rejection. This anonymous review process is b 1/ supervised by the organizer(s) of the symposium, who become the 2 0 1 editor(s) of the book. The authors then revise their papers according to 0. doi: 1 tchaem reerac-ormeamdey ndcaotpioyn, sa nodf bsuobthm itth et hree vfiinewal eprsa paenrds tthoe theed iteodrist,o rps,r ewpahroe 98 | check that all necessary revisions have been made. 9 8, 1 As a rule, only original research papers and original review y papers are included in the volumes. Verbatim reproductions of ar nu previously published papers are not accepted. a J e: at D ACS BOOKS DEPARTMENT n o ati c bli u P 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 0 pr0 facileness of (co)polymerization. However, the main deficiency of conventional 85. radical polymerization is a lack of macromolecular control and the difficulty of 6 0 8- making well-defined (co)polymers. 9 19 After several years of relatively slow progress in controlled radical k- b polymerization, the field began to undergo nearly exponential development in 1/ 02 1993, after the first disclosures of styrene radical polymerization mediated by 1 0. nitroxide and several organometallic derivatives. Most recently, reports of 1 oi: metal-catalyzed or atom transfer radical polymerizations have further enhanced d 8 | development of the field. 9 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 n a J field. This book comprises both the topical reviews and the contributions of e: at specialists at a symposium presented at the 213th National Meeting of the D n American Chemical Society, titled "Advances in Free Radical Polymerization", o ati sponsored by the Division of Polymer Chemistry, Inc., in San Francisco, c ubli California, April 13-17, 1997. The first five chapters provide a general P 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 xi 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 1 0 0 Financial support for the symposium from the following organizations is pr 5. gratefully acknowledged: ACS Polymer Division, Inc., ACS Petroleum 8 6 0 Research Fund, Amoco, Bayer, Aristech, BFGoodrich, Ciba-Geigy, Eastman 8- 99 Chemicals, Eastman Kodak, Elf Atochem, Exxon, Hoechst Celanese, ICI, 1 k- Kaneka, Loctite, Mitsui Chemicals, National Starch, Procter & Gamble, b 21/ Raychem, and S.C. Johnson. 0 1 0. 1 oi: KRZYSZTOF MATYJASZEWSKI d 8 | Department of Chemistry 9 9 Carnegie Mellon University 1 8, 4400 Fifth Avenue y ar Pittsburgh, PA 15213 u n a J e: at August 15, 1997 D n o ati c bli u P 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 1 0 0 h c 5. 8 6 8-0 The fundamentals of controlled/"living" polymerization are discussed and the 9 9 effects of slow initiation, transfer, termination and slow exchange on rates, 1 k- b molecular weights, polydispersities and end-functionalities are described. 1/ 2 0 Some special features of and requirements for controlled radical 1 0. oi: 1 polymerization are presented. Historical evolution of concepts leading to 8 | d controlled radical polymerization is reviewed. Developments of several basic 99 concepts in this field are summarized. Potential prospects for controlled 1 8, radical reactions are evaluated. y ar u n a J e: at D n o ati Radical polymerization is a very important commercial process for preparing high c bli molecular weight polymers because it can be used for many vinyl monomers under mild u P 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. 3 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 0 0 ch provides end-group control and enables the synthesis of block copolymers by sequential 5. 68 monomer addition. However, it does not necessarily provide for molecular weight control 0 98- and narrow molecular weight distributions (MWD). Additional prerequisites to achieve 9 1 k- these goals are that the initiator should be consumed at early stages of polymerization and b 21/ that exchange between species of various reactivities is fast in comparison with 0 1 0. propagation.(4-8) If these additional criteria are met, a controlled polymerization results. 1 oi: Polymerization can also be defined as controlled if side reactions occur, but only to an d 8 | extent which does not considerably disturb the control of the molecular structure of the 9 9 8, 1 polymer chain. ary Recently, many new "living" polymerization systems, such as carbocationic, ring- u n a opening metathesis, group transfer, and radical polymerizations, have been developed. J ate: The term "living" (with quotation marks) indicates synthesis of well-defined polymers D n under conditions in which chain breaking reactions undoubtedly occur, as in radical o cati polymerization, but polymerization systems which lead to well-defined polymers but are bli u not completely free of termination or transfer, as are radical polymerizations, should be P 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 n 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.

Description:
Content: Fundamentals of controlled/living radical polymerization / Krzysztof Matyjaszewski -- Radical addition to alkenes : a theoretical perspective / Leo Radom, Ming Wah Wong, and Addy Pross -- Factors influencing the addition of radicals to alkenes / Anne Ghosez-Giese and Bernd Giese -- Cascade
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