Table Of ContentIonic Liquids in Polymer
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In Ionic Liquids in Polymer Systems; Brazel, C., et al.;
ACS Symposium Series; American Chemical Society: Washington, DC, 2005.
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In Ionic Liquids in Polymer Systems; Brazel, C., et al.;
ACS Symposium Series; American Chemical Society: Washington, DC, 2005.
ACS SYMPOSIUM SERIES 913
Ionic Liquids in Polymer
g Systems
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2 | http://pub2005-0913.f Solvents, Additives, and Novel
1, 20121/bk- Applications
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n Se05 | Christopher S. Brazel, Editor
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152.135 uly 21, 2 The University of Alabama
217.66.Date: J Robin D. Rogers, Editor
y n The University of Alabama
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Sponsored by the ACS Division
Polymer Chemistry, Inc.
American Chemical Society, Washington, DC
In Ionic Liquids in Polymer Systems; Brazel, C., et al.;
ACS Symposium Series; American Chemical Society: Washington, DC, 2005.
Library of Congress Cataloging-in-Publication Data
Ionic liquids in polymer systems : solvents, additives, and novel applications /
Christopher S. Brazel, editor, Robin D. Rogers, editor.
p. cm.—(ACS symposium series; 913)
Includes bibliographical references and index.
g ISBN 0-8412-3936-3 (alk. paper)
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cs.01 1. Polymer solutions—Congresses. 2. Ionic solutions—Congresses. 3. Solvents—
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2 | htt2005- Division of Polymer Chemistry, Inc. IV. Series.
1, 20121/bk- 5Q4D73'.8710.94.S5645-d15c52 2 2005 2005040959
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n Se05 | Materials, ANSI Z39.48-1984.
152.135 ouly 21, 20 DCiosptryirbiugthetd © b2y 0O0x5f oArmd eUrniciavner Csithye mPirceasls Society
217.66.Date: J A10ll 7R oirg h1t0s8 R oefs tehrev eUd..S R. eCporpoygrriagphht iAc ccto ipsy ainllgo wbeedy ofnodr itnhtaetr npaelr musiett eodn lbyy, p Sroecvtiidoends
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w Copyright Office, Publications Division, 1155 16th Street, N.W., Washington,
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PRINTED IN THE UNITED STATES OF AMERICA
In Ionic Liquids in Polymer Systems; Brazel, C., et al.;
ACS Symposium Series; American Chemical Society: Washington, DC, 2005.
Foreword
The ACS Symposium Series was first published in 1974 to pro
vide a mechanism for publishing symposia quickly in book form. The
purpose of the series is to publish timely, comprehensive books devel
oped from ACS sponsored symposia based on current scientific re
search. Occasionally, books are developed from symposia sponsored by
g other organizations when the topic is of keen interest to the chemistry
cs.or01 audience.
s.aw0 Before agreeing to publish a book, the proposed table of con
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n Se05 | papers are included in the volumes. Verbatim reproductions of previ
152.135 ouly 21, 20 ously published papers are not accepted.
217.66.Date: J ACS Books Department
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In Ionic Liquids in Polymer Systems; Brazel, C., et al.;
ACS Symposium Series; American Chemical Society: Washington, DC, 2005.
Preface
org Ionic liquid (IL) research has been brought to the forefront of
cs.01 technologies, particularly in connection with green chemistry and
ubs.a3.pr0 engineering. The new capabilities allowed by ILs extend into disciplines
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7.66.ate: J 2004. They symposium was hosted by the ACS Division of Polymer
1D Chemistry, Inc.
d by 2ation By bringing together polymer scientists who also work with ILs, the
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D of the subject. The body of work represented in this book represents a
collection of research at a time where DLs are just beginning to be
applied to polymeric systems. The works range from ILs in free radical
polymerization and novel additives for materials with superior properties
to ILs as polymer solvents and porogens to assist in designing unique
molecular structures. Because ILs represent a wide-range of new chem
icals, many researchers are looking at traditional materials problems
from a new perspective, while others are taking ILs directly into more
recent fields such as reversible addition fragmentation chain transfer
(RAFT) polymerizations. The work represented in this book includes
ix
In Ionic Liquids in Polymer Systems; Brazel, C., et al.;
ACS Symposium Series; American Chemical Society: Washington, DC, 2005.
contributions by researchers across the world who are at the forefront of
IL technologies.
Christopher S. Brazel
Department of Chemical and Biological Engineering
The University of Alabama
Tuscaloosa, AL 35487-0203
(205) 348-9738 (telephone)
(205) 348-7558 (fax)
g [email protected]
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In Ionic Liquids in Polymer Systems; Brazel, C., et al.;
ACS Symposium Series; American Chemical Society: Washington, DC, 2005.
Chapter 1
Free Radical Polymerization of Styrene and Methyl
Methacrylate in Various Room Temperature
Ionic Liquids
Hongwei Zhang1, Kunlun Hong2, and Jimmy W. Mays1-3*
Departments of 1Material Science and Engineering and 3Chemistry,
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or University of Tennessee, Knoxville, TN 37996
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c0 2ChemicaI Science Division, Oak Ridge National Laboratory,
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http://pu05-0913.
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1, 20121/bk- Conventional free radical polymerization of styrene and
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n Se05 | Typical cations include imidazolium, phosphonium,
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Do and viscosities of the RTILs with the polymerization behavior
fail to yield discernible trends.
© 2005 American Chemical Society 1
In Ionic Liquids in Polymer Systems; Brazel, C., et al.;
ACS Symposium Series; American Chemical Society: Washington, DC, 2005.
2
Introduction
The first room temperature ionic liquid (RTIL); {Efi^lINCy (mp: 12°C)
was reported in 1914 (/) and since then a great deal of research effort has been
exerted to explore the possible applications of RTILs. Initially, they were used
mainly as electrolytes in batteries or for metal electrodepositions.
RTILs are also called molten salts and are liquids containing only cations
and anions at ambient temperature. They exhibit a relatively wide electro
chemical window, good electronic and ionic conductivity, a broad range of room
temperature liquid compositions, negligible vapor pressure and excellent
chemical, thermal, air and, in many cases, moisture stability (2), They are
g composed of weakly coordinating anions, e g. BF" and PF<f and, hence, are
or 4
s.1 highly polar yet non-coordinating solvents. Most imidazolium and pyridinium
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w quartz crystal microbalance sensors (tf), surfactants for neoteric biphasic systems
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(9), desulfurization agents (10% stationary phases for gas chromatography (//),
to solvents for nanoparticle production (12).
Using RTILs as polymerization media has recently attracted increasing
interest (13). Many polymerizations, including free radical (14),
living/controlled free radical (atom transfer radical polymerization (ATRP),
reversible addition-fragmentation chain transfer (RAFT) and nitroxide mediated
polymerization (NMP)) (15% electrochemical (16), condensation (/7), ring-
opening metathesis (18% block (19) and statistical (20) polymerizations have
been carried out in different RTILs. In addition to the unique properties
mentioned above, RTILs can also lead to significant improvements of
In Ionic Liquids in Polymer Systems; Brazel, C., et al.;
ACS Symposium Series; American Chemical Society: Washington, DC, 2005.
