Recent Advances in Anionic Polymerization: Proceedings of the International Symposium on Recent Advances in Anionic Polymerization, held April 13–18, 1986 at the American Chemical Society Meeting in New York, New York, U.S.A.

452 Pages·1987·13.11 MB·English

by  Erling Grovenstein Jr. (auth.)

Recent Advances
in Anionic Polymerization
Recent Advances
in Anionic Polymerization
Proceedings of the International Symposium on Recent Advances in
Anionic Polymerization, held April 13-18, 1986 at the American
Chemical Society Meeting in New York, New York, U.S.A.
Editors:
Thieo E. Hogen-Esch, Ph.D.
Department of Chemistry
University of Florida
Gainesville, Florida, U.S.A.
Johannes Smid, Ph.D.
Chemistry Department
State University of New York
College of Environmental Science and Forestry
Syracuse, New York, U.S.A.
Elsevier
New York • Amsterdam • London
Elsevier Science Publishing Co., Inc.
52 Vanderbilt Avenue, New York, New York 10017
Distributors outside the United States and Canada:
Elsevier Applied Science Publishers Ltd.
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© 1987 by Elsevier Science Publishing Co., Inc.
Softcover reprint of the hardcover 1st edition 1987
This book has been registered with the Copyright Clearance Center, Inc.
For further information, please contact the Copyright Clearance Center, Inc.,
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Library of Congress Cataloging-in-Publication Data
Recent advances in anionic polymerization, carbanions, mechanism and synthesis.
Sponsored by the American Chemical Society Polymer Division.
Includes indexes.
\. Addition polymerization-Congresses. 2. Carbanions-Congresses. I. Hogen-Esch,
Thieo E. II. Smid, Johannes. III. American Chemical Society. Division of Polymer
Chemistry .
QD28\.P6R398 1987 541.3'93 87-9119
ISBN-13: 978-94-010-7924-2 e-ISBN-13: 978-94-009-3175-6
DOl: 10.1007/978-94-009-3175-6
Current printing (last digit)
10 9 8 7 6 5 4 3 2
v
CONTENTS
Preface ix
CARBANIONS
1. Cation Effects in Organoa1ka1i Metal Chemistry............. 3
E. Grovenstein, Jr.
2. Structure and Dynamic Behavior of Organolithium Compounds.. 23
G. Fraenkel
3. Spectroscopic Studies of Some Cryptated Lithium Carbanions
and Related Species ........................................ 49
S. Hubert, C. Momtaz, P. Hemery, S. Boileau, and
J.P. Kintzinger
4. New Aspects of Carbanion Chemistry. Structure of Pentadienyl
Anions and Butenediyl Dianions and Their Roles in Organic
and Inorganic Syntheses. .................. ....... ......... 59
H. Yasuda, K. Tatsumi and A. Nakamura
5. Ion Pair Structure and Photochemistry of Partially Metallated
Poly (2-Vinylfluorene) in Solution ............. ............. 73
M. Matsuda and A. Watanabe
MECHANISMS
6. Clarification of Some Problems of Anionic Polymerization 93
M. Szwarc
7. The Effect of Molecular Weight on Association in Anionic
Polymerization ............................................. 109
S. Bywater and D.J. Worsfold
8. Anionic Polymerization of 4'-Vinylbenzocrown Ethers........ 121
F. Gils, M. Van Beylen and J. Smid
9. Kinetics and Thermodynamics of Anionic Polymerization of
2-Isopropenylpyridine in Toluene .................. .... ..... 137
A. Aboudalle, A. Soum, M. Fontanille and T.E. Hogen-Esch
10. Mechanistic Aspects of the Reversibility and Irreversibility
of the Anionic Polymerization of n-Methylstyrene ........... 147
J.-Y. Bergeron and J. Leonard
11. Donor-Acceptor Interactions of the Active Centres of Chain
Propagation in the Anionic Polymerization of Acrylonitrile
and Methacrylonitrile and Some Other Polar Vinyl Monomers .. 155
C.B. Tsvetanov, D.T. Dotcheva, D.K. Dimov, E.B. Petrova and
I.M. Panayotov
vi
12. Pyridine-Mediated Anionic Homo-and Copolymerization of
A1kylmethacry1ate ... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 173
G. Huynh-Ba and J.E. McGrath
STEREOCHEMISTRY
13. Stereospecificity in Anionic Polymerization 1B7
S. Bywater
14. Mechanism of Polymerization of MMA by Grignard Reagents and
Preparation of Highly Isotactic PMMA with Narrow Molecular
Weight Distribution ........................................ 195
K. Hatada, K. Ute, K. Tanaka, T. Kitayarna and Y. Okamoto
15. Kinetics and Mechanisms in the Anionic Polymerization of
Methacry1ic Esters ......................................... 205
A.H.E. Mi.iller
16. Stereoelective Anionic Polymerization of Chiral Vinyl
Monomers via Interconverting Ion Pair Epimers .............. 231
M.A. Buese and T.E. Hogen-Esch
17. Polymerization of Methylmethacrylate Initiated by Complexed
Alkali Alkoxides in the Homogeneous Phase and Related
Tacticities ................................................ 249
M. Viguier, A. Collet, F. Schue and B. Mula
lB. Role of E- and Z-Carbanions in the Stereochemistry of
Anionic Vinyl Polymerization ..................... .... .. .. . . . 261
I.M. Khan and T.E. Hogen-Esch
RING-OPENING POLYMERIZATION
19. Progress in Anionic Ring-Opening Polymerization 275
S. Penczek and S. Slornkowski
20. Chiral Anionic Coordinated Polymerization of Thiiranes:
Enantiomeric Resolution and Disulfide Linkage Formation 297
M. Sepulchre, A. Morntaz and N. Spas sky
21. Some Mechanistic Aspects of the Anionic Block
Copolymerization of Caprolactarn and Polyether Diols . ....... 313
M.K. Akkapeddi, G.J. Dege, T.D. Gallagher and M.S. Walsh
22. Anionic Polymerization of Si1oxanes. Non-Trivial Model
System for Studies of Common Phenomena ...... ............ ... 329
M. Mazurek
SYNTHESIS
23. Synthesis and Applications of Macromonomers 353
P. Rernpp and E. Franta
24. Investigations of Hydrocarbon Soluble Difunctional
Organolithium Initiators Based Upon 1,3-Bis(Phenyl Ethenyl)
Benzene . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 363
A.D. Broske, T.L. Huang, R.D. Allen, J.M. Hoover and J.E.
McGrath
vii
25. Synthesis of Poly(Methyl Methacrylate) Macrornonorner by
Group Transfer Polymerization and Polymerization of the
Macrornonorner. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 381
R. Asami, Y. Kondo and M. Takaki
26. Living Coupling Agents. Rational Synthesis of Heteroarrn
Star-Branched Polymers ..................................... 393
R.P. Quirk and F. Ignatz-Hoover
27. Synthesis and Solution Properties of V~crocyclic Polymers 403
P. Lutz, C. Strazielle and P. Rempp
28. Anionic Polymerizations of 2-Isopropenylnaphthalene 411
H.L. Hsieh and I.W. Wang
29. Anionic Polymerization of a-(Trifluorornethyl) Acrylate ..... 421
H. Ito and R. Schwalm
30. Synthesis and Characterization of Polysulphide Polymers 431
J.M. Catala, J.M. Pujol and J. Brossas
31. Synthesis of Cellulose-g-Polystyrene by Anionic
Polymerization ............................................. 441
R. Narayan and M. Shay
32. Ion-Containing Styrene-Methoxypolyethyleneglycol
Methacrylate ABA Triblock Copolymers .... ................... 451
I.M. Khan, D. Fish and J. Smid
Author Index .................................................... 459
Subject Index ................................................... 461
ix
PREFACE
Over the years the field of anionic polymerization has attracted
numerous outstanding scientists, and today it still is being pursued by
many researchers all over the world. The exciting discovery of
termination-less polymerization processes and living polymers culminating
in the development of narrow molecular weight polymers, star polymers, and
tailor-made block and graft copolymers, contributed immensely to the rapid
expansion of polymer science. Areas of active research in anionic
polymerization presently include the structure of ion pairs and their role
in regulating polymer structure, ring opening polymerization of
heterocyclic monomers, synthesis of well-defined block and graft copolymers
including the application of macromers in such systems, telechelic polymers
with functional end groups, and other topics. New developments in the
organic chemistry of carbanions such as dipolar carbanions impinge on the
field of anionic polymerization. More sophisticated characterization
techniques have been instrumental in obtaining better correlations between
the structure of polymers and that of intermediates leading to their
formation.
This book contains the proceedings of the international symposium on
"Recent Advances in Anionic Polymerization and Related Processes" which was
held at the 1986 spring meeting of the American Chemical Society. It was
the first Polymer Division-sponsored meeting exclusively devoted to anionic
polymerization since the Houston ACS meeting in the spring of 1980. The
proceedings of that meeting were published in the book "Anionic
Polymerization", ACS Symposium Series No. 166, edited by Dr. J.E. McGrath.
The chief emphasis of the recent New York symposium was directed towards
synthetic and mechanistic aspects of anionic polymerization, and included a
session on carbanion chemistry and one on group transfer polymerization.
The latter was a joint session with the symposium on Unconventional
Mechanisms and Methods of Polymerization. However, these lectures are not
i~cluded in this book. We trust that the critical reviews and the many
topics of current interest presented in the ensuing pages will be helpful
to interested students and scientists.
Two researchers who made important contributions to the field of
anionic polymerization and who had been invited to participate in this
symposium are not listed among the authors. Dr. Ralph t~ilkovich, a former
student of two of the most prolific researchers in anionic polymerization,
professors Michael Szwarc and t·1aurice Horton, passed away as the symposium
was being organized. r~ilkovich discovered and developed the thermoplastic
styrene-diene-styrene and other triblock copolymers which started a new era
in the synthesis of tailor-made block copolymers. He also did pioneering
work in developing macromonomers useful in the synthesis of graft
copolymers of controlled structure. Both topics were covered by ~:ilkovich
in the book edited by 11cGrath. For his outstanding and original research
Ralph I:ilkovich received the American Chemical Society Award for Creative
Invention at the Miami ACS meeting in the spring of 1985. Dr. David H.
Richards from England, known to many of us as Rick, died in the spring of
x
1986. He was well recognized for his very interesting research on
specially designed block copolymers which were synthesized by changing the
mode of propagation from an active anionic center to a cationic or radical
center. Both these individuals will be greatly missed by their colleagues
and friends.
We like to thank all those who contributed to this book and gratefully
acknowledge the secretarial assistance of Ragan Feidt and Lorraine
Williams. A grant from the Petroleum Research Fund administered by the
American Chemical Society was extremely helpful in attracting to the
symposium participants from outside the United States.
Chemistry Department Thieo E. Hogen-Esch
University of Florida
Gainesville, Florida
Chemistry Department Johannes Smid
Polymer Research Institute
State University of New York
Syracuse, New York
CARBANIONS
3
CATION EFFECTS IN ORGANOALKALI METAL CHEMISTRY
ERLING GROVENSTEIN, JR.
School of Chemistry
Georgia Institute of Technology
Atlanta, Georgia 30332
I. INTRODUCTION
Organoalkali metal compounds can be regarded as substances in which the
organic anion is joined to the counter alkali metal cation primarily by
electrostatic forces between cations and anions. This generalization [lJ is
believed to hold even for organolithium compounds with localized negative
charge, although here some small carbon-lithium covalency may enhance bonding
[2]. From the simplified structure R-M+, it is tempting to think that the
nature of M+ is unimportant, in other words, that one is concerned only with
the chemistry of "carbanions" in discussing the reaction of R-M+.
As the Arrhenius theory of ionization emphasizes, the chemistry of salts
in dilute aqueous solution ~ be discussed in terms of kinetically "free"
cations and anions; however, organoalkali metal compounds have inappreciable
lifetimes in protic solvents and ordinarily are studied in ethereal or
hydrocarbon solvents. In such media organoalkali metal compounds exist as
ion pairs and aggregates of ion pairs as Michael Szwarc [3] and others have
emphasized (see Scheme 1). It should be understood that, in ethereal
Scheme 1
ionic aggregate contact ion pair solvent-separated
ion pai r
or
peripherally solvated
contact ion pair
solvents, all of these ionic species are solvated such that the coordination
shell of the alkali metal cation is normally filled. Thus the contact ion
pair of lithium would be expected to contain three ethereal oxygens in its
peri phery.
Published 1987 by Elsevie': Scierlce ?:..tblisr!ing Co , Inc.
Recent Advances in Anioni,;:
T.E. Hogen-Esch and J. SmHl,