Table Of ContentMacromolecular Engineering
Recent Advances
Macromolecular Engineering
Recent Advances
Edited by
Munmaya K. Mishra
TexacoIne..R&D
Beacon.NewYork
Oskar Nuyken
TeehniealUniversityofMunieh
Garching.Germany
Shiro Kobayashi
TohokuUniversity
Aoba.Sendai,Japan
YusufYagci
Istanbul TeehniealUniversity
Maslak,Istanbul.Turkey
and
Bidulata Sar
PFI,lne.
f-Iopewe//Junction. NewYork
Springer Science+Business Media, LLC
Library ofCongress Caraloging-in-PublicationData
Onfile
Proceedings oftheInternational ConferenceonAdvancedPolymersviaMacromolecular Engineering,
heldJune24-28, 1995,at Poughkeepsie,NewYork
ISBN978-1-4613-5778-0 ISBN978-1-4615-1905-8(eBook)
DOI10.1007/978-1-4615-1905-8
©1995SpringerScience+BusinessMediaNewYork
OriginallypublishcdbyPlcnumPrcss,NewYorkin1995
SoftcoverreprintofthehardcoverIstedition1995
10987654321
AIIrightsreserved
Nopartofthisbookmaybereproduced,storedinaretrievalsystern,Of transmittedinanyformorbyany
means,electronic,mechanical,photocopying,microfilming,recording,orotherwise,withoutwritten
pcrmissionfromthePublisher
PREFACE
This volume Macromolecular Engineering: Recent Advances has been developed
based on the 1s t International Conference on "Advanced Polymers Via Macromolecular
Engineering" (APME '95), June 24-29, 1995 at the Vassar College campus, Poughkeepsie,
New York. In APME '95, 100 oral and over 50 poster presentations are to be delivered from
scientists around the globe. The scientific program covers recent advances in macromolecu
lar engineering. It is our vision that the knowledge of the past and the promise of the future
are blended together in APME '95 to enrich and stimulate the scientists, which will bring
about the progress of macromolecular engineering. Scientists from over 30 countries will
be joining together to share this vision.
Although over 150 papers are to be presented in APME '95 conference, we could not
include all the papers in this book for a variety of reasons, most importantly the authors
willingness to contribute to this volume in time to meet the deadline. However, the 24
comprehensive chapters included in this volume are a true reflection of some of the important
themes of macromolecular engineering that are part oft he APME '95 conference. We believe
macromolecular engineering is the key to developing new polymeric materials and, to this
end, it is hoped this volume will aid in this introspection.
An editorial task of this volume and the international conference of this magnitude
would not have been possible without the help of many of our co-workers, international
scientists, and support of several institutions. We would like to particularly thank to Akzo
Nobel Research (Netherlands), DuPont Company, Marcel Dekker, Inc., 3M Company,
Procter & Gamble Co., Texaco Inc., and Viscotek Corp. for their generous financial support.
Also, we would like to express our thanks to the Polymer Frontiers International, organizer
and sponsor of the APME '95 conference.
M. K. Mishra, USA
O. Nuyken, GERMANY
S. Kobayashi, JAPAN
Y. Yagci, TURKEY
B. Sar, USA
v
CONTENTS
1. Group Transfer Polymerization and Its Relationship to Other Living Systems
Owen W. Webster
2. Fundamentals and Practical Aspects of "Living" Radical Polymerization ....... 11
Krzysztof Matyjaszewski
LIVING CARBOCATIONIC COPOLYMERIZATIONS. Part 1
3. The Constant Copolymer Composition Technique (III) . . . . . . . . . . . . . . . . . . . . .. 25
A. Nagy, I. Orszagh, and J.P. Kennedy
LIVING CARBOCATIONIC COPOLYMERIZATIONS. Part 2
3. Application of the Constant Copolymer Composition Technique for the
Synthesis ofIsobutylene/p-Methylstyrene Copolymers ... . . . . . . . . . . . .. 35
1. Orszagh, A. Nagy, and J.P. Kennedy
4. Hexaanned Polystyrene Stars from a Newly Designed Initiator of Carbo cationic
Polymerization ................................................ 47
Eric Cloutet, Jean-Luc Fillaut, Didier Astruc, and Yves Gnanou
5. Photoinitiation ofIonic Polymerizations ................................. 67
Wolfram Schnabel
6. Synthesis and Photopolymerization of I-Propenyl Ether Monomers ........... 85
J.Y. Crivello, K.D. Jo, w.-G. Kim, and S. Bratslavsky
7. Design of Macromolecular Prodrug Forms of Antitumor Agents .............. 101
Tatsuro Ouchi
8. Transparent Multiphasic Oxygen Permeable Hydrogels Based on Siloxanic
Statistical Copolymers .......................................... 117
C. Robert, C. Bunel, M.A. Dourges, J.P. Vairon, and F. Boue
vii
viii Contents
9. Preparation of Tubular Polymers from Cyclodextrins ....................... 127
Akira Harada, Jun Li, and Mikiharu Kamachi
10. Multi-Component Polymers Containing Polyisobutylene via Multi-Mode
Polymerization ................................................ 143
Munmaya K. Mishra
11. Macrophotoinitiators: Synthesis and Their Use in Block Copolymerization ..... 151
YusufYagci
12. Amphiphilic Polymer Networks by Copolymerization of bis-Macromonomers .. 163
Peiwen Tan, Saskia R. Walraedt, Jan M.M. Geeraert, and Eric 1. Goethals
13. Stereospecific Polymerization and Copolymerization of Stereoregular PMMA
Macromonomers ............................................... 17 1
Koichi Hatada, Tatsuki Kitayama, Osamu Nakagawa, and Takafumi Nishiura
14. Acrylic Graft Copolymers via Macromonomers: Synthesis and Characterisation. 189
Wolfgang Radke, Sebastian Roos, Helga M. Stein, and Axel H. E. Muller
15. Anionic Synthesis of Macromonomers and Graft Copolymers with
Well-Defined Structures ......................................... 197
Roderic P. Quirk, Qizhuo Zhuo, Yuhsin Tsai, Taejun Yoo, and Yuechuan
Wang
16. New Superstructures from Block and Graft Copolymers with Precisely
Controlled Chain Architecture .................................... 207
C. D. Eisenbach, A. Goldel, H. Hayen, T. Heinemann, U. S. Schubert, and
M. Terskan-Reinold
17. Molecular Organization of Polystyrene and Polymethylmethacrylate with
Fluorocarbon Side Chains ....................................... 219
Sergei Sheiko, Alexei Turetskii, Jens Hopken, and Martin Moller
18. Synthesis of 1-10 Micron Polymer Particles by the New Grafting-Precipitation
Method (GPM) ................................................ 229
W. De Winter, D. Timmerman, and R. Declercq
19. Design and Control of the Structure of Polymers and Molecular Aggregates in
the Solid Lattice: Synthetic and Self-Assembly Approach .............. 243
S. Valiyaveettil, U. Scherf, V. Enkelmann, M. Klapper, and K. Mullen
20. Polyaddition ofH P0 and Its Derivatives to Diepoxides via Activated
3 4
Monomer Mechanism: Polymer Structures and Functionalization ........ 255
S. Penczek, P. Kubisa, and A. Nyk
Contents ix
21. Functional Polymers with Various Macrocyclic Chain Architectures and
Well-Defined Dimensions ... : ................................... 271
Alain Deffieux, Michel Schappacher, and Laurence Rique-Lurbet
22. Functiona1ized Polymers: Synthesis and Modification ...................... 291
Helmut Ritter
23. Polymers with Triazene Units in the Main Chain: Application for
Laser-Lithography ............................................. 303
Oskar Nuyken, JUrgen Stebani, Alexander Wokaun, and Thomas Lippert
24. Synthesis and Properties ofPoly(Aryl Ether Ketone) Possessing Crosslinking
Groups: Application for Electronic Device .......................... 319
Yoshihiro Taguchi, Hiroshi Uyama, and Shiro Kobayashi, and
Katsuhisa Osada
Index ................................................................. 329
1
GROUP TRANSFER POLYMERIZATION AND
ITS RELATIONSHIP TO OTHER LIVING
SYSTEMS
Owen W. Webster
DuPont Central Research and Development
Wilmington, Delaware 19880-0328
INTRODUCTION
The large number of organic function groups that can be attached to the ester function
of methacrylate and acrylate monomers makes this series of monomers attractive for
synthesis of polymers with diverse properties. When this diversity offunctionality is coupled
with living polymerization techniques the range of new product possibilities is staggering.
Polymer synthesis chemists have therefore been searching for living polymer systems for
methacrylates and acrylates that operate at above ambient temperature, use reasonably low
cost initiators, tolerate moderate amounts of impurities, control chain tacticity and allow the
functionality that is to be introduced to survive the polymerization process.
Davis, Haddleton, and Richards have recently reviewed the controlled polymeriza
tion of acrylates and methacrylates, (Ref. I). Muller has compared Group Transfer Polym
erization (GTP) to anionic polymerization (Ref. 2). In this review the major living
methacrylate polymerization techniques will be compared to GTP with an eye to possible
industrial utilization.
The term "living" will be used whenever all polymer chains in a system grow at the
same time, low polydispersity results and the molecular weight is controlled by the mono
mer/initiator ratio. To classify initiators, enolate species on the propagating chain ends will
be identified, although in practice these enolate ends may have been formed by addition of
other reagents to the MMA, (metal hydride, alkyl lithium etc.).
SILICON ENOLATES AS INITIATORS FOR METHACRYLATE
POLYMERIZATION - GROUP TRANSFER POLYMERIZATION
In 1983 DuPont announced a new procedure for polymerization of acrylic mono
mers (Ref. 3). In this procedure trimethylsilyl capped chain ends inserted monomer at
temperatures as high as 100°C. High enough so that river water can be used to cool a
batch reactor under reflux. The polymerization was living and thus providing routes to
Macromolecular Engineering. Edited by M.K. Mishra et al.
Plenum Press, New York, 1995 1
2 O. W. Webster
low polydispersity-block, star and telechelic polymers of predetermined molecular weight.
The name given to the procedure was Group Transfer Polymerization (GTP), a name that
unfortunately, to some among us, implies direct transfer of the silyl group to incoming
monomer (Eq. 1).
)-i0 C02Me
~_O)-S i~Me3 + N--u..c.a.;t. .. .. ~O - S'IM e3
-
OMe OMe OMe
/MMA
PMMA (1)
In the more widely accepted mechanism the silyl group (I 0·3M), which protects chain
ends from termination, does not directly transfer to incoming monomer but rapidly ex
changes with a small amount of enolate ended polymer, (10·5M) generated by the catalyst
(Eq. 2). On this basis dropping the term group transfer polymerization has been suggested
(Ref 4,5). However, in view of the large body of literature that uses the term GTP and the
fact that in the final product and all intermediate stages transfer of the silyl group has indeed
occurred, we recommend that the name group transfer polymerization should continue to be
used.
~OSiMe3 + Nu ~O
- + NuSiMe3
f\oMe
f\oMe
~ MMA
PMMA~OSiMe3 PMMAKO -+
/\ -:====-
NuSiMe3
OMe OMe (2)
Although bifluoride was first used as the nucleophilic catalysts for GTP it proved to
be too active for operation at above room temperatures. Tetrabutylamomnium biacetate or
bibenzoate are now the catalysts of choice. The extra mole of acid in the catalyst reacts
rapidly with the trimethylsilyl ketene acetal initiator to generate trimethylsilyl carboxylate,
a livingness enhancing agent Since the catalyst is used at levels less than I % based on
initiator the destruction of this small amount of ketene acetal has no noticeable effect on the
molecular weight of the polymer. Mn = [Monomer]/(Initiator) x m. w. of monomer.
GTP requires dry monomer with pendent functional groups free of acti ve hydrogen
(Ref 6). The initiator is expensive enough so that polymer prepared by GTP cannot
compete economically with free radical initiated product Molecular weights over 50,000
are difficult to obtain. GTP is used by DuPont to prepare block polymer dispersing agents
for pigments.
When one uses a block polymer from nucleophilic catalyzed GTP as a dispersing
agent, the trimethylsilyl groups on the chain ends hydrolyze to form hexamethyldisiloxane.
This innocuous material can be left in the polymer solution along with the small amount of
catalyst On the other hand, Lewis acid catalyzed GTP requires large amounts of Lewis acid,
ZnBr2' ZnCl2 or alkyl aluminum dichloride (up to 30% based on monomer, Ref 7). Since
these acids would have to be removed before the resins could be used, the cost would be
prohibitive.
Group Transfer Polymerization 3
TRANSITION METAL ENOLATES AS INITIATORS FOR
METHACRYLATE POLYMERIZATION
In significant work that introduces its use of transition metal enolates for living
methacrylate polymerization, Yasuda has shown that the polymerization of methyl methacry
late can be initiated by (CP*2SmH)2 addition to MMA to give enolate 1, (Ref. 8, Eq. 3). The
structure of! was confirmed by X-ray. -
Cp\ Me_o ~
SmHCp* 2 + 2 MMA
/SmO
Cpo "
·O~
~
PMMA OMe
1 (3)
No catalyst is needed for this group transfer like process. Polymers in the 100,000
molecular weight range with polydispersities as low as 1.05 have been obtained. In addition
block polymers with ethylene can be made (Ref. 9).
Novak (Ref. 10) has suggested that the polymerization ofMMA by (Sm. Cp*2)2 first
produces a bisenolate by election transfer and dimerization.
Meo,,==!, ,,=pSmCp*2
[SmCp*2h + 2 MMA _ (_~
Cp*2SmO OMe (4)
For comparison he prepared the bisalkyl initiator (Cp*2Sm(fl-h3-CH2CHCH)h-It initi
ated MMA in a living fashion giving quantitative yields ofPMMA with polydispersities of -1.1
oce.
after 2 hat A plot ofMn vs. monomer/initiator ratio shows the expected linear relationship.
Although the lanthanide initiators are unparalleled in their ability to polymerize MMA to high
molecular weight, low polydispersity PMMA. The cost of preparing lanthanide Cp* derivatives
and difficulty in handling these air sensitive materials, may hold back industrial development.
In work with more industrial potential Collins (Ref. 11) has shown that ester enolates
of Zirconium metallocenes initiate living polymerization of MMA in the presence of the
corresponding cationic methyl complex (eq. 5).
I-BUO\-! ~OMe
~ --.. PMMA
~ ~-Z~CP2
CP2 Zr-O /
Me Me MMA
~t-BU0H-r<
+ OMe
CP2 Zr .... O -
Me 0-ZrCP2
(5)
Me
Molecular weights in the 100,000 range were obtained with polydispersities -1.15.
When a chiral initiator system was used isotactic PMMA was formed. Since the metallocene
derivatives were made from cyc10pentadiene they would be more readily available than the
Sm metallocene derivatives made with pentamethy1cyc1opentadiene. Collins' polymeriza
occ.
tions were conducted at Can variations be found that will operate at 80CC?
Description:This volume Macromolecular Engineering: Recent Advances has been developed based on the 1 st International Conference on "Advanced Polymers Via Macromolecular Engineering" (APME '95), June 24-29, 1995 at the Vassar College campus, Poughkeepsie, New York. In APME '95, 100 oral and over 50 poster pres
