Polymer Modification

207 Pages·1997·7.94 MB·English

by  Michael P. Hallden-Abberton (auth.)

Polymer Modification
PolYlller Modification
Edited by
Graham Swift
Rhome and Haas Research
Spring House. Pennsylvania
Charles E. Carraher, Jf.
Florida Atlantic University
Boca Raton. Florida. and
Florida Center for Environmental Studies
Palm Beach Gardens. Florida
and
Christopher N. Bowman
University of Colorado at Boulder
Boulder. Colorado
SPRINGER SCIENCE+BUSINESS MEDIA, LLC
Library of Congress Cataloging-in-Publication Data
Polymer modification / edited by Graham Swift, Charles E. Carraher,
Jr., and Christopher N. Bowman.
p. cm.
Papers presented at a symposium held at the American Chemical
Society Meeting in Orlando, Fla., Aug. 1996.
Includes bibliographical references and index.
ISBN 978-1-4899-1479-8
1. Polymers—Congresses. I. Swift, Graham, 1939-
II. Carraher, Charies E. III. Bowman, Christopher N., 1967-
IV. American Chemical Society. Meeting (212th : 1996 : Orlando,
Fla.)
TP1081.P64 1998
668.9—dc21 97-35159
CIP
ISBN 978-1-4899-1479-8 ISBN 978-1-4899-1477-4 (eBook)
DOI 10.1007/978-1-4899-1477-4
© Springer Science+Business Media New York 1997
Originally published by Plenum Press, New York in 1997
Softcover reprint of the hardcover 1st edition 1997
http://www.plenum.com
10 987654321
All rights reserved
No part of this book may be reproduced, stored in a retrieval system, or transmitted in any form or by any
means, electronic, mechanical, photocopying, microfilming, recording, or otherwise, without written
permission from the Publisher
PREFACE
Polymer modifications represent a valuable synthetic approach to unique polymer
compositions, structure, and properties not readily available by the direct polymerization of
monomers. Modified polymeric products already exist in the commercial world (modified
celluloses, for example) so the approach is not new. However, it is an interesting and
chaU~nging opportunity to develop new materials for a variety of specialty applications using
the "chemistry on polymers" approach.
This book contains papers presented at the symposium on Polymer Modification held
at the National American Chemical Society Meeting in Orlando, Florida, August, 1996. The
chemistry presented is broad ranging, and includes grafting and chemical oxidation reactions,
and many other chemical modifications.
Hopefully, the book will be both a resource and an inspiration for the reader to
develop new opportunities for his or her particular applications.
CONTENTS
SURF ACE MODIFICATIONS
The Preparation of Methyl Methacrylate/Methacrylic Anhydride Copolymers from
PMMA and Dialkyl Amines via Reaction Extrusion .................................................. 3
Michael P. Hallden-Abberton
Grafting of Hindered Amine Groups on EPDM and Polyoctenamer via Photo-
Hydroperoxidation ..................................................................................................... 11
J. Lacoste, S. Chmela, J. Pellet, and J. F. Pilichowski
Reactive Gases as Reagents for Polymer Films Chemical Modifications ............................. 21
J. F. Pilichowski, S. Commereuc, 1. Lukac, G. Teissedre, and J. Lacoste
The Synthesis of Hydrophobe-Modified Hydroxyethyl Cellulose Polymers Using Phase
Transfer Catalysis ...................................................................................................... 31
Emmett M. Partain
The Synthesis and Characterization of Polyesters Derived from L-Lactide and
Variably-Sized Poly(Caprolactone) ......................................................................... ..45
Michael R. Lostocco and Samuel J. Huang
REACTIONS WITH VINYL POLYMERS
The Functionalization of Poly ole fins by Using Reactive Intermediates ............................... 61
T. C. Chung
Chemical Modification of Acrylamide Polymers in Aqueous Solution ................................ 77
D. W. Fong and D. J. Kowalski
Synthesis and Characterization ofPoly(Magnesium Acrylate) and Poly(Zirconyl Acrylate)
towards the Formation of Magnesium Partially Stabilized Zirconia Ceramics ......... 85
Xinhua Xu and Charles E. Carraher, Jr.
Preparation of Functionalized Polymers by Reactions ofPoly(Vinylbenzyl Chloride) ........ 97
Kristin L. Thunhorst, Richard D. Noble, and Christopher N. Bowman
Graft Copolymerization of Vinyl Monomers onto Polymers Containing Styrene .............. 109
David Jiang and Charles A. Wilkie
VJI
Chemical Cross-Linking by Glutaraldehyde between Amino Groups: Its Mechanism
and Effects ............................................................................................................... 1 19
Jun-ichi Kawahara, Keiichiro Ishikawa, Tadafumi Uchimaru, and Haruo Takaya
Poly(Chlorotrifluoroethylene) Substituted Reactions .......................................................... 133
Richard T. Taylor, J. A. Shah, John W. Green, and T. Kamolratanayothin
INORGANIC-CONTAINING AND SHAPED POLYMERS
Synthesis and Structural Characterization ofInorganic Tin Ionomers ............................... .155
Charles E. Carraher, Jr., Fengchen He, and Dorothy Sterling
Computer Modeling ofPoly(Acrylic Acid) and Its Salts .................................................... .165
Xinhua Xu, Charles E. Carraher, Jr., and Mark D. Jackson
Synthesis and Structural Characterization of Titanocene-Containing Polyethers
Based on Reaction with Ethylene Oxide-Containing Diols, Including
Poly(Ethylene Glycol) .............................................................................................. 171
Charles E. Carraher, Jr. and Lisa Reckleben
Synthesis of Novel Silanol Polymers and Copolymers by a Selective Oxidation ofSi-H
Bond from Corresponding Precursor Polymers ....................................................... 179
Eli M. Pearce, T. K. Kwei, and Shaoxiang Lu
Synthesis and Ion-Coupling Reactions of Telechelic Poly(Dimethylsiloxane) Having
Cyclic Onium Salt Groups ....................................................................................... 187
Yasuyuki Tezuka, Tomio Iwase, and Tomoo Shiomi
An Empirical and Modeling Study of Boron Speciation in Solution with a Reactive
Dendrimeric Polymer ............................................................................................... 197
Bryan M. Smith, Paul Todd, and Christopher N. Bowman
Author Index ....................................................................................................................... .207
Subject Index ....................................................................................................................... 209
viii
Polymer Modification
SURFACE MODIFICATIONS
THE PREPARATION OF METHYL METHACRYLATEI
METHACRYLIC ANHYDRIDE COPOLYMERS FROM PMMA
AND DIALKYL AMINES VIA REACTIVE EXTRUSION
Michael P. Hallden-Abberton
Rohm and Haas Co.,
Corporate Exploratory Research,
P.O. Box 219,
Bristol, Pennsylvania 19007-0219
INTRODUCTION
Although the imidization reaction of PMMA has been studied for many yearsl-4 re
cently, the study of this reaction by reactive extrusion processes has led to some interesting
and unexpected results.5-7,1l Specifically, the first step of this reaction is now believed to be
due to an unusual alkyl oxygen cleavage reaction resulting in the formation of methacrylic
acid and methacrylic anhydrides.7 In an attempt to corroborate this mechanism, we have
conducted some model reactions using dimethyl amine and PMMA in a twin screw, counter
rotating, non-intermeshing extruder. According to the proposed mechanism,7 the reaction
products should be derived from these alkyl-oxygen cleavage products. However, by use of a
dialkyl amine, the intermediate products should be prevented from cyclization to imide prod
ucts, and therefore should be trapped at an intermediate stage. This should allow some evi
dence of the reaction pathway to be observed. Also, analysis of the gaseous products should
be indicative of the reaction pathway.
REACTIVE EXTRUSION PROCEDURE WITH DIMETHYLAMINE
The test reaction was conducted according to the following procedure.1O A granular
PMMA sample (Mw = 200,000) was added at a rate of 30 g/min. to the feed zone of a 20
mm, counter-rotating, tangential, twin-screw extruder operating at 250 rpm. The polymer
was conveyed through a feed zone 10.2 diameters long, operated at a set temperature of
200°C, and over a melt blister 3 cm long, into a pressurized reaction zone 36.9 diameters
long, operated at a set temperature of 302°C, into which dimethyl amine (Matheson Chem.
Co.) was introduced by pumping at a rate of 5.2 cm3/min (3.3 g/min) at 2515 kPa at a point
5.7 diameters downstream from the end of the melt blister. The excess amine and gaseous
3