Polymer Modification PDF
Preview Polymer Modification
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
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