The Practical Approach in Chemistry Series SERIES EDITORS L. M. Harwood C. J. Moody Department of Chemistry Department of Chemistry University of Reading University of Exeter The Practical Approach in Chemistry Series Organocopper reagents Edited by Richard J. K. Taylor Macrocycle synthesis Edited by David Parker High-pressure techniques in chemistry and physics Edited by Wilfried B. Holzapfel and Neil S. Isaacs Preparation of alkenes Edited by Jonathan M. J. Williams Transition metals in organic synthesis Edited By Susan E. Gibson (née Thomas) Matrix-isolation techniques Ian R. Dunkin Lewis acid reagents Edited by Hisashi Yamamoto Organozinc acid reagents Edited by Paul Knochel and Philip Jones Amino acid derivatives Edited by Graham C. Barrett Asymmetric oxidation reactions Edited by Tsutomu Katsuki Nitrogen, oxygen and sulfur ylide chemistry Edited by J. Stephen Clark Organophosphorus reagents Edited by Patrick J. Murphy Polymer chemistry Edited by Fred J. Davis Polymer Chemistry A Practical Approach Edited by FRED J. DAVIS The School of Chemistry, The University of Reading, UK 1 1 Great Clarendon Street, Oxford OX2 6DP Oxford University Press is a department of the University of Oxford. It furthers the University’s objective of excellence in research, scholarship, and education by publishing worldwide in Oxford New York Auckland Bangkok Buenos Aires Cape Town Chennai Dar es Salaam Delhi Hong Kong Istanbul Karachi Kolkata Kuala Lumpur Madrid Melbourne Mexico City Mumbai Nairobi São Paulo Shanghai Taipei Tokyo Toronto Oxford is a registered trade mark of Oxford University Press in the UK and in certain other countries Published in the United States by Oxford University Press Inc., New York © Oxford University Press 2004 The moral rights of the author have been asserted Database right Oxford University Press (maker) First published 2004 All rights reserved. No part of this publication may be reproduced, stored in a retrieval system, or transmitted, in any form or by any means, without the prior permission in writing of Oxford University Press, or as expressly permitted by law, or under terms agreed with the appropriate reprographics rights organization. Enquiries concerning reproduction outside the scope of the above should be sent to the Rights Department, Oxford University Press, at the address above You must not circulate this book in any other binding or cover and you must impose this same condition on any acquirer A catalogue record for this title is available from the British Library Library of Congress Cataloging in Publication Data (Data available) ISBN 0 19 850309 1 (Hbk) 10987654321 Typeset by Newgen Imaging Systems (P) Ltd., Chennai, India Printed in Great Britain on acid-free paper by Biddles Ltd, King’s Lynn To my wife Jacqueline, my children Charlie, William, Gracie, and Briony, and to my late mother Mrs Josephine P. Davis This page intentionally left blank Preface It is some time since Laurence Harwood suggested to me the idea of this volume of the Practical Approach in Organic Chemistry series, and whilst initially I could see the value of such a contribution, as the subsequent delay in production testifies, I have had some difficulty in transposing this topic to a relatively small text. There are many scientific publications devoted entirely to the area of polymer synthesis, with tens of thousand pages devoted to the topic in the scientific literature every year I have focused on those aspects of the topic which I find interesting, and consequently there are certainly many omissions. I hope, however, that the examples I have included will give a flavour of what can be achieved (generally without recourse to highly spe- cialized equipment) in terms of the development of novel macromolecular systems. As with all the volumes in the Practical Approach Series, this book aims to provide a detailed and accessible laboratory guide suitable for those new to the area of polymer synthesis. The protocols contained within this manuscript provide information about solvent purification, equipment and reaction conditions, and list some potential problems and hazards. The latter point is particularly important and in most instances I have referred to the manufacturers’ safety data sheet (MSDS, which companies such as Merck and Aldrich provide on-line); however, often these vary in detail from source- to-source and from time-to-time, and of course local rules always must take precedance. I am particularly indebted to the contributors to this work for their excel- lent efforts and prompt responses to my requests. I am also grateful to my postgraduate students, particularly Dario Castiglione and Vidhu Mahendra for checking some of the experimental details, and to my colleague at Reading Dr Wayne Hayes for his constant enthusiasm and advice. Fred J. Davis Reading December 2003 This page intentionally left blank Contents Contributors xiii Abbreviations xvii 1. Polymer characterization 1 Ian L. Hosier, Alun S. Vaughan, Geoffrey R. Mitchell, Jintana Siripitayananon, and Fred J. Davis 1. Introduction 1 2. Synthetic routes to polymers 2 3. Molecular weight determination 4 4. Composition and microstructure 7 5. Optical microscopy 9 6. Electron microscopy 11 7. Analytical microscopy 14 8. Scanning probe microscopy 16 9. Thermal analysis 18 10. Molecular relaxation spectroscopy 21 11. X-ray and neutron scattering methods 24 12. Conclusions 32 References 33 2. General procedures in chain-growth polymerization 43 Najib Aragrag, Dario C. Castiglione, Paul R. Davies, Fred J. Davis, and Sangdil I. Patel 1. Introduction 43 2. Free-radical chain polymerization 44 3. Anionic polymerization 67 4. Ring-opening polymerizations initiated by anionic reagents 83 5. Coordination polymers 90 6. Conclusions 95 References 95 Contents 3. Controlled/‘living’ polymerization methods 99 Wayne Hayes and Steve Rannard 1. Introduction 99 2. Covalent ‘living’ polymerization: group transfer polymerization 101 3. Controlled free-radical polymerizations mediated by nitroxides 109 4. Controlled free-radical polymerizations: atom transfer free-radical polymerizations (ATRP) and aqueous ATRP 116 References 123 4. Step-growth polymerization—basics and development of new materials 126 Zhiqun He, Eric A. Whale, and Fred J. Davis 1. Introduction 126 2. The synthesis of an aromatic polyamide 127 3. Preparation of a main-chain liquid crystalline poly(ester ether) with a flexible side-chain 130 4. Non-periodic crystallization from a side-chain bearing copolyester 135 5. A comparison of melt polymerization of an aromatic di-acid containing an ethyleneglycol spacer with polymerization in a solvent and dispersion in an inorganic medium 138 References 143 5. The formation of cyclic oligomers during step-growth polymerization 145 Abderrazak Ben Haida, Philip Hodge, and Howard M. Colquhoun 1. Introduction 145 2. Synthesis and extraction of cyclic oligomers of poly(ether ketone) 146 3. Synthesis of some sulfone-linked paracyclophanes from macrocyclic thioethers 152 4. Summary 156 References 156 x Contents 6. The synthesis of conducting polymers based on heterocyclic compounds 158 David J. Walton, Fred J. Davis, and Philip J. Langley 1. Introduction 158 2. Electrochemical synthesis 159 3. Synthesis of polypyrrole 163 4. Synthesis of polyaniline 178 5. Synthesis of polythiophene 181 6. Conclusions 186 References 186 7. Some examples of dendrimer synthesis 188 Donald A. Tomalia 1. Introduction 188 2. Excess reagent method 190 3. Protection–deprotection method 193 References 199 8. New methodologies in the preparation of imprinted polymers 201 Cameron Alexander, Nicole Kirsch, and Michael Whitcombe 1. Introduction 201 2. Sacrificial spacer approach 203 3. Preparation of bacteria-imprinted polymers 210 References 214 9. Liquid crystalline polymers 215 Sangdil I. Patel, Fred J. Davis, Philip M. S. Roberts, Craig D. Hasson, David Lacey, Alan W. Hall, Andreas Greve, and Heino Finkelmann 1. Introduction 215 2. Synthesis of an acrylate-based liquid crystal polymer 217 3. The hydrosilylation reaction: a useful procedure for the preparation of a variety of side-chain polymers 225 xi Contents 4. Photochemical preparation of liquid crystalline elastomers with a memory of the aligned cholesteric phase 229 5. Defining permanent memory of macroscopic global alignment in liquid crystal elastomers 234 6. Summary 244 References 244 Index 246 xii Contributors cameron alexander School of Pharmacy and Biomedical Sciences, University of Portsmouth, White Swan Road, Portsmouth, PO1 2DT, UK najib aragrag The Department of Chemistry, The University of Reading, Whiteknights, Reading, Berkshire, RG6 6AD, UK abderrazak ben haida Department of Chemistry, University of Manchester, Oxford Road, Manchester, M13 9PL, UK dario c. castiliglione The Department of Chemistry, The University of Reading, Whiteknights, Reading, Berkshire RG6 6AD, UK howard colquhoun The Department of Chemistry, The University of Reading, Whiteknights, Reading, Berkshire RG6 6AD, UK paul r. davies School of Chemistry, The University of Reading, Whiteknights, Reading, Berkshire RG6 6AD, UK fred j. davis School of Chemistry, The University of Reading, Whiteknights, Reading, Berkshire RG6 6AD, UK heino finkelmann Institut für Makromol eculare Chemie, Universität Freiburg, Stefan-Meier-Strasse 31, Freiburg D-79104, Germany andreas greve Institut für Makromol eculare Chemie, Universitat Freiburg, Stefan-Meier-Strasse 31, Freiburg D-79104, Germany alan w. hall The Department of Chemistry, The University of Hull, Kingston-upon-Hull, Cottingham Road, Hull