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TEMPLATE POLYMERIZATION Stefan Polowi' nski Technical University of L'od'z
ChemTec Publishing
Copyright © 1997 by ChemTec Publishing ISBN 1-895198-15-1 All rights reserved. No part of this publication may be reproduced, stored or transmitted in any form or by any means without written permission of copyright owner. No responsibility is assumed by the Author and the Publisher for any injury or/and damage to persons or properties as a matter of products liability, negligence, use, or operation of any methods, product ideas, or instructions published or suggested in this book.
Printed in Canada ChemTec Publishing 38 Earswick Drive Toronto-Scarborough Ontario M1E 1C6 Canada Canadian Cataloguing in Publication Data Polowinski, Stefan Template polymerization Includes bibliographical references and index. ISBN 1-895198-15-1 1. Polymerization. 2. Biochemical templates I. Title QD381.P64
1997
547’.28
C96-900763-9
Table of Contents 1 Introduction References
1 3
2 General Mechanism of Template Polymerization 2.1 Template Polycondensation 2.2 Chain Template Polymerization 2.3 Template Copolymerization References
5 5 9 11 16
3 Templates and Orientation of Substrates on Template References
19 25
4 Examples of Template Polymerization 4.1 Polyacids as Templates 4.2 Polyimines and Polyamines as Templates 4.3 Polybase Ionenes as Templates 4.4 Poly(ethylene oxide) and Poly(vinyl pyrrolidone) as Templates 4.5 Poly(methyl methacrylate) as Template 4.6 Poly(vinylopyridines) as Templates 4.7 Other Templates 4.8 Multimonomers as Templates 4.9 Ring-opening Polymerization References
27 27 34 35
5 Examples of Template Copolymerization 5.1 Template Copolycondensation 5.2 Ring Opening Template Copolymerization 5.3 Radical Template Copolymerization 5.3.1 Copolymerization with Participation of Multimonomers 5.3.2 Copolymerization of Two Different Multimonomers 5.3.3 Copolymerization without Multimonomers References
59 59 59 60 60 68 69 75
6 Examples of Template Polycondensation References
77 82
36 44 45 47 49 52 56
7 Secondary Reactions in Template Polymerization References
83 88
8 Kinetics of Template Polymerization 8.1 Template Polycondensation Kinetics 8.2 Template Ring-opening Polymerization Kinetics 8.3 Template Radical Polymerization Kinetics 8.4 Kinetics of Multimonomer Polymerization References
89 89 89 90 111 112
9 Products of Template Polymerization 9.1 Polymers with Ladder-type Structure 9.2 Polymer Complexes References
115 115 121 126
10 Potential Applications References
129 131
11 Experimental Techniques Used in the Study of Template Polymerization 11.1 Methods of Examination of Polymerization Process 11.2 Methods of Examination of Template Polymerization Products 11.2.1 Polymeric Complexes 11.2.2 Ladder Polymers References INDEX
133 133 140 140 143 146 149
Introduction
1
1 INTRODUCTION
Template or matrix polymerization can be defined as a method of polymer synthesis in which specific interactions between preformed macromolecule (template) and a growing chain are utilized. These interactions affect structure of the polymerization product (daughter polymer) and the kinetics of the process.1 The term “template polymerization” usually refers to one phase systems in which monomer, template, and the reaction product are soluble in the same solvent. The growth of living organisms is associated with very complicated processes of polymerization. Low molecular weight substrates, such as sugars, amino acids, fats, and water in animals and carbon dioxide in plants are precursors of polymers (polypeptides, polynucleic acids, polysaccharides, etc.). They are organized in tissues and can be rep