Handbook of Condensation Thermoplastic Elastomers Edited by Stoyko Fakirov WILEY-VCH Verlag GmbH & Co. KGaA
Handbook of Condensation Thermoplastic Elastomer Edited by S. Fakirov
Further Titles of Interest Th. Meyer, J. Keurentjes (Eds.) Handbook of Polymer Reaction Engineering 2005, ISBN 3-527-31014-2 H.-G. Elias Macromolecules Vols.1-4 2005, ISBN 3-527-31172-6, 3-527-31173-4, 3-527-31174-2, 3-527-31175-0 M. F. Kemmere, Th. Meyer (Eds.) Supercritical Carbon Dioxide in Polymer Reaction Engineering 2005, ISBN 3-527-31092-4 M. Xanthos (Ed.) Functional Fillers for Plastics 2005, ISBN 3-527-31054-1 R. C. Advincula, W. J. Brittain, K. C. Caster, J. Rühe (Eds.) Polymer Brushes 2004, ISBN 3-527-31033-9 S. Fakirov (Ed.) Handbook of Thermoplastic Polyesters 2002, ISBN 3-527-30113-5 E. S. Wilks (Ed.) Industrial Polymers Handbook Products, Processes, Applications 2000, ISBN 3-527-30260-3
Handbook of Condensation Thermoplastic Elastomers Edited by Stoyko Fakirov WILEY-VCH Verlag GmbH & Co. KGaA
Editor Prof. Stoyko Fakirov University of Sofia Faculty of Chemistry 1164 Sofia Bulgaria All books published by Wiley-VCH are carefully produced. Nevertheless, authors, editor, and publisher do not warrant the information contained in these books, including this book, to be free of errors. Readers are advised to keep in mind that statements, data, illustrations, procedural details or other items may inadvertently be inaccurate. Library of Congress Card No.: Applied for British Library Cataloging-in-Publication Data: A catalogue record for this book is available from the British Library Bibliographic information published by Die Deutsche Bibliothek Die Deutsche Bibliothek lists this publication in the Deutsche Nationalbibliografie; detailed bibliographic data is available in the Internet at <http://dnb.ddb.de>. 2005 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim All rights reserved (including those of translation into other languages). No part of this book may be reproduced in any form nor transmitted or translated into machine language without written permission from the publishers. Registered names, trademarks, etc. used in this book, even when not specifically marked as such, are not to be considered unprotected by law. Printed in the Federal Republic of Germany Printed on acid-free paper Cover Design Grafik Design Schulz, Fußgönheim Printing Strauss GmbH, Mörlenbach Bookbinding Litges & Dopf, Heppenheim ISBN-13 978-3-527-30976-4 ISBN-10 3-527-30976-4
Preface Thermoplastic elastomers (TPE) belong to a relatively new and small class of engineering plastics. Nevertheless, they enjoy a steady growth because of their unusual and very important combination of properties. During service, TPE behave as elastomers (e.g., as vulcanized natural rubber) but, in contrast to the classical elastomers, they can be processed by means of the conventional techniques and equipment utilized for all thermoplastics. This peculiarity of TPE is related to their different type of crosslinking. Unlike the classical elastomers, TPE are crosslinked by thermally labile aggregates, which melt during processing and regenerate after cooling down. This is because TPE are always block copolymers comprising the so-called hard blocks (forming solid crystallites or glassy regions), and soft blocks (imparting the elastomeric properties). TPE can be produced using all chemical approaches for polymer synthesis. By means of polycondensation and polyaddition processes the three main types of TPE can be prepared: polyester-based, polyamide-based, and polyurethanes. The polyester-based TPE were first introduced in the USA by DuPont, the polyamide-based in France, and polyurethanes are developed and applied worldwide. All they have found new and interesting applications. While the polymerization-based TPE and, partly, the poly(ether ester)s (PEE) are relatively well covered in the literature, this is not the case of polyamide-based TPE and polyurethanes when new and specific applications are considered. The main goal of this project is to combine the efforts of scientists with yearlong experience worldwide to fill this gap. A peculiarity of this international team of contributors is that for the first time the research results of a well known polymer institute in Ukraine will get the deserved credit that, for understandable reasons, was not possible some years ago. For instance, the application opportunities of polyurethanes were broadened significantly by preparing systems with various chemical compositions and molecular structures as (semi) interpenetrating networks. Another peculiarity is the fact that for the first time detailed information regarding the most important polyamide-based TPE will
be offered by the team who created them. Last but not least, thermoplastic elastomers, being multi-block copolymers comprising entities built up of very flexible ( soft ) chains and others of much less flexible ( hard ) chains, are capable of displaying such unique properties as shape memory effects. For this reason, they belong to the group of intelligent ( smart ) materials with interesting and completely new technical and biomedical applications. This book covers the chemical aspects, physical structure and properties, application opportunities, life cycle assessment, recycling possibilities, and the future trends of the three classes of thermoplastic elastomers. It should be mentioned that the Contributors, the Editor, as well as the Publisher are well aware that, strictly speaking, the title Condensation Thermoplastic Elastomers is chemically not sufficiently correct for the covered classes of polymers. Nevertheless, it was preferred, e.g., to the chemically correct title Thermoplastic Elastomers by Polycondensation and Polyaddition, at least for the following reasons: (i) the polyurethane group behaves chemically much more as a typical polyester or polyamide group, rather than as a polyolefin, (ii) similarly to other cases (e.g., the synthesis of nylon 6) regardless of the chemical route of the synthesis, via polymerization or via polycondensation, the final polymer is distinguished by a chemical structure typical of polycondensates, and (iii) the selected title sounds more comprehensive and more attractive. As the Editor, I have enjoyed working with the individual contributors and have greatly appreciated their support, prompt response, and patience. By analogy with my previously edited books, this one could hardly be realized in its present shape without the generous advice and suggestions of my friend, Prof. J. Karger-Kocsis, who was involved in the design of this project from the very beginning, and to whom I would like to express my most cordial gratitude. This book could not have been produced without the constant support of my colleague of many years, Ms. S. Petrovich, who has maintained contact with contributors, polished the English, and helped in the processing of the book. For this, I express my sincere gratitude. The Authors, The Editor, and the Publisher would like to thank all those publishers, who generously gave their permission to reprint materials from their own publications. Details are given at the end of the book. Last but not least, I am grateful to the Foundation of Science and Technology of New Zealand, who made possible the sabbatical visit of the Editor at the University of Auckland, Department of Mechanical Engineering, Centre for Advanced Composite Materials, where this project was finalized. S. Fakirov Auckland, December 2004
Contents PART I Chapter 1 INTRODUCTION Creation and Development of Thermoplastic Elastomers, and Their Position Among Organic Materials E. Maréchal 1. Birth and development of TPEs: a brief survey... 3 2. Main routes to thermoplastic elastomer preparation... 5 2.1. Living anionic polymerization... 6 2.2. Living cationic polymerization... 6 2.3. Controlled radical polymerization... 7 2.4. Polycondensation and polyaddition... 7 2.5. Chemical modification and grafting... 8 2.6. Preparation by blending... 9 2.7. Preparation by dynamic vulcanization... 9 3. Techniques used in the characterization of TPEs... 10 3.1. Chromatography... 10 3.2. Spectrometric techniques... 11 3.3. Scattering techniques... 12 3.4. Microscopies... 13 3.5. Controlled degradation... 13 3.6. Thermal techniques... 13 4. Properties and processing of TPEs... 14 4.1. Injection molding... 14 4.2. Compression molding... 14 4.3. Extrusion... 14 4.4. Blow processings... 15 4.5. Thermoforming... 15 4.6. Reactive processings... 15 4.7. Degradation in processing... 15
viii Content 5. Position of TPEs among organic materials and their applications... 15 6. Future trends... 18 References... 20 Chapter 2 Polycondensation Reactions in Thermoplastic Elastomer Chemistry: State of the Art, Trends, and Future Developments E. Maréchal 1. Introduction... 33 2. Preparation of block copolymers by polycondensation. A critical review... 34 2.1. General considerations... 34 2.2. Direct polycondensation of α,ω-difunctional oligomers... 34 2.3. Polycondensation of an α,ω-difunctional oligomer with the precursors of another block... 38 2.4. Oligomer-coupling reactions... 42 2.5. Characterization techniques. Side reactions... 46 3. New structures... 50 3.1. Block copolymers containing liquid crystalline structures... 50 3.2. Liquid crystalline sequences as part of the backbone... 50 3.3. Liquid crystalline sequences as side chains... 52 3.4. Metallo-supramolecular block copolymers... 55 3.5. Block copolymers prepared from metal-containing macrocycles... 58 3.6. The use of microorganisms... 62 4. Conclusions... 64 References... 66 PART II Chapter 3 POLYESTER-BASED THERMOPLASTIC ELASTOMERS Polyester Thermoplastic Elastomers: Synthesis, Properties, and Some Applications Z. Roslaniec 1. Introduction... 77 2. Chemical structure of polyester elastomers... 78 3. Poly(alkylene oxide) flexible segment-based polyester elastomers... 79
Content ix 4. Modified poly(butylene terephthalate) rigid segment-based polyester elastomers... 80 5. Branched polyester elastomers... 83 6. Synthesis of poly(ether ester) block copolymers... 84 7. Other multiblock polyester elastomers... 89 8. Polyester thermoplastic elastomers from blends... 99 9. A new processing aspect: weldability of polyester elastomers... 100 10. Polyester elastomers for biomedical application... 101 11. Conclusions and outlook... 105 References... 106 Chapter 4 Terpoly(Ester-b-Ether-b-Amide) Thermoplastic Elastomers: Synthesis, Structure, and Properties R. Ukielski 1. Introduction... 117 2. Chemical structure of terpoly(ester-b-ether-b-amide)s... 118 3. Synthesis of triblock (GT-b-PO4-b-PA) n polymers... 119 4. Solubility of the blocks... 122 5. Structure-property relationships... 122 5.1. Thermal properties of (4GT-b-PO4-b-PA12) n... 125 5.2. Phase composition of terpoly(ester-b-ether-b-amide)s... 133 5.3. Mechanical properties of (4GT-b-PO4-b-PA12) n... 134 6. Conclusions and outlook... 137 References... 139 Chapter 5 High Performance Thermoplastic Aramid Elastomers: Synthesis, Properties, and Applications H. Yamakawa, H. Miyata 1. Introduction... 141 2. Development of thermoplastic aramid elastomers... 142 3. Type I poly(aramid-b-polyether) elastomers... 143 3.1. Synthesis of reactive aramid compounds... 143 3.2. Synthesis of aramid elastomers... 143 3.3. Thermal properties... 147 3.4. Mechanical properties... 150
x Content 3.5. Dynamic-mechanical properties... 151 3.6. Chemical properties... 152 4. Type II poly(aramid-b-polyether) elastomers... 153 4.1. Synthesis of reactive aramid compounds... 153 4.2. Synthesis of aramid elastomers... 154 4.3. Thermal properties... 154 4.4. Mechanical properties... 154 4.5. Chemical properties... 155 4.6. Aramid elastomers with other polyether soft segments... 155 5. Poly(aramid-b-polyester) elastomers... 156 5.1. Synthesis and properties of aramid-b-polyester elastomers... 156 5.2. A novel synthetic route to aramid-b-polyester elastomers... 158 6. Applications... 160 7. Conclusions... 161 References... 162 Chapter 6 Poly(Ether Ester) Thermoplastic Elatomers: Phase and Deformation Behavior on the Nano- and Microlevel S. Fakirov 1. Introduction... 167 2. Phase behavior of PEEs... 170 2.1. Number of phases present and their miscibility... 170 2.2. Amorphous phase distribution in PEE copolymers... 173 2.3. Does crystal thickening exist in segmented and multiblock copolymers?... 175 3. Deformation behavior of PEE as revealed by small-angle X-ray scattering... 177 3.1. Effect of chain flexibility on the deformation of PET, PBT, PEE, and PBT/PEE blend... 177 3.2. Relationship between macro- and nano-deformation in PEE... 182 3.3. Chord distribution of a neat EM400 bristle... 187 4. Nanostructure evolution during the straining cycle... 189 5. Conclusions and outlook... 193 Acknowledgement... 194 References... 194
Content xi Chapter 7 Condensation Thermoplastic Elastomers Under Load: Methodological Studies of Nanostructure Evolution by X-ray Scattering N. Stribeck 1. Introduction... 197 1.1. Phase separation... 197 1.2. Living nanostructure... 197 1.3. X-ray techniques in process monitoring... 198 1.4. Progress in technology and methodology... 198 2. Materials... 199 3. Basic notions... 199 3.1. Nanostructure topology... 199 3.2. Non topological parameters... 200 3.3. Isotropic vs. anisotropic SAXS patterns... 200 3.4. Multidimensional chord distributions... 201 3.5. Longitudinal and transverse structure... 202 3.6. Void scattering... 203 4. Theoretical... 203 4.1. Basic definitions in SAXS... 203 4.2. Projections and sections... 205 4.3. Projections useful for TPEs studied under uniaxial load... 206 4.4. Correlation functions and their derivatives... 207 4.5. Data processing... 209 5. Nanostructure evolution and processes observed with condensation TPEs... 210 5.1. Poly(ether ester)s during straining... 210 5.2. Swollen and drawn poly(ether amide)s... 217 Acknowledgement... 222 References... 222 Chapter 8 Dielectric Relaxation of Polyester-Based Thermoplastic Elastomers T. A. Ezquerra 1. Introduction... 227 2. Study of the relaxation behavior by means of dielectric spectroscopy... 228 3. Dielectric spectroscopy of poly(ether ester) thermoplastic elastomers... 228 4. Dielectric spectroscopy of multiblock thermoplastic elastomers... 230 5. Relaxation behavior of poly(ester carbonate) block copolymer across the melting region... 232
xii Content 6. Conclusion... 237 Acknowledgement... 237 References... 237 PART III Chapter 9 POLYAMIDE-BASED THERMOPLASTIC ELASTOMERS Thermoplastic Poly(Ether-b-Amide) Elastomers: Synthesis F. L. G. Malet 1. Introduction... 243 2. Chemical structure of TPE... 244 3. Synthetic methods... 245 3.1. Polymerization in solution... 245 3.2. Interfacial polymerization... 247 3.3. Direct polycondensation using condensing agents... 247 3.4. Anionic polymerization... 248 3.5. Thermal polymerization... 248 4. Thermal polymerization of TPE-A with ester links... 249 4.1. Polymerization processes... 250 4.2. Nature of the raw materials... 251 4.3. Influence of the catalyst... 253 4.4. Influence of the molar ratio... 254 4.5. Influence of the temperature... 255 4.6. Influence of the stirring... 256 4.7. Influence of the vacuum level... 256 5. Conclusion... 257 References... 257 Chapter 10 Poly(Ether-b-Amide) Thermoplastic Elastomers: Structure, Properties, and Applications R.-P. Eustache 1. Structure and characterization... 263 1.1. Crystallinity and morphology... 264 1.2. Microphase separation vs. hard and soft segment block length... 269
Content xiii 2. Properties... 272 2.1. Mechanical properties... 273 2.2. Physico-chemical properties... 275 2.3. Processing... 276 3. Applications... 277 3.1. Sporting goods... 278 3.2. Medicine... 279 3.3. Industry... 279 3.4. Breathable structures... 279 3.5. Fragrance carrier... 279 3.6. Polymer additives and polymer components... 280 4. Conclusions and outlook... 280 References... 280 Chapter 11 Semicrystalline Segmented Poly(Ether-b- Amide) Copolymers: Overview of Solid-State Structure-Property Relationships and Uniaxial Deformation Behavior J. P. Sheth, G. L. Wilkes 1. Introduction... 283 2. PTMO-PA12 based copolymers... 286 2.1. Mechanical properties... 287 2.2. Thermal analysis... 291 2.3. Structure determination by scattering and microscopy studies... 293 2.4. Uniaxial deformation behavior... 299 3. Other poly(ether-b-amide) copolymers... 310 3.1. Poly(ethylene oxide)-based PEBA... 310 3.2. PEBA based on aromatic PA segments of uniform length... 311 4. Conclusion... 318 References... 319