Handbook of Condensation Thermoplastic Elastomers

636 Pages·2005·6.821 MB·English

by  Stoyko Fakirov

Handbook of Condensation
Thermoplastic Elastomer
Edited by S. Fakirov
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Handbook of Condensation
Thermoplastic Elastomers
Edited by
Stoyko Fakirov
WILEY-VCH Verlag GmbH & Co. KGaA
Editor All books published by Wiley-VCH are carefully
produced. Nevertheless, authors, editor, and
Prof. Stoyko Fakirov publisher do not warrant the information
University of Sofia contained in these books, including this book, to
Faculty of Chemistry be free of errors. Readers are advised to keep in
1164 Sofia mind that statements, data, illustrations, proce-
Bulgaria dural details or other items may inadvertently be
inaccurate.
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© 2005 WILEY-VCH Verlag GmbH & Co.
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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 withyear-
long 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 wellknown
polymer institute in Ukraine will get the deserved credit that, for understand-
able 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 poly-
olefin, (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 poly-
condensates, 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 ofmy
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 INTRODUCTION
Chapter 1 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 Thermo-
plastic 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 POLYESTER-BASED THERMOPLASTIC
ELASTOMERS
Chapter 3 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)– polymers........................... 119
n
4. Solubility of the blocks ........................................................................ 122
5. Structure-property relationships.......................................................... 122
5.1. Thermal properties of –(4GT-b-PO4-b-PA12)– ........................... 125
n
5.2. Phase composition of terpoly(ester-b-ether-b-amide)s................. 133
5.3. Mechanical properties of –(4GT-b-PO4-b-PA12)–....................... 134
n
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