Ionomeric Thermoplastic Elastomers based on Ethylene-Propylene Copolymers. Preparation, Structure and Properties

204 Pages·4.248 MB·English

by  Wouters M.E.L.

Ionomeric Thermoplastic Elastomers based
on Ethylene-Propylene Copolymers
Preparation, Structure and Properties
CIP-DATA LIBRARY TECHNISCHE UNIVERSITEIT EINDHOVEN

Wouters, Mariëlle

Ionomeric thermoplastic elastomers based on ethylene-propylene
copolymers : preparation, structures and properties / by Maria E.L.
Wouters. - Eindhoven : Technische Universiteit Eindhoven, 2000. -
Proefschrift. - ISBN 90-386-3051-4
NUGI 813
Trefwoorden: polymeren ; mechanische eigenschappen / elastomeren ;
vernetting / morfologie / polymeren ; Röntgenverstrooiing
Subject headings: polymers ; mechanical properties / elastomers ;
crosslinking / morphology / polymers ; X-ray scattering

Omslagontwerp: Ben Mobach (TUE), Mariëlle Wouters
Druk: Universiteitsdrukkerij TUE

 2000, M.E.L. Wouters
Ionomeric Thermoplastic Elastomers based
on Ethylene-Propylene Copolymers

Proefschrift

ter verkrijging van de graad van doctor aan de
Technische Universiteit Eindhoven, op gezag van de
Rector Magnificus, prof.dr. M. Rem, voor een
commissie aangewezen door het College voor
Promoties in het openbaar te verdedigen
op maandag 11 december 2000 om 16.00 uur

door

Maria Elisabeth Louise Wouters

geboren te ‘s-Hertogenbosch
Dit proefschrift is goedgekeurd door de promotoren:

prof.dr. F.L. Binsbergen
en
prof.dr. P.J. Lemstra

Het onderzoek beschreven in dit proefschrift werd
mogelijk gemaakt door financiële steun van DSM
voor Paul,
voor mijn ouders

Contents
Summary vii
Glossary xi
Chapter 1 Introduction
1.1 General considerations 1
1.2 Thermoplastic elastomers 2
1.2.1 General introduction 2
1.2.2 Thermoplastic elastomers vs. conventional crosslinked rubbers 3
1.2.3 Types of TPEs 4
1.3 Ionomers 6
1.3.1 Definition 6
1.3.2 Historical aspects 6
1.3.3 EPDM based ionomers 8
1.4 Proposal to use the ionomeric principle for thermoplastic elastomers 8
1.5 Objective and outline of this thesis 9
1.6 References 11
Chapter 2 Grafting of Maleic Anhydride
2.1 Introduction 13
2.2 Grafting of Maleic Anhydride onto polyolefins in solution 14
2.2.1 Materials 14
2.2.2 Grafting procedure 15
2.2.3 Analysis 15
2.3 Results and Discussion 16
Effect of …
2.3.1 type of peroxide 17
2.3.2 peroxide concentration 19
2.3.3 reaction time 20
2.3.4 polymer concentration 21
2.3.5 maleic anhydride concentration 22
2.3.6 molecular weight of the polyolefin 24
2.4 Conclusions 25
2.5 References 25
ii
Chapter 3 Ionomer preparation
Neutralisation of MAn-g-EPM
3.1 Introduction 27
3.2 Ionomer preparation 28
3.2.1 Materials 28
3.2.2 Neutralisation procedure 28
3.2.3 Definitions concerning concentrations 28
3.3 Characterisation 29
3.3.1 Methods 29
3.3.2 Results and discussion 30
3.4 Conclusions 34
3.5 References 34
Chapter 4 Morphological models for ionomers
4.1 Introduction 35
4.2 Overview of proposed structural models for ionomers 35
4.3 Morphological models to fit SAXS data 37
4.3.1 Introduction 37
4.3.2 Evaluation of some morphological models 42
4.3.3 The model and fitting procedure 48
4.4 Conclusions 50
4.5 References 51
Chapter 5 Morphology of MAn-g-EPM based ionomers
5.1 Introduction 53
5.2 Aggregate formation in carboxylic acid based ionomers 54
5.3 Small Angle X-ray Scattering 55
5.3.1 Introduction 55
5.3.2 Experimental 55
5.3.3 Results 56
5.3.4 Discussion 59
5.3.5 Summary 67
5.4 Solid State NMR 67
5.4.1 Introduction 67
5.4.2 Solid state 1H NMR techniques 69
5.4.3 Experimental 71
5.4.4 Results and discussion 72
5.4.5 Conclusions 80
Contents iii
5.5 Transmission Electron Microscopy 81
5.5.1 Introduction 81
5.5.2 Experimental 82
5.5.3 Results and discussion 82
5.5.4 Conclusions 84
5.6 Conclusions 84
5.7 References 86
Chapter 6 Gel content of MAn-g-EPM based ionomers
6.1 Introduction 89
6.2 Effect of ionomer composition on gel content 89
6.2.1 Experimental 90
6.2.2 Results 90
6.2.3 Discussion 93
6.3 Conclusions 96
6.4 References 96
Chapter 7 Material properties of MAn-g-EPM based ionomers
7.1 Introduction 97
7.2 Effect of ionomer composition on processing properties 98
7.2.1 Experimental 98
7.2.2 Results 98
7.2.3 Discussion 102
7.2.4 Conclusions 103
7.3 Effect of ionomer composition on tensile properties 104
7.3.1 Experimental 104
7.3.2 Results 104
7.3.3 Discussion 108
7.3.4 Summary 109
7.4 Effect of ionomer composition on compression set 109
7.4.1 Experimental 109
7.4.2 Results 110
7.4.3 Discussion 112
7.4.4 Conclusion 112
7.5 Effect of ionomer composition on water absorption 112
7.5.1 Introduction 112
7.5.2 Experimental 112
7.5.3 Results 113
7.5.4 Discussion 116
7.5.5 Conclusions 119
7.6 Summary and conclusions 120
7.7 References 122
iv
Chapter 8 Structure-property relations in MAn-g-EPM based ionomers
8.1 Present picture of morphology and structure 123
8.2 Stress relaxation in ionomers by ion hopping 124
8.3 Relation of gel content and ionomer morphology 125
8.4 Relation of melt viscosity and ionomer morphology 125
8.5 Relation of mechanical properties and ionomer morphology 127
8.5.1 Tensile testing 127
8.5.2 Hardness 130
8.6 Relation of compression set and ionomer morphology 131
8.7 Effect of ionomer composition on water absorption 132
8.7.1 Introduction 132
8.7.2 Experimental 132
8.7.3 Results and discussion of SAXS measurements 132
8.8 Summary 135
8.9 Conclusions 138
8.10 References 138
Chapter 9 Balance between mechanical and processing properties of
MAn-g-EPM based ionomers
9.1 Introduction 139
9.2 Comparing macroscopic properties of MAn-g-EPM based ionomers
with suitable other systems 140
9.2.1 Overview of comparable systems 140
9.2.2 Processing properties 141
9.2.3 Tensile properties 142
9.2.4 Shore A hardness 143
9.2.5 Compression set 144
9.3 Summary and conclusions 145
9.4 References 146
Technology Assessment 147