Table Of ContentRAFT memorabilia
❉ living ❉ radical polymerization
in homogeneous and heterogeneous media
Hans de Brouwer
CIP-DATA LIBRARY TECHNISCHE UNIVERSITEIT EINDHOVEN
Brouwer, Hans de
RAFT memorabilia : living radical polymerization in homogeneous and
heterogeneous media / by Hans de Brouwer. - Eindhoven : Technische
Universiteit Eindhoven, 2001. -
Proefschrift. - ISBN 90-386-2802-1
NUGI 813
Trefwoorden: polymerisatie ; radikaalreacties / emulsiepolymerisatie /
reactiekinetiek / ketenoverdracht ; RAFT
Subject headings: polymerization ; radical reactions / emulsion polymerisation /
reaction kinetics / chain transfer ; RAFT
© 2001, Hans de Brouwer
Druk: Universiteitsdrukkerij, Technische Universiteit Eindhoven
Omslagontwerp: Hans de Brouwer
RAFT memorabilia
living radical polymerization
in homogeneous and heterogeneous media
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 woensdag 30 mei 2001 om 16.00 uur
door
Johannes A. M. de Brouwer
geboren te Goirle
Dit proefschrift is goedgekeurd door de promotoren:
prof.dr.ir. A. L. German
en
prof.dr. J. F. Schork
Copromotor:
dr. M. J. Monteiro
Het werk in dit proefschrift is financieel ondersteund
door de Stichting Emulsiepolymerisatie (SEP) / The
work in this thesis was financially supported by the
Foundation Emulsion polymerization (SEP)
look around, wonder why
we can live a life that's never satisfied
lonely hearts, troubled minds
looking for a way that we can never find
many roads are ahead of us
with choices to be made
but life's just one of the games we play
there is no special way
from Winter in July on the album Unknown Territory by Bomb the Bass
© 1991, Rhythm King Records
table of contents
Table of Contents
Chapter 1. INTRODUCTION ........................................................................... 11
1.1 The Ways of Science 11
1.2 Polymers 13
1.3 Free–Radical Polymerization 14
1.4 Objective and Outline of this Thesis 15
1.5 References 17
Chapter 2. RAFT PERSPECTIVES................................................................. 19
2.1 Living Radical Polymerization 19
2.1.1 Reversible Termination 22
2.1.2 Reversible Transfer 25
2.2 The Transfer Rate in RAFT Polymerization 35
2.2.1 The Influence of the Transfer Constant 35
2.2.2 Determination of the Transfer Constant 37
2.3 Retardation in RAFT Polymerization 43
2.3.1 Model Development 45
2.3.2 Investigations of Proposed Explanations 49
2.4 Conclusion 58
2.5 Experimental 59
2.6 References 60
Chapter 3. EXPERIMENTAL PROCEDURES.................................................... 63
3.1 Introduction 63
3.2 Synthetic Approaches to Dithioesters 64
3.2.1 Substitution Reactions with Dithiocarboxylate Salts. 64
3.2.2 Addition of Dithio Acids to Olefins 67
3.2.3 Thioalkylation of Thiols and Thiolates. 68
3.2.4 via Imidothioate Intermediates 71
3.2.5 with Sulfur Organo-Phosphorus Reagents 71
3.2.6 Friedel-Crafts Chemistry 72
3.2.7 via Bis(thioacyl)disulfides 74
3.3 Conclusion 76
3.4 Experimental Section 76
3.4.1 Synthesis of Benzyl Dithiobenzoate 76
3.4.2 Synthesis of 2-(ethoxycarbonyl)prop-2-yl Dithiobenzoate 77
3.4.3 Synthesis of 2-phenylprop-2-yl Dithiobenzoate 79
3.4.4 Synthesis of 2-cyanoprop-2-yl Dithiobenzoate 80
3.4.5 Synthesis of 4-cyano-4-((thiobenzoyl)sulfanyl)pentanoic Acid 82
3.4.6 Synthesis of a Polyolefin Macromolecular Transfer Agent 83
3.4.7 Synthesis of a Poly(ethylene oxide)-based RAFT Agent 84
3.5 References 84
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table of contents
Chapter 4. LIVING RADICAL COPOLYMERIZATION OF STYRENE AND MALEIC
ANHYDRIDE AND THE SYNTHESIS OF NOVEL POLYOLEFIN-BASED BLOCK
COPOLYMERS VIA RAFT POLYMERIZATION ................................................. 87
4.1 Polyolefin-based Architectures 87
4.2 Results and Discussion 91
4.2.1 The Macromolecular RAFT Agent 91
4.2.2 Styrene Polymerizations 92
4.2.3 UV Irradiation 95
4.2.4 Styrene – Maleic Anhydride Copolymerizations 97
4.3 Conclusions 100
4.4 Experimental 100
4.5 References 101
Chapter 5. LIVING RADICAL POLYMERIZATION IN EMULSION USING RAFT. 103
5.1 Emulsion Polymerization 103
5.1.1 Introduction 103
5.1.2 A Qualitative Description 104
5.1.3 Living Radical Polymerization in Emulsion 107
5.1.4 Research Target 112
5.2 Seeded Emulsion Polymerizations 113
5.2.1 Background Theory 113
5.2.2 Experimental Design 114
5.2.3 Results and Discussion 116
5.3 Ab Initio Emulsion polymerizations 122
5.3.1 Variations in Reaction Conditions 123
5.3.2 Variations in RAFT Concentration and Structure 123
5.4 Emulsion Polymerizations with Nonionic Surfactants. 127
5.5 Conclusion 129
5.6 Experimental 130
5.7 References 132
Chapter 6. LIVING RADICAL POLYMERIZATION IN MINIEMULSION USING
REVERSIBLE ADDITION–FRAGMENTATION CHAIN TRANSFER ................... 135
6.1 Miniemulsions 135
6.1.1 Introduction 135
6.1.2 Miniemulsion Preparation & Stability 136
6.1.3 Nucleation Processes 139
6.1.4 Living Radical Polymerization in Miniemulsions 141
6.2 Anionic Surfactants 143
6.2.1 Kinetics 145
6.2.2 Conductivity & pH Considerations 153
6.3 Cationic Surfactants 159
6.4 Nonionic Surfactants 160
6.5 Controlled Polymerization 162
6.5.1 Homopolymerizations & Kinetics 162
6.5.2 Block copolymers 166
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table of contents
6.6 Conclusions 171
6.7 Experimental 173
6.8 References 175
APPENDIX: POLYMERIZATION MODELS ...................................................... 177
A.1 Numerical Integration of Differential Equations 177
A.2 Models 180
A.2.1 Model withouth Chain Lengths 180
A.2.2 Exact Model 185
A.2.3 The Method of Moments 191
A.3 Monte Carlo Simulations 199
A.4 References 199
EPILOGUE .................................................................................................... 201
References 204
SUMMARY..................................................................................................... 205
SAMENVATTING............................................................................................ 209
ACKNOWLEDGEMENTS ................................................................................. 213
CURRICULUM VITAE .................................................................................... 215
PUBLICATIONS ............................................................................................. 216
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