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RAFT Memorabilia : Living Radical Polymerization in Homogeneous and Heterogeneous Media / by Hans De Brouwer

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RAFT Memorabilia : Living Radical Polymerization in Homogeneous and Heterogeneous Media / by Hans De Brouwer RAFT 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 7 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 8 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 9 table of contents 10 © 2001, Hans de Brouwer — introduction » you're gonna take control of the chemistry and you're gonna manifest the mystery you got a magic wheel in your memory I'm wasted in time and I'm looking everywhere «1 1. Introduction 1.1. The Ways of Science The beaker on the cover of this thesis is more than the obvious indicator of the experimental and chemical content of this work. Hopefully, you – as the reader of this booklet – will find that the technical quality of the scientific content gathered between the two covers matches that of this image, but its meaning goes deeper than this superficial reference. More subtly, it attempts to expose the problem of observation. How can a piece of colorless transparent glass leave such a clear and detailed picture on one's retina, other than by the elucidating action of projection, shadow and reflection? Where direct perception is impossible, the underlying reality is reconstructed from these secondary observations. In this way this simple beaker, or rather the image of the beaker, or even more accurately: the image of the projections of this beaker, symbolize the scientists' dilemma: how to gain knowledge on reality? How to unravel the truth when it goes under-cover among mirages, illusions and delusions and only manifests itself indirectly? The problem was already described allegorically by Plato in his Politeia.2 The Greek philosopher composed a parable about a group of captives that were forced to look at the dead end of a cave. On this wall they observed shadows. Projections of objects and people moving behind there backs, their shadows cast on the blind wall by a fire lit in the caves' entrance. These people had never seen anything else than their own shadows and those of the objects that were carried around behind them. They were chained such that they could not look around. How were they to know that a reality existed other than that of the shadows they observed? In the eye of the beholder these captives possess only a very limited view on reality while they are unaware of this restraint. Plato acknowledged the difficulty of this problem but 11 Chapter 1 — © 2001, Hans de Brouwer did not consider it impossible to know reality. For Plato it was enough to realize this situation and to attempt to gain deeper knowledge; somehow finding enlightenment, rising above the world of observation, realizing the existence of reality. Nietzsche was one of the first to explicitly classify this pursuit as a vial attempt to do the impossible.3 Science is unable to truly comprehend things but only allows the description of phenomena. All progress in science can be designated as improvements and refinements in this describing capability, devoid of any advance in understanding things, as he describes on several occasions in the gay science. Paragraph 112 in the third book, for instance, starts with the following: »Erklärung« nennen wir’s: aber »Beschreibung« ist es, was uns vor älteren Stufen der Erkenntnis und Wissenschaft auszeichnet. Wir beschreiben besser – wir erklären ebensowenig wie alle Früheren... According to Nietzsche, truth and reality are no longer universal and objectiv- ity is non-existent. In our post-modern era, even the existence of something
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