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Shining a Light on Catalytic Chain Transfer Shining a light on catalytic chain transfer Citation for published version (APA): Pierik, S. C. J. (2002). Shining a light on catalytic chain transfer. Technische Universiteit Eindhoven. https://doi.org/10.6100/IR552686 DOI: 10.6100/IR552686 Document status and date: Published: 01/01/2002 Document Version: Publisher’s PDF, also known as Version of Record (includes final page, issue and volume numbers) Please check the document version of this publication: • A submitted manuscript is the version of the article upon submission and before peer-review. There can be important differences between the submitted version and the official published version of record. People interested in the research are advised to contact the author for the final version of the publication, or visit the DOI to the publisher's website. • The final author version and the galley proof are versions of the publication after peer review. • The final published version features the final layout of the paper including the volume, issue and page numbers. Link to publication General rights Copyright and moral rights for the publications made accessible in the public portal are retained by the authors and/or other copyright owners and it is a condition of accessing publications that users recognise and abide by the legal requirements associated with these rights. • Users may download and print one copy of any publication from the public portal for the purpose of private study or research. • You may not further distribute the material or use it for any profit-making activity or commercial gain • You may freely distribute the URL identifying the publication in the public portal. If the publication is distributed under the terms of Article 25fa of the Dutch Copyright Act, indicated by the “Taverne” license above, please follow below link for the End User Agreement: www.tue.nl/taverne Take down policy If you believe that this document breaches copyright please contact us at: [email protected] providing details and we will investigate your claim. Download date: 29. Sep. 2021 Shining a Light on Catalytic Chain Transfer Sebastiaan C.J. Pierik CIP-DATA LIBRARY TECHNISCHE UNIVERSITEIT EINDHOVEN Pierik, Sebastianus C.J. Shining a light on catalytic chain transfer / by Sebastianus C.J. Pierik. – Eindhoven : Technische Universiteit Eindhoven, 2002. Proefschrift. – ISBN 90-386-2763-7 NUGI 813 Trefwoorden: radicaalpolymerisatie / emulsiepolymerisatie / polymerisatiekinetiek / ketenoverdracht / cobaltkatalysatoren; cobaloxime / methylmethacrylaat Subject headings: radical polymerization / emulsion polymerization / polymerization kinetics / chain transfer agents / cobalt catalysts; cobaloxime / methyl methacrylate Druk:Universiteitsdrukkery Technische Universiteit Eindhoven Ontwerp omslag: JWL Producties Foto omslag: Raymond Festen Shining a Light on Catalytic Chain Transfer PROEFSCHRIFT ter verkrijging van de graad van doctor aan de Technische Universiteit Eindhoven, op gezag van de Rector Magnificus, prof.dr. R.A. van Santen, voor een commissie aangewezen door het College voor Promoties in het openbaar te verdedigen op woensdag 20 maart 2002 om 16.00 uur door Sebastianus Christoffel Josephus Pierik geboren te Spaubeek Dit proefschrift is goedgekeurd door de promotoren: prof.dr. A.M. van Herk en prof.dr.ir. A.L. German Copromotor: prof.dr. T.P. Davis Table of contents 1 General introduction 9 1.1 Free-radical polymerization 9 1.2 Catalytic chain transfer polymerization 11 1.3 Aims of the investigation 12 1.4 Outline of this thesis 13 1.5 References 14 2 A review on catalytic chain transfer 15 2.1 Cobalt chemistry 15 2.2 Determination of chain transfer coefficients 17 2.3 Catalytic chain transfer 18 2.3.1 General introduction 18 2.3.2 A closer look into the mechanisms of catalytic chain transfer 21 2.3.2.1 Investigations of the general mechanism 21 2.3.2.2 Chain-length dependent termination and catalytic inhibition 22 2.3.2.3 Cobalt – carbon bond formation 32 2.3.2.4 Catalyst deactivation 34 2.4 Reactivity and application of macromonomers 35 2.5 References 37 3 Mechanistic aspects of low conversion catalytic chain transfer 41 polymerization of methacrylates 3.1 Introduction 41 3.2 Experimental Section 42 3.3 Effects of initiator impurities and oxygen 44 3.4 Effects of solvents and solvent impurities 45 3.4.1 Solvent effects 45 3.4.2 Effects of solvent impurities 49 Table of contents 3.5 Diffusion control 51 3.5.1 Diffusion control from a process technological point of view 51 3.5.2 Diffusion control according to North 52 3.5.2.1 Derivation of an expression for CT incorporating diffusion control 52 3.5.2.2 Comparison of experimental results and theoretical calculations 55 3.6 Cobalt – carbon bond formation 58 3.6.1 Derivation of an expression for CT incorporating Co – C bond formation 58 3.6.2 Theoretical calculations for CT 60 3.6.3 Experimentally observed effects of initiator concentration on CT 62 3.7 Conclusions 65 3.8 References 66 4 High conversion CCT polymerization of methyl methacrylate 69 4.1 Introduction 69 4.2 Experimental Section 70 4.3 High conversion experiments in bulk and solution 72 4.3.1 Possible mechanisms 72 4.3.1.1 Changes in catalyst activity 75 4.3.1.2 Catalyst deactivation 76 4.3.1.3 Additional growth of polymer chains 81 4.3.1.4 Preliminary conclusions 82 4.3.2 Effects of catalyst and solvent concentration 83 4.4 The effects of acid and peroxides on catalyst deactivation 86 4.4.1 General observations 86 4.4.2 Mechanism and modeling for BPO induced deactivation 88 4.4.3 Mechanism and modeling for HAc induced deactivation 91 4.5 Conclusions 94 4.6 References 95 Table of contents 5 Catalytic chain transfer of non-α-methyl containing monomers 97 5.1 Introduction 97 5.2 Experimental Section 98 5.3 Catalytic chain transfer polymerization of styrene 100 5.3.1 CCT of styrene in dark, ambient light and UV-light 100 5.3.2 Quantitative description of CCT polymerization of styrene 104 5.3.3 Reversibility of polystyrene – cobalt bonds 108 5.4 Catalytic chain transfer polymerization of acrylates 109 5.5 Conclusions 112 5.6 References 113 6 Catalytic chain transfer copolymerization of methacrylates and acrylates 115 6.1 Introduction 115 6.2 Experimental Section 116 6.3 Model for CCT copolymerization of acrylates and MMA 118 6.3.1 Fundamental reaction steps and basic equations 119 6.3.2 Expressions for <ktr> and <kp> 120 6.3.3 Expression for fCo 121 6.4 Inhibition in the copolymerization of MA and MMA with CoBF 124 6.5 CCT in MA – MMA and BA – MMA copolymerizations 125 6.6 Effect of CCT on reactivity ratios 127 6.6.1 Introduction 127 6.6.2 Computer simulations on possible effects 128 6.6.3 Determination of MMA – BA reactivity ratios 129 6.7 Effect of conversion on CCT copolymerization of MMA and BA 132 6.7.1 Introduction 132 6.7.2 General aspects of high conversion CCT copolymerization 133 6.7.3 Macromer incorporation 135 6.7.4 Summary 138 6.8 Conclusions 139 6.9 References 139 Table of contents 7 Catalytic chain transfer polymerization in emulsion systems 141 7.1 Introduction 141 7.2 Experimental Section 143 7.3 Catalyst properties 146 7.3.1 Determination of catalyst activity 146 7.3.2 Catalyst partitioning 146 7.3.3 Summary 147 7.4 CCT in emulsion polymerization 148 7.4.1 Introduction 148 7.4.2 Application of CoBF, Co(Et)4BF and Co(Ph)4BF in emulsion 149 polymerization 7.4.2.1 Effects of catalyst type on molecular weight 151 7.4.2.2 Effects of emulsifier concentration and catalyst type on nucleation 153 and particle size 7.4.3 Summary 155 7.5 CCT in miniemulsion polymerization 155 7.5.1 Introduction 155 7.5.2 AIBN-initiated homo- and copolymerization 157 7.6 Conclusions 161 7.7 References 161 8 Epilogue 163 8.1 Evaluation 163 8.2 Future research 164 8.3 Conclusion 165 Glossary 166 Summary 171 Samenvatting 175 Dankwoord / Acknowledgements 178 Curriculum Vitae 180 Chapter 1 General Introduction Synopsis: After a brief introduction in free radical polymerization in general and catalytic chain transfer polymerization in particular, the aims of the presented investigations are discussed. Next, a short outline of all chapters in this thesis is given. 1.1 Free-radical polymerization Free-radical polymerization is a very versatile polymerization mechanism that can be applied to a wide variety of vinyl monomers. The resulting polymeric materials can be used in applications ranging from packaging materials to coatings as well as automotive parts. These different applications require different material properties, which are determined amongst others by the microstructure of the polymer chain, the interactions between the chains and the types of additives. When we focus on the microstructure, we can distinguish polymers that differ in the structure of the backbone, in molecular weight, in composition and in end groups. In Scheme 1.1 the various microstructural features are presented and for each feature some examples are provided. Furthermore, all these features can be combined in one single polymer. When a polymer consists of more than one monomer, it is called a copolymer. In this class of polymers several variations are known as well. Two linear copolymers with the same overall composition can have a different distribution of the monomers over the polymer chain resulting in random, gradient or even block copolymers. From this short overview it is clear that in principle many very different microstructures can be obtained. However, in free-radical polymerization it is impossible to obtain a polymer in which all chains have exactly the same structure. They will differ in length, composition, end groups and backbone structure, even when all chains are initiated at exactly the same moment and in the same way.
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