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J. Schellekens CIP-DATA LIBRARY TECHNISCHE UNIVERSITEIT EINDHOVEN Schellekens, Michael A. J. Adhesion promoting polyolefin block copolymers : macromolecular design based on living radical polymerization / by Michael A. J. Schellekens Eindhoven : Technische Universiteit Eindhoven, 2002. Proefschrift. – ISBN 90-386-2903-6 NUGI 813 Trefwoorden: radicaalpolymerisatie / ATRP / ketenoverdracht; RAFT / blokcopolymeren / polymeerlagen; hechting / polyolefinen / methacrylaten Subject headings: radical polymerization / ATRP / chain transfer; RAFT / block copolymers / polymeric coatings; adhesion / polyolefins / methacrylates © 2002, M. A. J. Schellekens Druk: Universiteitsdrukkerij, Technische Universiteit Eindhoven Omslagontwerp: Mike Schellekens / JWL Producties Adhesion Promoting Polyolefin Block Copolymers Macromolecular Design based on Living Radical Polymerization 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 donderdag 2 mei 2002 om 16.00 uur door Michael Arnoldus Jacobus Schellekens geboren te Tilburg Dit proefschrift is goedgekeurd door de promotoren: prof.dr. R. van der Linde en prof.dr. D. M. Haddleton Copromotor: dr.ir. B. Klumperman Het werk beschreven in dit proefschrift is financieel ondersteund door Corus (IJmuiden) en DSM Research (Geleen). The work described in this thesis was financially supported by Corus (IJmuiden) and DSM Research (Geleen). Table of Contents Chapter 1 Introduction 9 1.1 Polymers: Historical Development 9 1.2 Polyolefins as Coating Materials 10 1.3 Block Copolymers for Adhesion Promotion 11 1.4 Objectives and Outline of this Thesis 12 1.5 References 15 Chapter 2 Synthesis of Functional Polyolefin Block and Graft Copolymers: a Literature Review 17 2.1 Introduction 17 2.2 Preparation of Function Polyolefin Copolymers 18 2.3 Chemical Modification of Polyolefins: Free Radical Grafting 19 2.4 Metallocene Catalyzed Copolymerization of Olefins with Functional Monomers 20 2.4.1 Catalysis by Organolanthanide(III) Complexes 20 2.4.2 Group VIII Transition Metals 21 2.4.3 Group IV Metallocene Catalysts 21 2.4.4 Ring-opening Metathesis Polymerization (ROMP) 23 2.4.5 Functional Polyolefins via Metallocene Catalysts and Borane Reagents 24 2.5 Functionalized Polyolefins via Living Anionic Polymerization 26 2.6 Living Radical Polymerization 27 2.6.1 Nitroxide-mediated Living Radical Polymerization 27 2.6.2 Atom Transfer Radical Polymerization (ATRP) 28 2.6.3 Reversible Addition-Fragmentation Chain Transfer (RAFT) Polymerization 31 2.7 Summary 34 2.8 References 35 Chapter 3 Synthesis of Polyolefin Block Copolymers via ATRP 39 3.1 Introduction 39 3.2 Control of Polymerization in ATRP and Kinetic Features 40 3.3 The Role of Components in Copper-based ATRP 43 3.3.1 Copper Catalyst and Ligand 43 3.3.2 Initiator 44 3.3.3 Mechanistic and Kinetic Issues 45 3.3.4 Screening of Catalyst Complexes 47 3.3.5 Effect of the Initiating Group on the Control of Polymerization 50 3.4 Determination of the Macroinitiator Conversion 53 3.4.1 Application of Gradient Polymer Elution Chromatography (GPEC) 53 Table of Contents 3.4.2 Reversed-phase and Normal-phase Applications 54 3.4.3 Characterization of the PEB-PMMA Block Copolymers by RP and NP-GPEC 55 3.4.4 Determination of the Macroinitiator Conversion with NP-GPEC 58 3.5 Determination of the Activation Rate Parameter 62 3.5.1 Strategy for the Determination of k act 62 3.5.2 Results and Discussion 64 3.6 Determination of the Deactivation Rate Parameter 71 3.7 Conclusions 73 3.8 Experimental 74 3.9 References 76 Chapter 4 Functional Polyolefin Block Copolymers via ATRP 79 4.1 Adhesion Promoting Polyolefin Block Copolymers 79 4.2 Polymerization of Functional Monomers via ATRP 80 4.2.1 Glycidyl Methacrylate 81 4.2.2 2-Hydroxyethyl Methacrylate 83 4.2.3 2-(Dimethylamino)ethyl Methacrylate 86 4.2.4 Methacrylic Acid 88 4.2.5 Maleic Anhydride 90 4.3 Removal of Copper-based Catalysts from Functional Polymers 91 4.4 Chain-end Functional Polyolefins via Anionic Polymerization of Isoprene 93 4.5 Functional Poly(ethylene-co-propylene)-Polymethacrylate Block Copolymers 96 Prepared by ATRP 4.5.1 Target Degree of Polymerization 97 4.5.2 Recipe Design and Reaction Procedures 99 4.5.3 Results and Discussion 100 4.6 Conclusions 102 4.7 Experimental 102 4.8 References 104 Chapter 5 Feasibility Studies of RAFT Polymerization 107 5.1 Introduction 107 5.2 Mechanistic and Kinetic Features of RAFT Polymerization 108 5.3 Synthesis of Maleic Anhydride Containing Polyolefin Block Copolymers 112 5.3.1 Studies Involving a Model Polyolefin Precursor 113 5.3.2 Poly(ethylene-co-propylene)-Poly(styrene-co-(maleic anhydride)) Block 119 Copolymers 5.4 Block Copolymer Synthesis: RAFT versus ATRP 123 5.5 Conclusions 129 5.6 Experimental 129 5.7 References 131 Table of Contents Chapter 6 Application Studies of Block Copolymers for Adhesion Promotion 133 6.1 Introduction 133 6.2 Adsorption Studies of Polyolefin Block Copolymers 135 6.2.1 Factors Influencing Adsorption From Solution 135 6.2.2 Adsorption Characteristics of Polyolefin Block Copolymers onto Aluminum 140 6.2.3 Monolayer Characterization Studies 147 6.3 Application of Polyolefin Block Copolymers for Adhesion Promotion 157 6.3.1 Adhesion Promotion Studies: Strategy and Problems Involved 157 6.3.2 Effect of Block Copolymer Design on Adhesion Promotion 160 6.4 Conclusions 164 6.5 Experimental 165 6.6 References 167 Epilogue 171 Summary 175 Samenvatting 179 Dankwoord 183 Curriculum Vitae 185 Table of Contents 1 Introduction 1.1 Polymers: Historical Development The evolution of chemistry as a new class of science originates from the classification th of the elements by Lavoisier in 1789. In the beginning of the 20 century, after the existence of atoms and molecules in respect of simple inorganic compounds was generally accepted, one came to realize that organic molecules are composed of atoms that are linked in small chains by chemical bonds. At this time, man had already discovered nature’s polymeric materials like natural rubber and cellulose, and had even synthesized numerous polymeric materials such as phenolic resins (Bakeliet), alkyd resins, polystyrene and poly(vinyl chloride). However, no clear understanding was yet obtained about the precise structure of these complex organic materials. In 1920, Staudinger was the first to propose the polymer concept,1 in which thermoplastic materials are visualized as a mixture of long chain molecules built from so-called monomer units that are covalently connected. About ten years later, when this polymer concept was generally accepted, it was the work of Carothers on step-growth polymerization for the production of nylons that triggered the development of polymer chemistry on an industrial scale. With the world-wide commercial introduction of real synthetic polymers like poly(vinyl chloride), polystyrene and poly- olefins, the demand for so-called plastics witnessed a tremendous growth. Within 50 years, the annual world production of synthetic polymeric materials such as plastics, fibers and rubbers increased with a factor of about 200, 300 and 3000, respectively. Polyolefins Although the first polyolefins were prepared at the end of the 19th century,2,3 due to their high cost price these materials did not attain much commercial interest until the 1930s. It was the discovery of a new technique comprising the polymerization of olefins under high pressure that eventually resulted in the first full-scale production in 1942 of a polyethylene material that later became known as low density polyethylene (LDPE).4 In 1954, an 9

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