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About Morphology of Grafted Ethylene-Propylene(-Diene) Copolymers-Based Latexes : Preparation, Structure and Properties About morphology of grafted ethylene-propylene(-diene) copolymers-based latexes : preparation, structure and properties Citation for published version (APA): Tillier, D. L. (2005). About morphology of grafted ethylene-propylene(-diene) copolymers-based latexes : preparation, structure and properties. Technische Universiteit Eindhoven. https://doi.org/10.6100/IR583584 DOI: 10.6100/IR583584 Document status and date: Published: 01/01/2005 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: 27. Sep. 2021 About Morphology of Grafted Ethylene-Propylene(-Diene) Copolymers-Based Latexes - Preparation, Structure and Properties - Delphine L. Tillier CIP-DATA LIBRARY TECHNISCHE UNIVERSITEIT EINDHOVEN Tillier, Delphine L. About morphology of grafted ethylene-propylene(-diene) copolymers-based latexes : preparation, structure and properties / by Delphine L. Tillier. – Eindhoven : Technische Universiteit Eindhoven, 2005. Proefschrift. – ISBN 90-386-2866-8 NUR 913 Trefwoorden: emulsiepolymerisatie ; latices / polymeermofologie ; kern- schaaldeeltjes / EPDM rubber / deeltjesgrootteverdeling / vernetten / slagbestendige materialen / slagsterkte modificeerders / polymethylmethacrylate ; PMMA Subject headings: emulsion polymerization ; latexes / polymer morphology ; core-shell particles / EPDM rubber / particle size distribution / crosslinking / impact-resistant materials / impact modifiers / poly(methyl methacrylate) ; PMMA © 2005, Delphine L. Tillier Printed by PrintService Ipskamp, The Netherlands. Cover designed by Delphine Tillier, Soazig Périn and Jan-Willem Luiten, JWL Producties This research was financially supported by the Foundation of Emulsion Polymerization (SEP) and the European Graduate School (EGS). An electronic copy of this thesis is available from the site of the Eindhoven University Library in PDF format (www.tue.nl/bib). About Morphology of Grafted Ethylene-Propylene(-Diene) Copolymers-Based Latexes - Preparation, Structure and Properties - 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 17 februari 2005 om 16.00 uur door Delphine Lucienne Tillier geboren te Domont, Frankrijk Dit proefschrift is goedgekeurd door de promotoren: prof.dr. C.E. Koning en prof.dr. A.M. van Herk Copromotor: dr. J. Meuldijk A mes parents Table of Contents 1. General introduction 1 1.1 Existing impact modifiers 2 1.2 Preparation of impact modifiers 4 1.3 Objective and outline of this thesis 4 References 7 2. Principles of emulsion polymerization 9 2.1 Introduction 10 2.2 Overall description of emulsion polymerization 11 2.2.1 Emulsion polymerization processes 11 2.2.2 Kinetics and mechanisms 12 2.3 Seeded emulsion polymerization 16 2.3.1 General description 16 2.3.2 Production of core-shell particles by seeded emulsion polymerization 16 2.4 Conclusions 19 References 20 3. Production of colloidally stable latexes from low molecular weight ethylene-propylene(-diene) copolymers 23 3.1 Introduction 24 3.2 Experimental section 28 3.2.1 Chemicals 28 3.2.2 Preparation of an artificial latex from a low molecular weight EP(D)M 29 3.2.3 Characterization of polymers 31 3.2.4 Characterization of latexes – Particle size distribution 32 3.3 Results and discussion 32 3.3.1 Optimization of the surfactant system 32 3.3.2 Influence of polymer viscosity on particle size distribution 37 3.4 Conclusions 40 References 42 4. About crosslinking of EP(D)M-based latexes 45 4.1 General introduction 46 4.1.1 General mechanism of crosslinking 46 4.1.2 Aim of this chapter 53 4.2 Experimental section 53 4.2.1 Chemicals 53 4.2.2 Preparation of a seed latex 55 4.2.3 Chemically-initiated crosslinking 56 4.2.4 Crosslinking initiated by a pulsed electron-beam 57 4.2.5 Characterization of the latexes 59 4.3 Results and discussion 62 4.3.1 Chemically-initiated crosslinking 62 4.3.2 Crosslinking initiated by a pulsed electron-beam 72 4.4 Conclusions 77 References 79 5. About morphology in EP(D)M-based latexes 83 5.1 Introduction 84 5.2 Experimental section 85 5.2.1 Chemicals 85 5.2.2 Preparation of the seed latex 86 5.2.3 Seeded emulsion polymerization of MMA onto EP(D)M 87 5.2.4 Characterization 89 5.3 Results and discussion 93 5.3.1 Grafting mechanism 93 5.3.2 Efficiency of the grafting reaction 97 5.3.3 Morphology of the EP(D)M-g-PMMA particles 101 5.4 Conclusions 112 References 114 6. Toughening effect of EP(D)M-PMMA core-shell structures in a brittle PMMA matrix 117 6.1 Introduction 118 6.2 Experimental section 118 6.2.1 Chemicals 118 6.2.2 Synthesis of the composite latex particles 119 6.2.3 Synthesis of a PMMA homopolymer latex 119 6.2.4 Blending and specimen preparation 120 6.2.5 Characterization 120 6.3 Results and discussion 121 6.3.1 Molecular characterization of PMMA 121 6.3.2 Incorporation of the rubbery particles into a PMMA matrix 122 6.3.3 Mechanical properties of PMMA/rubber blends 123 6.3.4 Fracture mechanism 125 6.4 Conclusions 127 References 129 7. Highlights and technological assessment 131 7.1 Highlights 132 7.2 Technological assessment 133 References 135 Summary 137 Samenvatting 141 Acknowledgements 145 Curriculum vitae 149 General introduction Abstract The aim of this chapter is to introduce the background of the project. The developments in the field of impact modification are presented, followed by an overview of the research exposed in the next chapters. 2 Chapter 1 1.1 Existing impact modifiers For many applications, high performance materials, e.g. coatings1,2 and engineering plastics3,4, require high impact strength. The paint of a car, for instance, should withstand being hit by a piece of gravel without film rupture. Thermoplastic materials, such as polycarbonate (PC), have a tendency to undergo brittle failure under environmental stress cracking conditions, e.g. by the presence of a sharp notch. Therefore such materials need some adjustments to extend their applications under high impact conditions, for example in the automotive industry. Improvement of impact strength may be achieved with tougheners, which consist of an elastomeric part, providing impact resistance, and a rigid part, providing good adhesion with a polymer matrix. Core-shell tougheners with a crosslinked core, as opposed to linear tougheners, have a fixed morphology and are the preferred impact modifiers especially in injection molded engineering plastics and in coatings. The first attempts to produce rubber-toughened materials were completed in the late 1940’s, leading to the high-impact grade of polystyrene (HIPS)5. The wide range of high impact resistant polymers includes ABS (acrylonitrile/butadiene/styrene) and MBS (methyl methacrylate/butadiene/styrene). An early form of ABS consisted of a physical mixture of styrene/acrylonitrile (SAN) and acrylonitrile/butadiene copolymers. In the 1950’s, ABS was produced via emulsion polymerization6, resulting in SAN grafted onto spherical polybutadiene latex particles. Those grafts greatly improved the compatibility of the elastomeric particles and the SAN matrix. Since then, the diversity and ease of processing of these copolymers turned ABS into one of the most popular engineering polymers. ABS polymers now find applications in coatings, adhesives, or impact modifiers. Unmodified, ABS copolymers are also used in automotive applications or electrical equipments, such as vacuum cleaners, phones or computers. An important application of both ABS and MBS resides in the impact modification of poly(vinyl chloride) (PVC) and polycarbonate (PC). MBS and ABS modifiers are General introduction 3 mostly used in transparent applications where weather resistance is not required. Moreover, MBS and ABS modifiers are particularly efficient for low temperature impact
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