Model prediction, experimental determination, and control of emulsion copolymer microstructure Citation for published version (APA): van Doremaele, G. H. J. (1990). Model prediction, experimental determination, and control of emulsion copolymer microstructure. Technische Universiteit Eindhoven. https://doi.org/10.6100/IR340343 DOI: 10.6100/IR340343 Document status and date: Published: 01/01/1990 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: 08. Oct. 2021 MODEL PREDICTION, E ERIMENTAL DETERMINATION, ND CONTROL OF EMULSION POLYMER MICROSTRUCTURE i 1 G.H.J. VAN DOREMAELE MODEL PREDICTION, EXPERIMENTAL DETERMINATION, AND CONTROL OF EMULSION COPOLYMER MICROSTRUCTURE CIP • Gegevens Koninklijke Bibliotheek, Den Haag van Doremaek; Gerardus Hemicus 1osephus Model Prediction, Experimental Detennination, and Control of Emulsion Copolymer Microstructure / Gerardus Henricus 1osephus van Doremaele. [S.1. : s.n.]. • 111. Proefschrift Eindhoven. Met lit. opg. Met samenvatting in het Nederlands. ISBN 90-9003718-7 SISO 542 UDC 541.64(043.3) Trel'w.: emulsiecopolymerisatie. @1990 G.HJ. van Doremaele, Berlicum Niets uit deze uitgave mag worden vermenigvuldigd en/of openbaar. gemaakt door middel van druk, fotokopie, microfilm of op welke andere wijze dan ook zonder voorafgaande schriftelijke toestemming van de auteur. No part of this publication may be reproduced or transmitted in any form or by any means, electroniç or mechanical, including photocopy, reoonting, or any information storage · and retrieval system, without pennission from the copyright owner. Cover Experimentally determined Molar Mass Chemical Composition Distribution of a styrene - methyl acrylate emulsion copolymer. MODEL PREDICTION, EXPERIMENTAL DETERMINATION, AND CONTROL OF EMULSION COPOLYMER MICROSTRUCTURE PROEFSCHRIFf ter verkrijging van de graad van doctor aan de Technische Universiteit Eindhoven, op gezag van de Rector Magnificus, prof. ir. M. Tels, voor een commissie aangewezen door het College van Dekanen in het openbaar te verdedigen op vrijdag 9 november 1990 te 16.00 uur door GERARDUS HENRICUS JOSEPHUS VAN OOREMAELE geboren te Berlicum druk: wlbro dlssertaliedrukkerij, helmond. Dit proefschrift is goedgekeurd door de promotoren: prof. dr. ir. A.L German prof. dr. J.M. Asua en de copromotor: dr. A.M. van Herk Het in dit proefschrift beschreven onderzoek werk uitgevoerd onder auspiciën van de Stichting Scheikundig onderzoek in Nederland (SON) met financiële steun van de Nederlandse Organisatie voor Wetenschappelijk Onderzoek (NWO). Aan mijn ouders quo quis doctior, eo modestior est. Hoe geleerder iemand is, des te bescheidener is hij. Latijns spreekwoord Contents Contents Chapter 1 Introduetion 1.1 Short historie overview 1 1.2 Background of the investigation 3 1.3 Choice of model systems 5 1.4 Aim of this investigation 7 1.5 Outline of this thesis 8 References 10 Chapter 2 Theoretieal Background 2.1 Emulsion polymerization 13 2.2 The ultimate and the penultimate model for copolymerization 18 References 21 Chapter 3 Experimental Copolymerization Procedures and Development of Experimental Methods of Copolymer Analysis 3.1 Procedures foliowed in solution and emulsion copolymerization 24 3.1.1 Purification of chemieals 3.1.2 Preparation of reference copolymers by solution copolymerization 3.1.3 Emulsion copolymerization equipment and procedures 25 3.2 Copolymer analysis 29 3.2.1 Cross-fractionation metbod for determining copolymer MMCCD 29 3.2.1.1 SEC 31 3.2.1.2 Gradient 1LC/FID 32 3.2.1.3 Cross-fractionation data treatment 36 3.2.1.4 Accuracy and reliability of gradient 1LC/FID 36 3.2.1.5 Gradient HPLC 41 3.2.2 1H and 13C NMR investigation of the intramolecular structure of solution S-MA copolymers and determination of reactivity ratios 43 Contents 3.2.2.1 Introduetion 43 3.2.2.2 Experimental section 46 3.2.2.3 Results and discussion 47 3.2.3 Determination of reactivity ratiosof MA-BA solution copolymerization and a feastbility study on the determination of the sequence distribution in MA-BA copolymers 62 3.2.3.1 Introduetion 62 3.2.3.2 Experimental section 63 3.2.3.3 Results and discussion 64 3.3 Conclusion 66 Relerences 67 Chapter 4 Model Evalustion of Emulsion Copolymerization Klnetics and Copolymer Microstructure 4.1 Introduetion 71 4.2 Model description 74 4.2.1 Physical and chemical outline 74 4.2.2 Basic principles of the theoretica! model 77 4.3 Model development 78 4.4 Model calculations 92 45 Conclusions 97 Appendix 4.A: MMO calculation 98 Appendix 4.B: discussion 101 Glossary of symbols 102 References 107 Chapter 5 Monomer Partitioning 5.1 Introduetion; theoretica! aspeets of monomer partitioning 111 5.2 Experimental seetion 117 5.3 Results; monomer partitioning 118 5.4 Results; bulk copolymerizations 125 55 Conclusions 127 References 128 Chapter 6 The Effect of Composition Drift on Copolymerization Rate 6.1 Introduetion 129 6.2 Experimental 131 6.3 Results and discussion 132 6.4 Condusion 143 References 144 Contents Chapter 7 Mierostruetural lnvestlgatlon of Batch Emulslon Styrene-Ac:ryUc Copolymers 7.1 Introduetion 146 7.2 Experimental section 148 7.3 Model ealculations: monomer reactivity ratios and monomer partitioning 149 7.4 Experimentally determined emulsion eopolymer microstructure in eomparison with model ealculations 151 7.4.1 (Molar mass) chemieal eomposition distribution 151 7.4.2 Sequence distribution of S-MA emulsion eopolymers 162 7.5 Conclusions 166 References 167 Chapter 8 Copolymer Composition Control by means of Semi-Continuons Emulsion Copolymerization 8.1 Introduetion 169 8.2 Experimental section 172 8.3 Results 174 8.3.1 Semi-eontinuous emulsion copolymerization with constant addition rates 175 8.3.2 Semi-eontinuous emulsion copolymerization with optima! addition profile 177 8.4 Discussion 186 8.5 Conclusion 187 References 188 Appendix A Partiele Morphology of Composite and Copolymer Latices 189 Appendix B lnvestigation of the Methoxy Proton Region in 1H NMR Spectra of 8-MA Copolymers by means of COLOC and NOESY NMR 201 Summary 211 Samenvatting 213 Dankwoord 216 Curriculum Vitae 218 Introduetion 1 Chapter 1 Introduetion 1.1 Short historie overview Conventional radical emulsion polymerization involves the dispersion of a monomer, an unsaturated organic molecule, in a continuous aqueous phase stabilized by an oil-in-water emulsifier, foliowed by free radical addition polymerization started with usually a water soluble initiator. This results in a reaction medium consisting .of submicron polymer particles swollen with the monomer and dispersed in an aqueous phase. The final product is called a latex and consists of a colloidal dispersion of polymer particles in water. The first attempts for emulsion polymerization were started during World War I in order to provide an artificial product as a substitute of natural rubber. Luther and Heuck presented the first viabie emulsion polymerization methodl). Synthetic latices were first produced in the mid-1930s in Germany. The commercial use of heterogeneaus emulsion (co )polymerization started in the United States during the period around World War 11 with the production of styrene-butadiene copolymer, developed under the guidance of the Office of the Rubber Reserve Program. Since then a huge number of papers bas appeared on emulsion polymerization, which is still growing in industrial importance. A detailed bistorical survey bas been given by Blackler>. Industrial and scientific interest in homogeneaus radical copolymerization in salution and bulk dates back to the 1920s3,4.S>. Copolymerization offers the possibility of modifying the properties of homopolymers into tailor made products. Nowadays emulsion copolymerization is a widely used process. Modem 2 Chapter 1 synthetic latlees find a braad range of applications in the coating. ink, plastic and adhesive industry. For application as elastomers, commodity