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Heterophase Polymerization Heterophase Polymerization Basic Concepts and Principles Hugo Hernandez Klaus Tauer Published by Jenny Stanford Publishing Pte. Ltd. Level 34, Centennial Tower 3 Temasek Avenue Singapore 039190 Email: [email protected] Web: www.jennystanford.com British Library Cataloguing-in-Publication Data A catalogue record for this book is available from the British Library. Heterophase Polymerization: Basic Concepts and Principles All rights reserved. This book, or parts thereof, may not be reproduced in any form Copyright © 2021 by Jenny Stanford Publishing Pte. Ltd. or by any means, electronic or mechanical, including photocopying, recording or any information storage and retrieval system now known or to be invented, without written permission from the publisher. For photocopying of material in this volume, please pay a copying fee through the Copyright Clearance Center, Inc., 222 Rosewood Drive, Danvers, MA 01923, USA. In this case permission to photocopy is not required from the publisher. ISBN 978-981-4877-32-9 (Hardcover) ISBN 978-1-003-11929-6 (eBook) Contents Preface by Hugo Hernandez Preface by Klaus Tauer Introdu cing an Alternative U nderstanding of vii Heterophase Polymerization ix 1. Molecular Description of Heterophase Polymerization x1i 1.1 Introduction to Heterophase Polymerization 1 1.2 Molecular Forces 5 1.3 Molecular Diffusion 10 1.3.1 Brownian Motion and the Laws of Diffusion 10 1.3.2 Brownian Dynamics (BD) Simulation 17 1.3.3 Macromolecular Diffusion 19 1.3.4 Molecular Diffusion by Molecular Dynamics Simulation 23 1.4 Molecular Phases 26 1.5 Molecular Behavior at Interfaces 32 1.6 Polymerization 36 2. 1M.7e chanHisemtesr oofp Hheatseer oPpohlyamsee rPiozlaytmioenr ization 4619 2.1 Particle Formation 70 2.1.1 Precipitation Nucleation 77 2.1.2 Aggregative Nucleation 79 2.1.3 Heterogeneous Nucleation 82 2.2 Molecular Transfer 87 2.2.1 Capture 88 2.2.2 Desorption 95 2.2.3 Equilibrium 105 2.3 Kinetics of Polymerization 117 2.3.1 Step-Growth Polymerization Kinetics 122 2.3.2 Chain-Growth Polymerization Kinetics 126 2.3.3 Diffusion-Controlled Polymerization Kinetics 131 vi Contents 2.3.4 Heterophase Polymerization Kinetics 133 3. 2M.4u ltiscaPlaer Mticolde eDliynnga omf iHces terophase Polymerization 113545 3.1 Atomistic Scale 159 3.2 Molecular Scale 162 3.2.1 Monte Carlo Simulation 162 3.2.2 Molecular Dynamics Simulation 164 3.3 Macromolecular Scale 167 3.4 Supramolecular and Colloidal Scale 170 3.5 Microscopic Scale 176 3.6 Mesoscopic Scale 181 3.7 Macroscopic Scale 184 3.7.1 First-Principles Modeling 186 3.7.2 Semi-empirical Modeling 188 3.7.3 Equilibrium Thermodynamics Modeling 190 3.7.4 Empirical Modeling 190 3.8 Multiscale Integration 192 3.8.1 Model Order Reduction 192 3.8.2 Sequential Multiscale Simulation 193 3.8.3 Stochaabs itniict iToransformation across Scales 194 4. Recent A3d.8v.a4n ceFsu alnl d Future PMeursltpiescctailvee Ssi imn u lation 198 Heterophase Polymerization 221 4.1 Surfactants and Dispersants 224 4.2 Controlled Radical Polymerization 228 4.3 Kinetics and Mechanisms 232 4.4 Process Engineering 234 4.5 Green Chemistry and Engineering 238 4.6 Product Innovation in Polymer Dispersions 245 4.7 Novel Applications of Heterophase Polymerization 249 4.8 Future Perspectives in Heterophase Index Polymerization 252 281 Preface vii Preface by Hugo Hernandez By the time I graduated as a chemical engineer, I never imagined working with polymers, much less writing a book on this field. My first job was at a chemical company where different types of polymers, including polymer latexes, were manufactured. At first, polymers appeared to me as fascinating although mysterious materials, behaving completely different from the usual chemical substances I knew so far. I still remember the time when, by curiosity, I read the first scientific paper on emulsion polymerization. At that moment I was not able to understand much, but it was clear to me that I had found a fascinating but challenging topic. Then, I set a goal and began a journey toward understanding such complex systems. Eventually, I had the chance of working in research and development, particularly on different research projects involving emulsion polymerization. Even though I had learned after reading a lot of books and papers, as well as from my own experience in the lab, pilot, and industrial plant, I still wanted to obtain a deeper knowledge. That is when I decided to pursue my doctoral studies working on emulsion polymHeerteizraotpiohna.s e Polymerization In February 2006, I received an acceptance letter by Dr. Klaus Tauer, group leader of the “ ” group at the Colloid Chemistry Department of the Max Planck Institute of Colloids and Interfaces, for beginning my studies at the International Max Planck Research School on Biomimetic Systems. During the 4 years that I stayed at the Max Planck Institute, first as a doctoral student and then as a postdoc, I had the chance to dedicate myself to learning, in as much depth as possible, about polymersn, octohlilnogids, physical chemistry, and mathewmaast iwcarli tmteond ienl instgo.n Iet was also during that time when I realized that science is unfinished, and from what I had learned so far . Following the principles of good scientific practice established by the Max Planck Society, and with the guidance of Dr. Tauer, I officially began publishing my contributions to science in 2007. In 2015, inspired by the ideas of freedom of research, transparency, and public sharing of knowledge promoted at the viii Preface Max Planck Institute, I decided to create ForsChem Research (www. forschem.org). The main goal of this not-for-profit initiative is searching for a better understanding of different natural phenomena from a molecular perspective (and involving a lot of math, of course). All results obtained in this initiative are open and available to anyone interested in reading them. The idea of writing a book on emulsion polymerization was first mentioned to me by Dr. Tauer in 2010. Even though we did not have the chance to finish the project then, we decided to resume it again in 2019, but this time considering the broader field of heterophase polymerization. Thus, we tried our best to summarize our vision on heterophase polymerization, so that future generations might find it easier to understand and achieve even further progress. I am very much grateful to Dr. Klaus Tauer, my doctoral supervisor and co-author of this book, who devoted his lifework and curiosity to the science and technology of heterophase polymerization. I also want to thank Silvia, my beloved wife, for continuously supporting and encouraging me toward working on this book. I also want to thank my mother and my late father for all their teachings and support. I am also grateful to Jaime Aguirre, my master’s thesis advisor, for being my scientific peer and dear friend. I also want to acknowledge all the scientists that have contributed to this fascinating field (some of which I had the opportunity to meet), as well as all other colleagues that helped me in one way or another along this road. Finally, I would like to thank all the readers of this book for your patience (I hope you read it all) and, most of all, for your scientific curiosity. November 2020 Preface ix Preface by Klaus Tauer When a graduate starts career in the field of heterophase polymerization, she or he faces quite a challenge, because to be successful in this field, she or he has to deal intensively with two scientific areas, namely colloid science and polymer science. Typically, the beginner will find the basics of heterophase polymerization in standard textbooks that focus primarily on emulsion polymerization. One of its pillars is the Smith–Ewart model, which is more than 70 years old. That is exactly how I started my professional career in a research institute in 1977. I quickly noticed some problems wdituhb ituhmis msaopdieenl,t ipaea ritnicituiulamrly rteog adroduibntg isi ttsh ea psptalircta obnil itthye tpoa tvha rtioo uwsi svdaormiants of emulsion polymerization. Following Renè Descartes “ ” (“ ”), I started new projects to investigate particle nucleation and swelling of latex particles. All knowledge is preliminary, and hence with the availability of new experimental data, the modification of older models is necessary. Clearly, the same must apply to emulsion polymerization. We tried to do so in this book, at least partly. However, the history of emulsion polymerization research shows that more and more specific mechanisms to overcome some of the problems have been developed. Exemplarily, some new mechanistic assumptions for particle nucleation and radical entry appear, at least to me, to be detached from the generally valid scientific ideas. Just when nucleation is considered, this is a very general natural phenomenon and there is no reason to consider for emulsion polymerization a principally different framework. Visiting many scientific meetings over the last 40 years, I made the following remarkable observation concerning the relationship between heterophase polymerization and polymer science, on the one hand, and colloid science, on the other hand. For research polymer chemists, this topic is too boring and not hot enough mainly because it is a well-established industrial polymerization technique. For colloid chemists, heterophase polymerization is a “horrible” system because the parameters such as surface area and