Table Of ContentHeterophase Polymerization
Heterophase Polymerization
Basic Concepts and Principles
Hugo Hernandez
Klaus Tauer
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Heterophase Polymerization: Basic Concepts and Principles
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ISBN 978-981-4877-32-9 (Hardcover)
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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
