Alex van Herk is Senior researcher at the Institute of Chemical and Engineering Sciences, an A*Star institute in Singapore and part time Professor in Polymer Reaction Engineering at the Eindhoven University of Technology, Netherlands.

List of Contributors xi Abbreviations xiii List of Frequently Used Symbols xvii Introduction to the Second Edition xix Introduction to the First Edition xxi 1 Historic Overview 1Finn Knut Hansen 1.1 The Early Stages 1 1.2 The Second Half of the Twentieth Century 9 1.2.1 Product Development 9 1.2.2 Kinetic Theory 11 1.2.3 Emulsion Polymerisation in Monomer Droplets 19 1.2.4 Industrial Process Control and Simulation 21 2 Introduction to Radical (Co)Polymerisation 23A.M. van Herk 2.1 Mechanism of Free Radical Polymerisation 23 2.2 Rate of Polymerisation and Development of Molecular Mass Distribution 25 2.2.1 Rate of Polymerisation 25 2.2.2 Kinetic Chain Length 26 2.2.3 Chain Length Distribution 27 2.2.4 Temperature and Conversion Effects 30 2.3 Radical Transfer Reactions 31 2.3.1 Radical Transfer Reactions to Low Molecular Mass Species 31 2.3.2 Radical Transfer Reactions to Polymer 32 2.4 Radical Copolymerisation 34 2.4.1 Derivation of the Copolymerisation Equation 34 2.4.2 Types of Copolymers 37 2.4.3 Polymerisation Rates in Copolymerisations 39 2.5 Controlled Radical Polymerisation 41 3 Emulsion Polymerisation 43A.M. van Herk and R.G. Gilbert 3.1 Introduction 43 3.2 General Aspects of Emulsion Polymerisation 44 3.3 Basic Principles of Emulsion Polymerisation 46 3.4 Particle Nucleation 47 3.5 Particle Growth 51 3.5.1 The Zero-One and Pseudo-Bulk Dichotomy 52 3.5.2 Zero-One Kinetics 53 3.5.3 Pseudo-Bulk Kinetics 55 3.5.4 Systems between Zero-One and Pseudo-Bulk 57 3.6 Ingredients in Recipes 57 3.6.1 Monomers 58 3.6.2 Initiators 58 3.6.3 Surfactants 58 3.6.4 Other Ingredients 59 3.7 Emulsion Copolymerisation 59 3.7.1 Monomer Partitioning in Emulsion Polymerisation 59 3.7.2 Composition Drift in Emulsion Co- and Terpolymerisation 63 3.7.3 Process Strategies in Emulsion Copolymerisation 64 3.8 Particle Morphologies 66 3.8.1 Core-Shell Morphologies 68 4 Emulsion Copolymerisation, Process Strategies 75Jose Ramon Leiza and Jan Meuldijk 4.1 Introduction 75 4.2 Monomer Partitioning 79 4.2.1 Slightly and Partially Water Miscible Monomers 79 4.2.2 Consequences of Monomer Partitioning for the Copolymer Composition 84 4.3 Process Strategies 86 4.3.1 Batch Operation 86 4.3.2 Semi-Batch Operation 89 4.3.3 Control Opportunities 92 5 Living Radical Polymerisation in Emulsion and Miniemulsion 105Bernadette Charleux, Michael J. Monteiro, and Hans Heuts 5.1 Introduction 105 5.2 Living Radical Polymerisation 106 5.2.1 General/Features of a Controlled/Living Radical Polymerisation 106 5.2.2 Reversible Termination 108 5.2.3 Reversible Chain Transfer 116 5.3 Nitroxide-Mediated Polymerisation in Emulsion and Miniemulsion 119 5.3.1 Introduction 119 5.3.2 Control of Molar Mass and Molar Mass Distribution 120 5.3.3 Synthesis of Block and Random or Gradient Copolymers via (Mini)Emulsion Polymerisation 125 5.3.4 Surfactant-Free Emulsion Polymerisation Using the Polymerisation-Induced Self-Assembly Technique 126 5.4 ATRP in Emulsion and Miniemulsion 126 5.4.1 Introduction 126 5.4.2 Direct ATRP 127 5.4.3 Reverse ATRP 130 5.4.4 Next Generation ATRP Techniques: SRNI and AGET 132 5.4.5 Some Concluding Remarks on ATRP in Emulsion 135 5.5 Reversible Chain Transfer in Emulsion and Miniemulsion 136 5.5.1 Low C ex Reversible Chain Transfer Agents 136 5.5.2 High C ex Reversible Chain Transfer Agents 137 5.6 Conclusion 143 6 Particle Morphology 145Yuri Reyes Mercado, Elena Akhmastkaya, Jose Ramon Leiza, and Jose M. Asua 6.1 Introduction 145 6.2 Synthesis of Structured Polymer Particles 146 6.2.1 Emulsion Polymerisation 146 6.2.2 Miniemulsion Polymerisation 147 6.2.3 Physical Methods 148 6.3 Two-Phase Polymer-Polymer Structured Particles 148 6.3.1 Effect of Grafting 152 6.4 Two-Phase Polymer-Inorganic Particles 153 6.5 Multiphase Systems 156 6.6 Effect of Particle Morphology on Film Morphology 162 6.6.1 Modelling Film Morphology 165 Acknowledgements 165 7 Colloidal Aspects of Emulsion Polymerisation 167Brian Vincent 7.1 Introduction 167 7.2 The Stabilisation of Colloidal Particles against Aggregation 168 7.3 Pair-Potentials in Colloidal Dispersions 170 7.3.1 Core-Core Interactions 170 7.3.2 Structural Interactions: (i) Those Associated with the Solvent 171 7.3.3 Structural Interactions: (ii) Electrical Double Layer Overlap 173 7.3.4 Structural Interactions: (iii) Adsorbed Polymer Layer Overlap 175 7.4 Weak Flocculation and Phase Separation in Particulate Dispersions 179 7.5 Aggregate Structure and Strength 184 8 Analysis of Polymer Molecules including Reaction Monitoring and Control 187Peter Schoenmakers 8.1 Sampling and Sample Handling 188 8.1.1 Sampling 188 8.1.2 Sample Preparation 188 8.2 Monomer Conversion 189 8.3 Molar Mass 190 8.3.1 Molar-Mass Distributions 191 8.4 Chemical Composition 197 8.4.1 Average Chemical Composition 197 8.4.2 Molar-Mass Dependent Chemical Composition 199 8.4.3 Chemical-Composition Distributions 202 8.4.4 Two-Dimensional Distributions 207 8.5 Detailed Molecular Characterization 210 8.5.1 Chain Regularity 210 8.5.2 Branching 212 9 Particle Analysis 213Ola Karlsson and Brigitte E.H. Schade 9.1 Introduction 213 9.2 Particle Size and Particle Size Distribution 214 9.2.1 Introduction 214 9.2.2 Average Particle Diameter 216 9.2.3 Particle Size Distribution 216 9.3 Sampling 216 9.4 Particle Size Measurement Methods 217 9.4.1 Ensemble Techniques 218 9.4.2 Particle Separation Methods 224 9.5 Comparison of Methods 233 9.5.1 Choice of a Method 235 9.6 Particle Shape, Structure and Surface Characterisation 236 9.6.1 Introduction to Particle Shape, Structure and Surface Characterisation 236 9.6.2 Classification of the Samples 238 9.6.3 General Considerations - Sample Preparation If the Latex is Film Forming 238 9.7 Discussion of the Available Techniques 239 9.7.1 Optical Microscopy (OM) 239 9.7.2 Atomic Force Microscopy (AFM) 240 9.7.3 Electron Microscopy 243 9.7.4 Indirect Analysis of Particle Morphology 248 9.7.5 Surface Characterisation 249 9.7.6 Cleaning of Latexes 250 9.7.7 Analyses of Particle Charge 250 9.7.8 Additional Techniques Used for Latex Particle Surface Characterisation 250 9.7.9 Zeta Potential 251 10 Large Volume Applications of Latex Polymers 253Dieter Urban, Bernhard Schuler, and Jürgen Schmidt-Thümmes 10.1 Market and Manufacturing Process 253 10.1.1 History and Market Today 253 10.1.2 Manufacturing Process 254 10.2 Paper and Paperboard 254 10.2.1 The Paper Manufacturing Process 254 10.2.2 Surface Sizing 255 10.2.3 Paper Coating 256 10.3 Paints and Coatings 262 10.3.1 Technology Trends 263 10.3.2 Raw Materials for Water-Borne Coating Formulations 264 10.3.3 Decorative Coatings 269 10.3.4 Protective and Industrial Coatings 271 10.4 Adhesives 271 10.4.1 Design of Emulsion Polymer Adhesives 272 10.4.2 Formulation Additives 276 10.4.3 Adhesive Applications 277 10.4.4 Adhesive Test Methods 279 10.5 Carpet Backing 280 10.5.1 Carpet Backing Binders 281 10.5.2 Carpet Backing Compounds 281 10.5.3 Application Requirements 282 Acknowledgements 282 11 Specialty Applications of Latex Polymers 283Christian Pichot, Thierry Delair, and Haruma Kawaguchi 11.1 Introduction 283 11.2 Specific Requirements for the Design of Specialty Latex Particles 284 11.2.1 Nature of the Polymer 284 11.2.2 Particle Size and Size Distribution 285 11.2.3 Particle Morphology 285 11.2.4 Nature of the Interface 286 11.2.5 Surface Potential 287 11.2.6 Colloidal Stability 287 11.2.7 Functionality 287 11.3 Preparation Methods of Latex Particles for Specialty Applications 288 11.3.1 Radical-Initiated Polymerisation in Heterogeneous Media 288 11.3.2 Modification of Particles and Related Methods 290 11.3.3 Formulation of Colloidal Dispersions from Pre-Formed Polymers 293 11.4 Applications 294 11.4.1 Non-Biomedical Applications 294 11.4.2 Biological, Biomedical and Pharmaceutical Applications 299 11.5 Conclusions 304 References 307 Index 337