The second edition of this book includes a new chapter on morphology of latex particles, a rapidly progressing area where modelling the thermodynamic and kinetic aspects of phase separation and morphology has developed into a mature and powerful tool to predict and control morphology of latex particles.
Another area that is rapidly progressing is the application of controlled radical polymerisation in emulsion polymerization. Controlled radical polymerisation is used in aiding encapsulation of inorganic particles like pigment particles and clay platelets. These latest developments are included in the second edition.
Table of Contents
List of Contributors xiAbbreviations xiii
List of Frequently Used Symbols xvii
Introduction to the Second Edition xix
Introduction to the First Edition xxi
1 Historic Overview 1
Finn 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 23
A.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 43
A.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 75
Jose 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 105
Bernadette 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 Cex Reversible Chain Transfer Agents 136
5.5.2 High Cex Reversible Chain Transfer Agents 137
5.6 Conclusion 143
6 Particle Morphology 145
Yuri 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 167
Brian 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 187
Peter 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 213
Ola 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 253
Dieter Urban, Bernhard Schuler, and J¨urgen Schmidt-Th¨ummes
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 283
Christian 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
