Advances in Polymer SciencesAlso Available Electronically 7
Aims and Scope 8
Preface 9
Contents 11
Historical Overview of (Mini)emulsion Polymerizations and Preparation of Hybrid Latex Particles 12
1 Introduction 13
2 Emulsion Polymerization 16
2.1 General Aspects of Emulsion Polymerization 16
2.2 Principles of the Emulsion Polymerization Process 17
2.3 Particle Nucleation 17
2.4 Particle Morphologies 18
3 Miniemulsion and Microemulsion Polymerization 20
4 Encapsulation of Inorganic Particles 21
4.1 Early Accounts of Encapsulation Through Emulsion Polymerization 21
4.2 Encapsulation of Inorganic Particles with Emulsion Polymerization 23
4.2.1 General Principles 23
4.2.2 Efficiency of Encapsulation 25
4.2.3 Special Approaches 26
5 Conclusions 27
References 28
Physical Methods for the Preparation of Hybrid Nanocomposite Polymer Latex Particles 30
1 Assembly of Nanoparticles onto Prefabricated ``Larger'' Particles via Heterocoagulation 31
1.1 Electrostatic Interactions 32
1.2 Hydrophobic Interactions 36
1.2.1 Self-Assembly of Amphiphilic Particles Driven by the Hydrophobic Effect 37
1.3 Secondary Molecular Interactions 41
1.3.1 Hydrogen Bonding 41
1.3.2 41
1.3.3 Specific Recognition of Complementary DNA Strands 42
1.3.4 Avidin--Biotin Recognition 42
2 Assembly of Nanoparticles onto Prefabricated Larger Particles via Repetitive Heterocoagulation: the Layer-by-Layer Technique 44
3 Assembly of Nanoparticles onto Emulsion Monomer Droplets and their Subsequent Polymerization 45
3.1 Pickering Stabilization: Adhesion of Particles to ``Soft'' Interfaces 45
3.1.1 Interaction of a Single Spherical Particle with a ``Soft'' Interface 46
3.1.2 Droplets Armored with a Layer of Adhered Particles 49
3.2 Polymerization of Emulsion Droplets Armored with Inorganic Nanoparticles: Pickering Suspension and MiniemulsionPolymerization 49
4 Assembly of Nanoparticles onto the Surface of Polymer Colloids Throughout Emulsion Polymerization: Solids-Stabilized, or Pickering, Emulsion Polymerization 53
5 Hybrid Polymer Colloids Through Assembly of Colloidal Building Blocks via Interface-Driven Templating 55
6 Outlook 57
References 57
Organic/Inorganic Composite Latexes: The Marriage of Emulsion Polymerization and Inorganic Chemistry 64
1 Introduction and Scope 67
2 Polymer--Silica Nanocomposite Particles 69
2.1 Emulsion Polymerization in the Presence of Silica Particles 70
2.1.1 Silica Particles Functionalized by Methacryloxy Propyl Trimethoxysilane 70
2.1.2 Macromonomer-Mediated Synthesis of Polymer--Silica Colloidal Clusters 74
2.1.3 Utilization of Auxiliary Comonomers 77
2.1.4 Cationic Initiators 78
2.1.5 Soap-Free Latexes 79
2.2 Coating of Polymer Latexes with a Silica Shell 81
3 Synthesis of Magnetic Latex Particles 83
3.1 Encapsulation of Iron Oxide Nanoparticles by Emulsion Polymerization 85
3.1.1 Surfactant Bilayer (Admicellar Polymerization) 85
3.1.2 Other Surface Coatings of Iron Oxide Nanoparticles 90
3.1.3 Emulsion Polymerization-Related Procedures 90
3.1.4 Heterocoagulation Followed by Emulsion Polymerization 96
3.1.5 Miscellaneous 97
3.2 Synthesis of Iron Oxide Nanoparticles in the Presence of Preformed Polymer Particles 98
4 Pigmented Latexes 100
4.1 Polymer Encapsulation of TiO2 Pigments 101
4.2 Titania-Coated Polymer Spheres and Hollow Titania Shells 103
4.3 Other Pigments 104
5 Polymer--Clay Nanocomposite Latexes 106
5.1 PCNs Elaborated by Conventional Emulsion Polymerization 107
5.2 Soap-Free Latexes Stabilized by Clay Platelets 111
6 Synthesis of Quantum Dot Tagged Latex Particles 113
6.1 Encapsulation of QDs Through Emulsion Polymerization 114
6.1.1 Conventional Emulsion Polymerization 114
6.1.2 Emulsion Polymerization-Related Procedures 116
6.1.3 Miscellaneous 117
6.2 Synthesis of Quantum Dots in the Presence of Polymer Particles 117
7 Synthesis of Metallic Latex Particles 120
7.1 Polymer Encapsulation of Metallic Particles Through Emulsion Polymerization 120
7.2 Polymer Particles as Template for the Synthesis of Metallic Shells and Metallic Nanoparticles 121
8 Summary and Outlook 125
References 126
Preparation of Hybrid Latex Particles and Core--Shell Particles Through the Use of Controlled Radical Polymerization Techniques in Aqueous Media 135
1 Introduction 138
2 Controlled/Living Radical Polymerization in Aqueous Dispersed Systems 138
2.1 Main Controlled/Living Radical Polymerization Methods 138
2.1.1 Main Methods Operating via a Reversible Termination Mechanism 139
2.1.2 Main Methods Operating via a Reversible Transfer Mechanism 141
2.2 Controlled/Living Radical Polymerization in Aqueous Dispersed Systems 142
2.2.1 Miniemulsion Polymerization 142
2.2.2 Emulsion Polymerization 143
3 Organic/Inorganic Hybrid Particles 144
3.1 Silica Nanoparticles 145
3.2 Iron Oxide 146
3.3 Other Metallic Oxides 148
3.4 Clays 151
4 (Nano)structured Particles 152
5 (Nano)capsules 155
5.1 Solid-Templated Synthesis 156
5.2 Oil-Templated Synthesis 157
6 Core--Shell Particles with Hydrophilic Shell and Hydrophobic Core via a Convergent Method 160
6.1 Reversible Transfer Methods 160
6.1.1 Reversible Addition--Fragmentation Chain Transfer Polymerization 161
6.1.2 Organotellurium-Mediated Radical Polymerization and Reverse Iodine Transfer Polymerization 172
6.2 Reversible Termination Methods 172
6.2.1 Nitroxide-Mediated Radical Polymerization 172
6.2.2 Atom Transfer Radical Polymerization 178
7 Core--Shell Particles via a Divergent Method: Grafting of Polymer Brush at the Surface of Polymer Particles 180
7.1 Grafting from Technique 181
7.1.1 Atom Transfer Radical Polymerization in Water 181
7.1.2 Atom Transfer Radical Polymerization in Organic Medium 186
7.1.3 Nitroxide-Mediated Radical Polymerization in Organic Medium 187
7.2 Grafting to Technique 188
8 Conclusion 188
References 189
Miniemulsion Polymerization as a Means to Encapsulate Organic and Inorganic Materials 194
1 Introduction 195
2 Encapsulation of Material Soluble in the Dispersed Phase 196
2.1 Dyes 197
2.1.1 Biomedical Application of Dye-Labeled Nanoparticles 201
2.2 Metal Complexes 203
2.3 Functional Organic Molecules 204
3 Capsule Formation 207
3.1 Capsule Formation by Phase Separation 208
3.2 Capsule Formation by Polymerization From or at the Interface 210
3.2.1 Initiation at the Interface 210
3.2.2 Generation of Polymer at the Interface: Polymerization and Polyaddition 212
3.3 Polymer Precipitation on Preformed Nanodroplets 215
4 Encapsulation of Material Insoluble in the Dispersed Phase 217
4.1 Organic Pigments and Carbon-Based Material 219
4.2 Inorganic Material 221
4.2.1 Silica 223
4.2.2 Clay 227
4.2.3 Iron Oxides (Magnetic Nanoparticles) 228
5 Summary 235
References 236
Organic--Inorganic Hybrid Magnetic Latex 246
1 Introduction 248
2 Applications of Magnetic Particles 250
2.1 Biomedical Applications of Magnetic Latex 250
2.1.1 In Vivo Applications 250
2.1.2 In Vitro Applications 252
3 Iron Oxide Magnetic Nanoparticles 254
3.1 Mechanical Size Reduction Method 255
3.2 Chemical Methods 255
3.2.1 Chemical Coprecipitation Method 255
3.2.2 Thermal Decomposition Method 258
3.2.3 Polyol Method 258
3.2.4 Aerosol Method 259
3.2.5 Microemulsion Method 259
4 Synthesis of Magnetic Latex 260
4.1 Magnetic Latex Fabrication in Preformed Polymers 260
4.1.1 Solvent Evaporation Process 260
4.1.2 Sol--Gel Method 261
4.1.3 Layer-by-Layer Process 261
4.2 In Situ Synthesis 262
4.2.1 Incorporation of Iron Oxide by the Precipitation Process 262
4.2.2 Deposition of Magnetic Metals 265
4.3 Polymerizations of Monomer in the Presence of Magnetic Nanoparticles 266
4.3.1 Suspension Polymerization 266
4.3.2 Dispersion Polymerization 269
4.3.3 Emulsion Polymerization 271
4.3.4 Microemulsion Polymerization 281
4.3.5 Miniemulsion Polymerization 281
5 Concluding Remarks 285
References 286
Index 291