Vinyl Acetate Emulsion Polymerization and Copolymerization with Acrylic Monomers

 Content: 1.1 History of Emulsion Polymerization 3 --
 1.2 History of Emulsion Polymerization of Vinyl Acetate 6 --
 1.3 A Short Review of the Free Radical Addition Polymerization 10 --
 1.3.1 Initiation 10 --
 1.3.2 Propagation 11 --
 1.3.3 Termination 12 --
 1.3.3.1 Biradical Coupling 12 --
 1.3.3.2 Disproportionation 12 --
 1.3.4 Degree of Polymerization 13 --
 1.3.5 Chain Transfer 14 --
 2 General Emulsion Polymerization 21 --
 2.2 Emulsion Polymerization of Hydrophobic Monomers 23 --
 2.2.1 Smith-Ewart Kinetic Theory 28 --
 2.2.2 Gardon Kinetic Theory 33 --
 2.2.3 Other Kinetic Effects 35 --
 2.2.3.1 Effect of Electrolyte Concentration 35 --
 2.2.3.2 Effect of the Structure of the Emulsifier 36 --
 2.2.3.3 Effect of Nonionic Emulsifiers 36 --
 2.2.3.4 Monomer Solubilization and the Duration of Interval I 36 --
 2.2.3.5 Effect of Monomer-to-Water Ratio 37 --
 2.2.3.6 Effect of Temperature 37 --
 2.2.3.7 Effect of Agitation 38 --
 2.2.3.8 Effect of Conversion 38 --
 2.2.3.9 Gel Effect 39 --
 2.3 Inverse Emulsion Polymerization 39 --
 3 Emulsion Homopolymerization of Vinyl Acetate 45 --
 3.1 General Aspects 45 --
 3.2 Literature Survey on the Mechanism of Vinyl Acetate Emulsion Homopolymerization 48 --
 3.3 Branching Mechanisms in Vinyl Acetate Emulsion Polymerization 109 --
 3.4 Radiation-Induced Vinyl Acetate Emulsion Polymerization 116 --
 4 Properties and Roles of Ingredients in Vinyl Acetate Emulsion Homopolymerization 127 --
 4.1 Vinyl Acetate Monomer 127 --
 4.1.1 Synthesis and Manufacture of Vinyl Acetate Monomer 127 --
 4.1.2 Physical Properties of Vinyl Acetate Monomer 129 --
 4.1.3 Chemical Properties of Vinyl Acetate Monomer 130 --
 4.1.3.1 Hydrolysis of Vinyl Acetate 130 --
 4.1.3.2 Transesterification of Vinyl Acetate 130 --
 4.1.3.3 Addition Reactions 131 --
 4.1.3.4 Oxidation of Vinyl Acetate 131 --
 4.1.3.5 Decomposition of Vinyl Acetate 131 --
 4.1.3.6 Other Reactions of Vinyl Acetate 131 --
 4.1.4 Inhibition of Vinyl Acetate Monomer 132 --
 4.1.5 Storage and Handling of Vinyl Acetate Monomer 132 --
 4.1.5.1 Bulk Storage in the Plant 132 --
 4.1.5.2 Materials of Construction 133 --
 4.1.5.3 Tank Cars, Trucks, and Drums 133 --
 4.1.5.4 Physiological Properties 133 --
 4.1.6 Analysis of Vinyl Acetate Monomer 134 --
 4.2 Polyvinyl Acetate Polymer 134 --
 4.2.1 Physical and Mechanical Properties 134 --
 4.2.2 Solubility in Solvents and Fractionation 135 --
 4.2.3 Polymer Molecular Weight Determination by Viscometry 135 --
 4.2.4 Hydrolysis 136 --
 4.2.5 Mechanical and Thermal Degradation 137 --
 4.2.6 Light Stability and Biological Degradation 137 --
 4.3 Initiators 138 --
 4.3.1 Thermal Dissociation Type Free Radical Initiators 138 --
 4.3.1.1 Persulfates 139 --
 4.3.1.2 Peroxides 140 --
 4.3.2 Redox Type Free Radical Initiators 140 --
 4.3.2.1 Persulfate-Bisulfite 142 --
 4.3.2.2 Peroxide-Iron (II) Salt 142 --
 4.3.3 Other Free Radical Initiators 143 --
 4.3.4 Other Methods of Initiation 143 --
 4.4 Water 144 --
 4.5 Emulsifiers 144 --
 4.5.1 Anionic Emulsifiers 146 --
 4.5.1.1 Sodium Alcohol Sulfate 146 --
 4.5.1.2 Alkyl Aryl Sodium Sulfonate 146 --
 4.5.1.3 Dialkyl Ester of Sodium Sulfosuccinic Acid 147 --
 4.5.1.4 Fluorinated Anionic Emulsifiers 147 --
 4.5.1.5 Phosphate Ester Anionic Emulsifiers 147 --
 4.5.2 Cationic Emulsifiers 147 --
 4.5.3 Nonionic Emulsifiers 148 --
 4.5.3.1 Polyoxyethylenated Alkylphenol Nonionic Emulsifiers 148 --
 4.5.3.2 Polyoxyethylenated Alcohol Nonionic Emulsifiers 149 --
 4.5.3.3 Ethylene Oxide-Propylene Oxide Block Copolymer Nonionic Emulsifiers 149 --
 4.5.3.4 Other Nonionic Emulsifiers 149 --
 4.5.4 Amphoteric Emulsifiers 149 --
 4.6 Protective Colloids 149 --
 4.6.1 Polyvinyl Alcohol 150 --
 4.6.2 Hydroxyethl Cellulose 154 --
 4.7 pH and Ionic Strength Controllers 155 --
 4.8 Others 156 --
 4.8.1 Chain Transfer Agents 156 --
 4.8.2 Retarders 156 --
 4.8.3 Antifoams 156 --
 4.8.4 Plasticizing and Coalescing Aids 157 --
 4.8.5 Biocides and Fungicides 157 --
 4.8.6 Antioxidants and Ultraviolet Light Absorbers 158 --
 4.8.7 Latex Postadditives 158 --
 5 Vinyl Acetate Copolymerization with Acrylic Monomers 165 --
 5.1 Modification of Polyvinyl Acetate Latex Properties by Copolymerization 165 --
 5.2 Acrylic Monomers 166 --
 5.2.1 Inhibition of Acrylic Monomers 167 --
 5.2.1.1 Inhibitor Selection 168 --
 5.2.1.2 Inhibitor Removal by Distillation 168 --
 5.2.1.3 Inhibitor Removal by Washing 169 --
 5.2.1.4 Inhibitor Removal by Ion-Exchange 169 --
 5.2.2 Acrylic Homopolymer Properties 169 --
 5.3 Copolymerization and Reactivity Ratios 170 --
 5.3.1 Copolymerization 170 --
 5.3.2 Copolymer Composition Equation 171 --
 5.3.3 Experimental Determination of Reactivity Ratios 173 --
 5.3.4 Variation of Copolymer Composition with Conversion 174 --
 5.3.5 Q-e Scheme 176 --
 5.3.6 Comonomer and Emulsifier Addition Strategies 177 --
 5.3.7 Effects of Comonomer Addition Rates 178 --
 5.3.7.1 Control of Copolymerization Rate 178 --
 5.3.7.2 Control of Copolymer Composition 179 --
 5.3.7.3 Coagulum Formation 180 --
 5.4 Vinyl Acetate/Acrylic Batch and Semicontinuous Emulsion Copolymerizations 181 --
 5.5 Particle Morphology of Copolymers 198 --
 5.6 Film Properties of Copolymers 200 --
 6 Colloidal Stability of Vinyl Acetate Homo- and Copolymer Latices 207 --
 6.1 Basic Phonemena 207 --
 6.1.1 Electrical Double Layer Interaction Energies 208 --
 6.1.1.1 Surface Charge Density 211 --
 6.1.1.2 Surface Potential 211 --
 6.1.2 van der Waals Interaction Energies 214 --
 6.1.3 Potential Energy Curves 216 --
 6.2 Steric Stabilization 220 --
 6.2.1 Mechanism of Steric Stabilization 220 --
 6.2.2 Steric Interaction Energy 223 --
 6.2.3 Effect of the Size of Particle and Stabilizing Polymer 225 --
 6.2.4 Depletion Flocculation 227 --
 6.3 Coagulation of Polymer Colloids 227 --
 6.3.1 Coagulation of Electrostatically Stabilized Colloids 227 --
 6.3.1.1 Critical Coagulation Concentration 228 --
 6.3.1.2 Effects of Organic Electrolytes 229 --
 6.3.2 Coagulation of Sterically Stabilized Colloids 229 --
 6.3.3 Coagulation of Colloids by Freezing and Thawing 230 --
 6.3.4 Effect of a Shear Gradient on Colloid Stability 231 --
 6.4 Coagulation during the Process of Particle Formation 232 --
 6.5 Colloidal Stability of Vinyl Acetate Homo- and Copolymer Latices 233 --
 7 Experimental Determination of Latex Properties 243 --
 7.1 Total Solids Content 243 --
 7.2 Density 243 --
 7.3 pH 243 --
 7.4 Viscosity 244 --
 7.4.1 Brookfield Viscometers 244 --
 7.4.2 Cone-Plate and Double-Cone Viscometers 245 --
 7.4.3 Rheogonimeters 245 --
 7.4.4 Orifice-Type Vicometers 245 --
 7.5 Surface Tension 246 --
 7.6 Mean Particle Size and Particle Size Distribution 247 --
 7.6.1 Optical Microscopy --
 Dark Field Microscopy 248 --
 7.6.2 Electron Microscopy 249 --
 7.6.3 Fractional Creaming 250 --
 7.6.4 Soap Titration 250 --
 7.6.5 Light Scattering 251 --
 7.6.6 Quasi-Elastic Light Scattering (Photon Correlation Spectroscopy) 252 --
 7.6.7 Turbidity 252 --
 7.6.8 Hydrodynamic Chromatography 253 --
 7.6.9 Size Exclusion Chromatography 253 --
 7.7 Free Monomer Content 253 --
 7.8 Coagulum Content 254 --
 7.9 Mercaptan Content 254 --
 7.10 Colloidal Stability 254 --
 7.10.1 Chemical Stability 254 --
 7.10.2 Mechanical Stability 254 --
 7.11 Monomer Conversion during Polymerization 255 --
 7.12 Latex Cleaning 256 --
 7.13 Average Molecular Weight and Molecular Weight Distribution 256 --
 7.13.1 Osmometry 257 --
 7.13.2 Light Scattering Methods 257 --
 7.13.3 Viscometry 257 --
 7.13.4 Ultracentrifugation 257 --
 7.13.5 Gel Permeation (Size-Exclusion) Chromatography 258 --
 7.13.6 Field-Flow Fractionation 258 --
 7.14 Graftr and Cross-Linked Polymer Content 258 --
 7.14.1 Graft Polymer Content 258 --
 7.14.2 Cross-Linked Polymer Content 259 --
 7.15 Chemical Composition of Copolymers 259 --
 7.15.1 Infrared Spectroscopy 259 --
 7.15.2 Nuclear Magnetic Resonance Spectroscopy 259 --
 7.15.3 Pyrolysis Gas Chromatography 260 --
 7.15.4 Chemical Composition Distribution 260 --
 7.15.5 Monomer Sequence Distribution 260 --
 7.16 Surface Tension of Dried Latex Films 260 --
 7.16.1 Critical Surface Tension of Polymer 261 --
 7.16.2 Surface Tension Components of Polymers 261 --
 7.17 Thermal Properties of Latex Films 263 --
 7.18 Mechanical Properties of Latex Films 264 --
 8 Factors Affecting the Final Properties of Polyvinyl Acetate-Based Latices 273 --
 8.1 Practical Approaches to Desired PVAc Latex Properties 273 --
 8.1.1 Brief Description of VAc Emulsion Polymerization 273 --
 8.1.2 To Reduce Particle Size 279 --
 8.1.3 To Increase Particle Size 279 --
 8.1.4 To Increase Latex Viscosity 280 --
 8.1.5 To Increase Molecular Weight of Polymer 280 --
 8.1.6 Conditions for Unstable Latices 280 --
 8.2 Effect of the Type of the Polyvinyl Alcohol and Cellulosic Protective Colloids on PVAc Homopolymers 281 --
 8.3 Choice and the Role of Acrylic Ester Comonomers and Stabilization of PolyVAc Copolymer Latices by Monomeric Carboxylic Groups 286 --
 8.4 Role of Monomer Addition Methods and Feed Rates on PVAc-Acrylate Copolymer Composition in the Semicontinuous Process 288 --
 Appendix 1 Properties of Vinyl Acetate Monomer 297 --
 Appendix 2 Commercial Vinyl Acetate Specifications 301 --
 Appendix 3 Wet Analysis of Vinyl Acetate Monomer 303 --
 Appendix 4 Solubility of Polyvinyl Acetate in Various Solvents 307 --
 Appendix 5 Polyvinyl Acetate Latex Specifications 309 --
 Appendix 6 Acrylic Ester Monomer Specifications 311 --
 Appendix 7 Wet Analysis of Acrylic Ester Monomers 313.
 Abstract:             
              Integrating knowledge with research developments, this book provides the background for understanding the mechanism and kinetics of emulsion polymerization initiated in the aqueous phase and some of the practical problems of latex production. It presents an overview of industrial practices, applications, and the fundamental material.                 Read more...