Principles and Applications of Emulsion Polymerization

by Chern, Chorng-Shyan

• ISBN13: 9780470124314
• ISBN10: 0470124318
• Edition: 1st
• Format: Hardcover
• Copyright: 2008-08-04
• Publisher: Wiley

Summary

Up-to-date coverage of methods of emulsion polymerization This book provides a comprehensive reference on emulsion polymerization methods,focusing on the fundamental mechanisms and kinetics of each process, as well as howthey can be applied to the manufacture of environmentally friendly polymeric materials. Topics covered include: * Conventional emulsion polymerization * Miniemulsion polymerization * Microemulsion polymerization * Industrial emulsion polymerization processes (primarily the semibatch and continuous reactions systems) * The role of various colloidal phenomena in emulsion polymerization * Important end-use properties of emulsion polymer (latex) products * Information on industrial applications in paints, coatings, adhesives, paper and board, and more This is a hands-on reference for graduate students and professionals in polymerchemistry, chemical engineering, and materials science who are involved in researchon coatings, adhesives, rubber, latex, paints, finishes, and other materials that can becreated using various methods of emulsion polymerization.

Author Biography

Chorng-Shyan Chern, PhD, is Professor in the Department of ChemicalEngineering at the National Taiwan University of Science and Technology in Taipei. Hereceived his PhD from the Georgia Institute of Technology, and was associated withUnited Merchants, S.C. Johnson Wax, and Union Carbide during his industrial career. His major research interests involve nucleation, growth, and stability of latex particlesduring emulsion polymerization.

Table of Contents

Preface	p. xi
Introduction	p. 1
Free Radical Polymerization	p. 1
Free Radical Polymerization Mechanisms	p. 1
Free Radical Polymerization Kinetics	p. 3
Emulsion Polymerization	p. 5
Conventional Emulsion Polymerization	p. 5
Emulsion Polymerization Processes	p. 6
Miniemulsion Polymerization	p. 8
Microemulsion Polymerization	p. 9
Inverse Emulsion Polymerization	p. 10
Colloidal Stability	p. 11
A Critical but Often Ignored Issue	p. 11
Electrostatic Interactions	p. 12
Steric Interactions	p. 13
Mechanical Stability	p. 14
Some Performance Properties for Industrial Applications	p. 15
Rheology	p. 15
Film Formation	p. 16
References	p. 19
Interfacial Phenomena	p. 23
Thermodynamic Consideration	p. 23
Emulsification of Oil in Water	p. 23
Interfaces	p. 25
Surfactant Molecules Adsorbed at an Interface	p. 26
Surfactants	p. 26
Critical Micelle Concentration (CMC)	p. 27
Hydrophile-Lipophile Balance (HLB)	p. 27
Solubility Parameter	p. 29
Colloidal Stability	p. 32
Van der Waals Forces	p. 32
Electrostatic Interactions	p. 36
Steric Interactions	p. 44
Kinetics of Flocculation	p. 48
References	p. 50
Particle Nucleation Mechanisms	p. 53
Micellar Nucleation	p. 54
Harkins-Smith-Ewart Theory	p. 54
Competitive Absorption of Free Radicals by Micelles and Particle Nuclei	p. 57
Homogeneous Nucleation	p. 60
Formation of Particle Nuclei in the Continuous Aqueous Phase	p. 60
Hansen-Ugelstad-Fitch-Tsai (HUFT) Model	p. 63
Coagulative Nucleation	p. 65
General Features of Coagulative Nucleation	p. 65
Coagulative Nucleation Model Development	p. 66
Mixed Mode of Particle Nucleation Mechanisms	p. 68
Surfactant-Free Emulsion Polymerization	p. 71
Experimental Work on Particle Nucleation	p. 76
A Dilemma about Particle Nucleation Mechanisms	p. 76
Some Representative Experimental Data of Particle Nucleation	p. 77
Some Potential Techniques for Studying Particle Nucleation	p. 82
Effects of Surfactant Concentration on Particle Nucleation	p. 86
Nonionic and Mixed Surfactant Systems	p. 87
Nonionic Surfactant Systems	p. 88
Mixed Anionic and Nonionic Surfactant Systems	p. 89
References	p. 91
Emulsion Polymerization Kinetics	p. 95
Emulsion Polymerization Kinetics	p. 96
Smith-Ewart Theory	p. 96
Pioneering Kinetic Models for Predicting Average Number of Free Radicals per Particle	p. 100
Absorption of Free Radicals by Latex Particles	p. 103
Collision- and Diffusion-Controlled Models	p. 104
Propagation-Controlled Model	p. 106
Some Controversial Issues	p. 108
Desorption of Free Radicals Out of Latex Particles	p. 109
Desorption of Free Radicals in Emulsion Homopolymerization Systems	p. 110
Desorption of Free Radicals in Emulsion Copolymerization Systems	p. 112
Effect of Interfacial Properties on Desorption of Free Radicals	p. 113
Growth of Latex Particles	p. 114
Thermodynamic Consideration	p. 114
Concentrations of Comonomers in Emulsion Copolymerization Systems	p. 116
Competitive Growth of Latex Particles	p. 119
Polymer Molecular Weight	p. 120
References	p. 123
Miniemulsion Polymerization	p. 128
Polymerization in Monomer Droplets	p. 129
Stability of Monomer Emulsions	p. 130
Ostwald Ripening Effect	p. 130
Role of Costabilizer in Stabilizing Monomer Emulsions	p. 132
Type of Costabilizers in Miniemulsion Polymerization	p. 133
Miniemulsion Polymerization Mechanisms and Kinetics	p. 135
Initial Conditions for Miniemulsion Polymerization Systems	p. 135
Particle Nucleation Mechanisms	p. 136
Effect of Functional Monomers and Initiators on Particle Nucleation	p. 140
Polymerization Kinetics	p. 142
Versatility of Miniemulsion Polymerization	p. 145
Catalytic Chain Transfer Reaction	p. 147
Living Free Radical Polymerization	p. 147
Step Polymerization	p. 148
References	p. 150
Microemulsion Polymerization	p. 154
Introduction	p. 154
Formation and Microstructure of Microemulsions	p. 155
Formation of Microemulsions	p. 155
Factors that Govern Microemulsion Structures	p. 157
O/W Microemulsion Polymerization	p. 158
General Features	p. 158
Polymerization Mechanisms and Kinetics	p. 159
W/O Microemulsion Polymerization	p. 167
Polymerization in Continuous or Bicontinuous Phases of Microemulsions	p. 169
References	p. 170
Semibatch and Continuous Emulsion Polymerizations	p. 175
Semibatch Emulsion Polymerization	p. 175
Pseudo-Steady-State Polymerization Behavior	p. 175
Polymerization Mechanisms and Kinetics	p. 177
Mathematical Modeling Studies	p. 186
Continuous Emulsion Polymerization	p. 187
General Features of Continuous Emulsion Polymerization Processes	p. 187
Particle Nucleation and Growth Mechanisms	p. 191
Development of Commercial Continuous Emulsion Polymerization Processes	p. 194
References	p. 196
Emulsion Polymerizations in Nonuniform Latex Particles	p. 200
Origin of Nonuniform Latex Particles	p. 200
Seeded Emulsion Polymerizations	p. 201
Factors Affecting Particle Morphology	p. 202
Effect of Initiators	p. 202
Effect of Monomer Addition Methods	p. 203
Effect of Polymer Molecular Weight	p. 204
Effect of Volume Fractions of Polymer Pairs	p. 205
Effect of Polymerization Temperature	p. 205
Morphology Development in Latex Particles	p. 205
Thermodynamic Considerations	p. 205
Nonequilibrium Morphology Development	p. 206
Techniques for Characterization of Particle Morphology	p. 210
Polymerization Kinetics in Nonuniform Latex Particles	p. 211
Pioneering Studies	p. 212
Effect of Distribution of Free Radicals in Nonuniform Latex Particles	p. 213
References	p. 220
Applications of Emulsion Polymers	p. 223
Physical Properties of Emulsion Polymers	p. 224
Effect of Polymer Molecular Weight	p. 224
Effect of Polymer Morphology	p. 225
Effect of Crosslinking Reactions	p. 229
Rheological Properties of Emulsion Polymers	p. 230
Film Formation of Emulsion Polymers	p. 233
Foaming and Antifoaming Agents	p. 236
Wetting	p. 238
Surface Modifications	p. 241
Stability of Latex Products	p. 242
References	p. 245
Index	p. 248
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