كتاب Vinyl Acetate Emulsion Polymerization and Copolymerization With Acrylic Monomers

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Vinyl Acetate Emulsion Polymerization and Copolymerization With Acrylic Monomers
H. Yildirim Erbil

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Contents
1 Introduction
1.1 History of Emulsion Polymerization
1.2 History of Emulsion Polymerization of Vinyl Acetate
1.3 A Short Review of the Free Radical Addition Polymerization
1.3.1 Initiation
1.3.2 Propagation
1.3.3 Termination
1.3.3.1 Biradical Coupling
1.3.3.2 Disproportionation
1.3.4 Degree of Polymerization
1.3.5 Chain Transfer
References
2 General Emulsion Polymerization
2.1 Basic Aspects
2.2 Emulsion Polymerization of Hydrophobic Monomers
2.2.1 Smith-Ewart Kinetic Theory
2.2.2 Gardon Kinetic Theory
2.2.3 Other Kinetic Effects
2.2.3.1 The Effect of Electrolyte Concentration
2.2.3.2 Effect of the Structure of the Emulsifier
2.2.3.3 The Effect of Nonionic Emulsifiers
2.2.3.4 Monomer Solubilization and the Duration
of Interval I
2.2.3.5 The Effect of Monomer-to-Water Ratio
2.2.3.6 The Effect of Temperature
2.2.3.7 The Effect of Agitation
2.2.3.8 The Effect of Conversion
2.2.3.9 Gel Effect
2.3 Inverse Emulsion Polymerization
References
3 Emulsion Homopolymerization of Vinyl Acetate
3.1 General Aspects
3.2 Literature Survey on the Mechanism of Vinyl
Acetate Emulsion Homopolymerization
3.3 Branching Mechanisms in Vinyl Acetate Emulsion
Polymerization
2000 by CRC Press LLC3.4 Radiation-Induced Vinyl Acetate Emulsion Polymerization
References
4 Properties and Roles of Ingredients in Vinyl Acetate Emulsion
Homopolymerization
4.1 Vinyl Acetate Monomer
4.1.1 Synthesis and Manufacture of Vinyl Acetate Monomer
4.1.2 Physical Properties of Vinyl Acetate Monomer
4.1.3 Chemical Properties of Vinyl Acetate Monomer
4.1.3.1 Hydrolysis of Vinyl Acetate
4.1.3.2 Transesterification of Vinyl Acetate
4.1.3.3 Addition Reactions
4.1.3.4 Oxidation of Vinyl Acetate
4.1.3.5 Decomposition of Vinyl Acetate
4.1.3.6 Other Reactions of Vinyl Acetate
4.1.4 Inhibition of Vinyl Acetate Monomer
4.1.5 Storage and Handling of Vinyl Acetate Monomer
4.1.5.1 Bulk Storage in the Plant
4.1.5.2 Materials of Construction
4.1.5.3 Tank Cars, Trucks, and Drums
4.1.5.4 Physiological Properties
4.1.6 Analysis of Vinyl Acetate Monomer
4.2 Polyvinyl Acetate Polymer
4.2.1 Physical and Mechanical Properties
4.2.2 Solubility in Solvents and Fractionation
4.2.3 Polymer Molecular Weight Determination
by Viscometry
4.2.4 Hydrolysis
4.2.5 Mechanical and Thermal Degradation
4.2.6 Light Stability and Biological Degradation
4.3 Initiators
4.3.1 Thermal Dissociation Type Free Radical Initiators
4.3.1.1 Persulfates
4.3.1.2 Peroxides
4.3.2 Redox Type Free Radical Initiators
4.3.2.1 Persulfate–Bisulfite
4.3.2.2 Peroxide–Iron (II) Salt
4.3.3 Other Free Radical Initiators
4.3.4 Other Methods of Initiation
4.4 Water
4.5 Emulsifiers
4.5.1 Anionic Emulsifiers
4.5.1.1 Sodium Alcohol Sulfate
4.5.1.2 Alkyl Aryl Sodium Sulfonate
4.5.1.3 Dialkyl Ester of Sodium Sulfosuccinic Acid
2000 by CRC Press LLC4.5.1.4 Fluorinated Anionic Emulsifiers
4.5.1.5 Phosphate Ester Anionic Emulsifiers
4.5.2 Cationic Emulsifiers
4.5.3 Nonionic Emulsifiers
4.5.3.1 Polyoxyethylenated Alkylphenol Nonionic
Emulsifiers
4.5.3.2 Polyoxyethylenated Alcohol Nonionic
Emulsifiers
4.5.3.3 Ethylene Oxide–Propylene Oxide Block
Copolymer Nonionic Emulsifiers
4.5.3.4 Other Nonionic Emulsifiers
4.5.4 Amphoteric Emulsifiers
4.6 Protective Colloids
4.6.1 Polyvinyl Alcohol
4.6.2 Hydroxyethyl Cellulose
4.7 pH and Ionic Strength Controllers
4.8 Others
4.8.1 Chain Transfer Agents
4.8.2 Retarders
4.8.3 Antifoams
4.8.4 Plasticizing and Coalescing Aids
4.8.5 Biocides and Fungicides
4.8.6 Antioxidants and Ultraviolet Light Absorbers
4.8.7 Latex Postadditives
References
5 Vinyl Acetate Copolymerization with Acrylic Monomers
5.1 Modification of Polyvinyl Acetate Latex Properties by
Copolymerization
5.2 Acrylic Monomers
5.2.1 Inhibition of Acrylic Monomers
5.2.1.1 Inhibitor Selection
5.2.1.2 Inhibitor Removal by Distillation
5.2.1.3 Inhibitor Removal by Washing
5.2.1.4 Inhibitor Removal by Ion-Exchange
5.2.2 Acrylic Homopolymer Properties
5.3 Copolymerization and Reactivity Ratios
5.3.1 Copolymerization
5.3.2 Copolymer Composition Equation
5.3.3 Experimental Determination of Reactivity Ratios
5.3.4 Variation of Copolymer Composition with Conversion
5.3.5 The Q-e Scheme
5.3.6 Comonomer and Emulsifier Addition Strategies
5.3.7 Effects of Comonomer Addition Rates
2000 by CRC Press LLC5.3.7.1 Control of Copolymerization Rate
5.3.7.2 Control of Copolymer Composition
5.3.7.3 Coagulum Formation
5.4 Vinyl Acetate/Acrylic Batch and Semicontinuous Emulsion
Copolymerizations
5.5 Particle Morphology of Copolymers
5.6 Film Properties of Copolymers
References
6 Colloidal Stability of Vinyl Acetate Homo- and Copolymer Latices
6.1 Basic Phonemena
6.1.1 Electrical Double Layer Interaction Energies
6.1.1.1 Surface Charge Density
6.1.1.2 Surface Potential
6.1.2 van der Waals Interaction Energies
6.1.3 Potential Energy Curves
6.2 Steric Stabilization
6.2.1 Mechanism of Steric Stabilization
6.2.2 Steric Interaction Energy
6.2.3 Effect of the Size of Particle and Stabilizing Polymer
6.2.4 Depletion Flocculation
6.3 Coagulation of Polymer Colloids
6.3.1 Coagulation of Electrostatically Stabilized Colloids
6.3.1.1 Critical Coagulation Concentration
6.3.1.2 Effects of Organic Electrolytes
6.3.2 Coagulation of Sterically Stabilized Colloids
6.3.3 Coagulation of Colloids by Freezing and Thawing
6.3.4 Effect of a Shear Gradient on Colloid Stability
6.4 Coagulation during the Process of Particle Formation
6.5 Colloidal Stability of Vinyl Acetate Homo- and Copolymer
Latices
References
7 Experimental Determination of Latex Properties
7.1 Total Solids Content
7.2 Density
7.3 pH
7.4 Viscosity
7.4.1 Brookfield Viscometers
7.4.2 Cone-Plate and Double-Cone Viscometers
7.4.3 Rheogonimeters
7.4.4 Orifice-Type Vicometers
7.5 Surface Tension
2000 by CRC Press LLC7.6 Mean Particle Size and Particle Size Distribution
7.6.1 Optical Microscopy — Dark Field Microscopy
7.6.2 Electron Microscopy
7.6.3 Fractional Creaming
7.6.4 Soap Titration
7.6.5 Light Scattering
7.6.6 Quasi-Elastic Light Scattering
(Photon Correlation Spectroscopy)
7.6.7 Turbidity
7.6.8 Hydrodynamic Chromatography
7.6.9 Size Exclusion Chromatography
7.7 Free Monomer Content
7.8 Coagulum Content
7.9 Mercaptan Content
7.10 Colloidal Stability
7.10.1 Chemical Stability
7.10.2 Mechanical Stability
7.11 Monomer Conversion during Polymerization
7.12 Latex Cleaning
7.13 Average Molecular Weight and Molecular Weight Distribution
7.13.1 Osmometry
7.13.2 Light Scattering Methods
7.13.3 Viscometry
7.13.4 Ultracentrifugation
7.13.5 Gel Permeation (Size-Exclusion) Chromatography
7.13.6 Field-Flow Fractionation
7.14 Graft and Cross-Linked Polymer Content
7.14.1 Graft Polymer Content
7.14.2 Cross-Linked Polymer Content
7.15 Chemical Composition of Copolymers
7.15.1 Infrared Spectroscopy
7.15.2 Nuclear Magnetic Resonance Spectroscopy
7.15.3 Pyrolysis Gas Chromatography
7.15.4 Chemical Composition Distribution
7.15.5 Monomer Sequence Distribution
7.16 Surface Tension of Dried Latex Films
7.16.1 Critical Surface Tension of Polymer
7.16.2 Surface Tension Components of Polymers
7.17 Thermal Properties of Latex Films
7.18 Mechanical Properties of Latex Films
References
8 Factors Affecting the Final Properties of Polyvinyl AcetateBased Latices
2000 by CRC Press LLC8.1 Practical Approaches to Desired PVAc Latex Properties
8.1.1 Brief Description of VAc Emulsion Polymerization
8.1.2 To Reduce Particle Size
8.1.3 To Increase Particle Size
8.1.4 To Increase Latex Viscosity
8.1.5 To Increase Molecular Weight of Polymer
8.1.6 Conditions for Unstable Latices
8.2 The Effect of the Type of the Polyvinyl Alcohol and Cellulosic
Protective Colloids on PVAc Homopolymers
8.3 The Choice and the Role of Acrylic Ester Comonomers
and Stabilization of PolyVAc Copolymer Latices by Monomeric
Carboxylic Groups
8.4 The Role of Monomer Addition Methods and Feed Rates
on PVAc-Acrylate Copolymer Composition
in the Semicontinuous Process
References
Appendix 1 Properties of Vinyl Acetate Monomer
Appendix 2 Commercial Vinyl Acetate Specifications
Appendix 3 Wet Analysis of Vinyl Acetate Monomer
Appendix 4 Solubility of Polyvinyl Acetate in Various Solvents
Appendix 5 Polyvinyl Acetate Latex Specifications
Appendix 6 Acrylic Ester Monomer Specifications
Appendix 7 Wet Analysis of Acry

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