Emulsion Polymerization and Emulsion Polymers

Transcription

1 Inventor Nr i^f- Emulsion Polymerization and Emulsion Polymers Edited by Peter A. Lovell Manchester Materials Science Centre, University of Manchester and UMIST, Manchester, UK and Mohamed S. El-Aasser Emulsion Polymers Institute and Department of Chemical Engineering, Lehigh University, Bethlehem, PA, USA Bibliothek Fachbereich Chemie Technische Universitat Darmstadt JOHN WILEY AND SONS Chichester New York Weinheim Brisbane Singapore Toronto

2 Contents Contributors xiii Preface xvii Glossary of Common Abbreviations, Acronyms and Symbols... xxi Section I: Basic Science 1 Chapter 1 Free-radical Polymerization 3 Peter A. Lovell 1.1 Introduction Chain Polymerization Chemistry of Free-radical Polymerization Kinetics of Homogeneous Free-radical Polymerization Stereochemistry of Polymerization , Free-radical Copolymerization Homogeneous Free-radical Polymerization Processes References 35 Chapter 2 Features of Emulsion Polymerization 37 Mohamed S. El-Aasser and E. David Sudol 2.1 Introduction "Classical" Emulsion Polymerization Basic Ingredients Emulsion Polymerization Processes Overall Description of Emulsion Polymerization Basic Issues in Emulsion Polymerization Other Controversial Issues in Emulsion Polymerization References 55

3 vi CONTENTS Chapter 3 Stabilization of Polymer Colloid Dispersions 59 Ronald H. Ottewill 3.1 Introduction Electrical Double Layer The Potential Energy of Interaction Between Particles Coagulation of Polymer Colloids The Influence of Various Electrolytes on Colloid Stability Steric Stabilization Depletion Effects Non-adsorbing Molecules Apologia References 117 Section II: Theory 123 Chapter 4 Harkins, Smith-Ewart and Related Theories 125 Alexander S. Dunn 4.1 Historical Development of Emulsion Polymerization The Literature of Emulsion Polymerization Theories of Emulsion Polymerization Emulsion Polymerization Kinetics Swelling of Latex Particles Polymerizations with Non-ionic Emulsifiers Polymerizations using Oil-soluble Initiators Exact Solutions of the Recursion Equation Appendix 4.1: Derivation of the Smith-Ewart Equations Appendix 4.2: Derivation of the Morton-Kaizerman-Altier Equation Appendix 4.3: Gardon's Equations References 159 Chapter 5 Modelling Rates, Particle Size Distributions and Molar Mass Distributions 165 Robert G. Gilbert 5.1 Introduction Mechanisms and Evolution Equations Comparison with Experiment Conclusions References 201

4 CONTENTS Section III: Practice 205 Chapter 6 Formulation Components 207 Andrew Klein and Eric S. Daniels 6.1 Introduction Monomers Crosslinking Systems Water Initiation Surfactants Protective Colloids Rheological Modifiers Chain Transfer Agents Buffers Post-additives Biocides and Fungicides Antioxidants and Ultraviolet Light Absorbers The Use of Experimental Design in Latex Synthesis and Formulation Summary References 234 Chapter 7 Batch and Semi-batch Processes 239 Peter A. Lovell 7.1 Introduction Distinction Between Batch and Semi-batch Processes Batch Processes Semi-batch Processes References 273 Chapter 8 Continuous Processes 277 Gary W. Poehlein 8.1 Introduction Continuous^Reactor Systems Perfectly Mixed CSTR The CSTR as a Research Tool CSTR Modelling and Control Issues Tubular Reactors Other Reactor Systems References 291 vii

5 viii CONTENTS Chapter 9 Control of Particle Morphology 293 Victoria L. Dimonie, Eric S. Daniels, Olga L. Shaffer and Mohamed S. El-Aasser 9.1 Introduction r^ "Core-Shell" Model of Particle Growth in Emulsion Polymerization Prediction of Composite Latex Particle Morphology Importance of Polymerization Process Parameters in Controlling Particle Morphology Characterization Techniques Utilized for the Study of Composite Latex Morphologies Summary References 323 Chapter 10 Process Modelling and Control 327 F. Joseph Schork 10.1 Mathematical Modelling Reactor Design and Operation On-line Sensors Process Control References 340 Chapter 11 Latex Polymer Characterization 343 Anton L. German, Alex M. van Herk, Harold A. S. Schoonbrood and Annemieke M. Aerdts 11.1 Monomer Conversion Molecular Characterization Macroscopic Characterization References 377 Chapter 12 Measurement of Particle Size and Particle Size Distribution 385 Edward A. Collins 12.1 Introduction Essential Background Key Particle Size Methods Guidelines to Instrument Selection Comparative Analysis Recent Developments and Trends References 432

6 CONTENTS ix Chapter 13 Latex Rheology 437 Edward J. Schaller 13.1 Introduction to Rheology Dispersion Rheology Thickeners for Latex Formulations References 463 Chapter 14 The Formation and Properties of Latex Films Mitchell A. Winnik 14.1 Introduction How Latex Dispersions Dry Packing and Deformation Healing of the Interfaces Mechanical Properties and Crosslinked Latex Films Final Comments Acknowledgements References 515 Section IV: Major Industrial Uses 519 Chapter 15 Diene-based Synthetic Rubbers 521 David C. Blackley 15.1 Some General Considerations Styrene-Butadiene Rubbers Acrylonitrile-Butadiene Rubbers Polychloroprene Rubbers Carboxylated Rubber Latexes References 560 Chapter 16 Vinyl Acetate Polymerization 563 Gerald A. Vandezande, Oliver W. Smith and David R. Bassett 16.1 Introduction Initiator Investigations Molar Mass and Branching Copolymerization Particle Size and Distribution Particle Structure Film Formation Stabilization of Poly(Vinyl Acetate) Dispersions Copolymers of Vinyl Acetate and Branched Vinyl Esters.. 578

7 x CONTENTS Summary References 584 Chapter 17 Vinyl Chloride Polymerization 589 John Ugelstad, Preben C. M0rk and Arvid Berge 17.1 Introduction Chain Transfer to Monomer Initiators and Emulsifiers Ordinary Emulsion Polymerization Seeded Emulsion Polymerization Competitive Growth Miniemulsion Polymerization References 616 Chapter 18 Acrylic and Styrene-Acrylic Polymers 619 Patricia M. Lesko and Peter R. Sperry 18.1 Introduction Acrylic Monomers Acrylic Emulsion Polymerization Latex Characterization Latex Film Formation Rheology Applications of Acrylic Latex Polymers Future Directions in Acrylic Emulsion Polymer Technology Acknowledgments References 651 Chapter 19 Rubber-toughened Plastics 657 Peter A. Lovell and Dorian Pierre 19.1 Introduction Deformation Mechanisms and Fracture Mechanics The Rationale for Rubber-toughening of Plastics Routes to Rubber-toughened Plastics Acrylonitrile-Butadiene-Styrene Copolymer Materials Rubber-toughened Acrylic (RTPMMA) Materials Rubber-toughened Epoxy Resins Rubber-toughened Polycarbonates Other Rubber-toughened Plastics References 690

8 CONTENTS Section V: Related Heterogeneous Polymerization 697 Chapter 20 Miniemulsion Polymerization 699 E. David Sudol and Mohamed S. El-Aasser 20.1 Definitions Pros and Cons of Miniemulsion Polymerization Miniemulsion Polymerization Prospects References 721 Chapter 21 Inverse Emulsion and Microemulsion Polymerization 723 Frangoise Candau 21.1 Introduction Structure and Stability of Inverse Dispersions Inverse Emulsion Polymerization Inverse Microemulsion Polymerization Copolymerization Reactions References 739 Chapter 22 Dispersion Polymerization 743 John L. Cawse 22.1 Scope and Definition Essential Formulation Components A Typical Formulation and Process Dispersion Properties Copolymerization and Crosslinking in Dispersion Polymerization Mechanism of Particle Formation Kinetics Applications Acknowledgement References 759 Chapter 23 Unconventional Emulsion Polymerizations 763 Jenci Kurja, Hennie F. Zirkzee and Ian A. Maxwell 23.1 Introduction Unconventional Free-radical Emulsion Polymerizations Ionic Emulsion Polymerizations Transition Metal Catalyzed Emulsion Polymerizations xi

9 xii CONTENTS 23.5 Enzyme-catalyzed Emulsion Polymerizations Concluding Remarks References 775 Author Index 777 Subject Index 787