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
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 4 1.2 Chain Polymerization 4 1.3 Chemistry of Free-radical Polymerization 5 1.4 Kinetics of Homogeneous Free-radical Polymerization... 14 1.5 Stereochemistry of Polymerization 23 1.6, Free-radical Copolymerization 26 1.7 Homogeneous Free-radical Polymerization Processes 34 1.8 References 35 Chapter 2 Features of Emulsion Polymerization 37 Mohamed S. El-Aasser and E. David Sudol 2.1 Introduction 38 2.2 "Classical" Emulsion Polymerization Basic Ingredients 38 2.3 Emulsion Polymerization Processes 39 2.4 Overall Description of Emulsion Polymerization 40 2.5 Basic Issues in Emulsion Polymerization 41 2.6 Other Controversial Issues in Emulsion Polymerization... 49 2.7 References 55
vi CONTENTS Chapter 3 Stabilization of Polymer Colloid Dispersions 59 Ronald H. Ottewill 3.1 Introduction 60 3.2 Electrical Double Layer 61 3.3 The Potential Energy of Interaction Between Particles... 67 3.4 Coagulation of Polymer Colloids 73 3.5 The Influence of Various Electrolytes on Colloid Stability 79 3.6 Steric Stabilization 101 3.7 Depletion Effects Non-adsorbing Molecules 113 3.8 Apologia 117 3.9 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 126 4.2 The Literature of Emulsion Polymerization 128 4.3 Theories of Emulsion Polymerization 128 4.4 Emulsion Polymerization Kinetics 135 4.5 Swelling of Latex Particles 145 4.6 Polymerizations with Non-ionic Emulsifiers 146 4.7 Polymerizations using Oil-soluble Initiators 149 4.8 Exact Solutions of the Recursion Equation 150 4.9 Appendix 4.1: Derivation of the Smith-Ewart Equations... 151 4.10 Appendix 4.2: Derivation of the Morton-Kaizerman-Altier Equation 156 4.11 Appendix 4.3: Gardon's Equations 157 4.12 References 159 Chapter 5 Modelling Rates, Particle Size Distributions and Molar Mass Distributions 165 Robert G. Gilbert 5.1 Introduction 165 5.2 Mechanisms and Evolution Equations 166 5.3 Comparison with Experiment 187 5.4 Conclusions 200 5.5 References 201
CONTENTS Section III: Practice 205 Chapter 6 Formulation Components 207 Andrew Klein and Eric S. Daniels 6.1 Introduction 208 6.2 Monomers 208 6.3 Crosslinking Systems 219 6.4 Water 220 6.5 Initiation 221 6.6 Surfactants 222 6.7 Protective Colloids 226 6.8 Rheological Modifiers 227 6.9 Chain Transfer Agents 228 6.10 Buffers 229 6.11 Post-additives 229 6.12 Biocides and Fungicides 230 6.13 Antioxidants and Ultraviolet Light Absorbers 230 6.14 The Use of Experimental Design in Latex Synthesis and Formulation 232 6.15 Summary 233 6.16 References 234 Chapter 7 Batch and Semi-batch Processes 239 Peter A. Lovell 7.1 Introduction 240 7.2 Distinction Between Batch and Semi-batch Processes 240 7.3 Batch Processes 240 7.4 Semi-batch Processes 256 7.5 References 273 Chapter 8 Continuous Processes 277 Gary W. Poehlein 8.1 Introduction 277 8.2 Continuous^Reactor Systems 279 8.3 Perfectly Mixed CSTR 280 8.4 The CSTR as a Research Tool 283 8.5 CSTR Modelling and Control Issues 285 8.6 Tubular Reactors 288 8.7 Other Reactor Systems 290 8.8 References 291 vii
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^ 294 9.2 "Core-Shell" Model of Particle Growth in Emulsion Polymerization 295 9.3 Prediction of Composite Latex Particle Morphology 300 9.4 Importance of Polymerization Process Parameters in Controlling Particle Morphology 309 9.5 Characterization Techniques Utilized for the Study of Composite Latex Morphologies 318 9.6 Summary 322 9.7 References 323 Chapter 10 Process Modelling and Control 327 F. Joseph Schork 10.1 Mathematical Modelling 328 10.2 Reactor Design and Operation 329 10.3 On-line Sensors 330 10.4 Process Control 335 10.5 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 345 11.2 Molecular Characterization 347 11.3 Macroscopic Characterization 374 11.4 References 377 Chapter 12 Measurement of Particle Size and Particle Size Distribution 385 Edward A. Collins 12.1 Introduction 386 12.2 Essential Background 388 12.3 Key Particle Size Methods 398 12.4 Guidelines to Instrument Selection 419 12.5 Comparative Analysis 423 12.6 Recent Developments and Trends 427 12.7 References 432
CONTENTS ix Chapter 13 Latex Rheology 437 Edward J. Schaller 13.1 Introduction to Rheology 438 13.2 Dispersion Rheology 443 13.3 Thickeners for Latex Formulations 454 13.4 References 463 Chapter 14 The Formation and Properties of Latex Films... 467 Mitchell A. Winnik 14.1 Introduction 468 14.2 How Latex Dispersions Dry 471 14.3 Packing and Deformation 482 14.4 Healing of the Interfaces 500 14.5 Mechanical Properties and Crosslinked Latex Films 511 14.6 Final Comments 514 14.7 Acknowledgements 514 14.8 References 515 Section IV: Major Industrial Uses 519 Chapter 15 Diene-based Synthetic Rubbers 521 David C. Blackley 15.1 Some General Considerations 522 15.2 Styrene-Butadiene Rubbers 531 15.3 Acrylonitrile-Butadiene Rubbers 545 15.4 Polychloroprene Rubbers 551 15.5 Carboxylated Rubber Latexes 558 15.6 References 560 Chapter 16 Vinyl Acetate Polymerization 563 Gerald A. Vandezande, Oliver W. Smith and David R. Bassett 16.1 Introduction 563 16.2 Initiator Investigations 564 16.3 Molar Mass and Branching 566 16.4 Copolymerization 568 16.5 Particle Size and Distribution 571 16.6 Particle Structure 572 16.7 Film Formation 574 16.8 Stabilization of Poly(Vinyl Acetate) Dispersions 575 16.9 Copolymers of Vinyl Acetate and Branched Vinyl Esters.. 578
x CONTENTS 16.10 Summary 584 16.11 References 584 Chapter 17 Vinyl Chloride Polymerization 589 John Ugelstad, Preben C. M0rk and Arvid Berge 17.1 Introduction 589 17.2 Chain Transfer to Monomer 591 17.3 Initiators and Emulsifiers 592 17.4 Ordinary Emulsion Polymerization 593 17.5 Seeded Emulsion Polymerization 603 17.6 Competitive Growth 605 17.7 Miniemulsion Polymerization 608 17.8 References 616 Chapter 18 Acrylic and Styrene-Acrylic Polymers 619 Patricia M. Lesko and Peter R. Sperry 18.1 Introduction 620 18.2 Acrylic Monomers 622 18.3 Acrylic Emulsion Polymerization 625 18.4 Latex Characterization 630 18.5 Latex Film Formation 631 18.6 Rheology 637 18.7 Applications of Acrylic Latex Polymers 640 18.8 Future Directions in Acrylic Emulsion Polymer Technology 650 18.9 Acknowledgments 651 18.10 References 651 Chapter 19 Rubber-toughened Plastics 657 Peter A. Lovell and Dorian Pierre 19.1 Introduction 658 19.2 Deformation Mechanisms and Fracture Mechanics 658 19.3 The Rationale for Rubber-toughening of Plastics 664 19.4 Routes to Rubber-toughened Plastics 665 19.5 Acrylonitrile-Butadiene-Styrene Copolymer Materials... 667 19.6 Rubber-toughened Acrylic (RTPMMA) Materials 672 19.7 Rubber-toughened Epoxy Resins 679 19.8 Rubber-toughened Polycarbonates 686 19.9 Other Rubber-toughened Plastics 688 19.10 References 690
CONTENTS Section V: Related Heterogeneous Polymerization 697 Chapter 20 Miniemulsion Polymerization 699 E. David Sudol and Mohamed S. El-Aasser 20.1 Definitions 700 20.2 Pros and Cons of Miniemulsion Polymerization 703 20.3 Miniemulsion Polymerization 704 20.4 Prospects 720 20.5 References 721 Chapter 21 Inverse Emulsion and Microemulsion Polymerization 723 Frangoise Candau 21.1 Introduction 724 21.2 Structure and Stability of Inverse Dispersions 725 21.3 Inverse Emulsion Polymerization 726 21.4 Inverse Microemulsion Polymerization 734 21.5 Copolymerization Reactions 738 21.6 References 739 Chapter 22 Dispersion Polymerization 743 John L. Cawse 22.1 Scope and Definition 744 22.2 Essential Formulation Components 744 22.3 A Typical Formulation and Process 747 22.4 Dispersion Properties 747 22.5 Copolymerization and Crosslinking in Dispersion Polymerization 755 22.6 Mechanism of Particle Formation 756 22.7 Kinetics 758 22.8 Applications 759 22.9 Acknowledgement 759 22.10 References 759 Chapter 23 Unconventional Emulsion Polymerizations 763 Jenci Kurja, Hennie F. Zirkzee and Ian A. Maxwell 23.1 Introduction 763 23.2 Unconventional Free-radical Emulsion Polymerizations... 767 23.3 Ionic Emulsion Polymerizations 769 23.4 Transition Metal Catalyzed Emulsion Polymerizations... 770 xi
xii CONTENTS 23.5 Enzyme-catalyzed Emulsion Polymerizations 771 23.6 Concluding Remarks 774 23.7 References 775 Author Index 777 Subject Index 787