Reactive polymers fundamentals and applications : a concise guide to industrial polymers ·...

REACTIVE POLYMERS

FUNDAMENTALS AND

APPLICATIONS

A CONCISE GUIDE TO

INDUSTRIAL POLYMERS

Johannes Karl Fink

Montanuniversitat Leoben, Austria

Second Edition

AMSTERDAM • BOSTON • HEIDELBERG • LONDON

NEW YORK • OXFORD • PARIS • SAN DIEGO

SAN FRANCISCO • SINGAPORE • SYDNEY • TOKYO

William Andrew is an Imprint of ElsevierELSEVIER

Contents

PDL Series Editor's Preface xix

Preface xxi

1. Unsaturated Polyester Resins 11.1 History 11.2 Monomers 1

1.2.1 Monomers for an Unsaturated Polyester 11.2.2 Vinyl Monomers 41.2.3 Specialities 51.2.4 Synthesis 71.2.5 Manufacture 8

1.3 Special Additives 91.3.1 Inhibitors 91.3.2 Thickeners 101.3.3 Emission Suppressants 111.3.4 Fillers 111.3.5 Reinforcing Materials 141.3.6 Additives for Molding Applications 161.3.7 Low-profile Additives 171.3.8 Interpenetrating Polymer Networks 181.3.9 Poly(urethane) Hybrid Networks 19

1.3.10 Flame Retardants 201.3.11 Production Data 22

1.4 Curing 221.4.1 Initiator Systems 221.4.2 Promoters 241.4.3 Initiator Promoter Systems 251.4.4 Polymerization 25

1.5 Properties 291.5.1 Structure-properties Relationships 291.5.2 Hydrolytic Stability 291.5.3 Recycling 30

1.6 Applications and Uses 311.6.1 Decorative Specimens 311.6.2 Polyester Concrete 311.6.3 Reinforced Materials 321.6.4 Coatings 32

1.7 Special Formulations 331.7.1 Electrically Conductive Resins 331.7.2 Poly(e-caprolactone)-perfluoropolyether Copolymers 331.7.3 Toner Compositions 331.7.4 Pour Point Depressants 341.7.5 Biodegradable Polyesters 341.7.6 Neutron Shielding 341.7.7 Bone Cement 34

V

VI

Contents

35

I.7.S Conipatthih/ers ^5

1.7.9 Reactive Melt Modification of Poly*propylene)

1.7.10 'loner Resins 3?

References

49

2. Poly(urcthane)s*

^

2A History 492.2 Monomers .„

49

2.2.1 Diisocyatiales2.2.2 Polyols

5°

2.2J Other Polyols38

2.2.4 Polyaniines59

2.2.5 Chain Extenders59

2.2.6 Catalysts59

2.2.7 Blowing61

23 Speeial Additives67

2.3.1 Fillers68

2.3.2 Reinforcing Materials69

2.3.3 Flame Retardunts70

2.4 Curing7^

2.4.1 Recycling71

2.5 Properties73

2.5.1 Mechanical Properties73

2.5.2 Thermal Properties73

2.5.3 Weathering Resistance73

2.6 Applications and Uses73

2.6.1 Casting73

2.6.2 Foams73

2.6.3 Membranes 74

2.7 Special Formulations74

2.7.1 Interpenetrating Networks 74

2.7.2 Methucrylate Copolymers 75

2.7.3 Grafting with Isocyanates ..75

2.7.4 Coatings 75

2.7.5 Medical Applications 76

2.7.6 Oil Spill Cleanup 78

2.7.7 Footwear 78

2.7.8 Waterbome Poly(urelhane).s 78

2.7.9 Stamps 79

2.7.10 Ceramic Foams 80

2.7.11 Adhesion Modification 80

2.7.12 Electrolytes ".".80References g ]

3. Epoxy Resins 95

3.1 History g$

3.2 Monomers <jg

3.2.1 Epoxides3.2.2 Phenols J.ll.^'ZZZZZ^'Z 95

3.2.3 Specialities "95.3.2.4 Manufacture gg

3.3 Special Additives "jqq3.3.1 Crosslinking Agents

"

jqq

3.3.2 Toughening Agents

Contents vii

3.3.3 Antiplasticizers 105

3.3.4 Lubricants 105

3.3.5 Adhesion Improvers 106

3.3.6 Conductivity Modifiers 106

3.3.7 Reinforcing Materials 106

3.3.8 Graphene 108

3.3.9 Interpenetrating Polymer Networks 108

3.3.10 Organic and Inorganic Hybrids 110

3.3.11 Flame Retardants 110

3.3.12 Production Data 112

3.4 Curing 112

3.4.1 Initiator Systems 112

3.4.2 Compounds with Activated Hydrogen 113

3.4.3 Coordination Catalysts 117

3.4.4 Ionic Curing 117

3.4.5 Photoinitiators 118

3.4.6 Derivatives of Michler's Ketone 120

3.4.7 Epoxy Systems with Vinyl Groups 122

3.4.8 Curing Kinetics 122

3.4.9 Thermal Curing 124

3.4.10 Microwave Curing 124

3.5 Properties 124

3.5.1 Hybrid Polymers and Mixed Polymers 125

3.5.2 Recycling 125

3.6 Applications and Uses 127

3.6.1 Coatings 127

3.6.2 Foams 127

3.6.3 Adhesives 128

3.6.4 Molding Techniques 128

3.6.5 Stabilizers for Poly(vinyl chloride) 128

3.7 Special Formulations 128

3.7.1 Development of Formulations 128

3.7.2 Restoration Materials 128

3.7.3 Epoxy Polymer Concrete 128

3.7.4 Biodegradable Epoxy-polyester Resins 129

3.7.5 Swellable Epoxies 129

3.7.6 Membrane Materials 129

3.7.7 Controlled-release Formulations for Agriculture 129

3.7.8 Shape Memory Composites 129

3.7.9 Electronic Packaging Application 129

3.7.10 Ion-selective Electrodes 130

3.7.11 Solid Polymer Electrolytes 130

3.7.12 Optical Resins 131

3.7.13 Reactive Solvents 133

3.7.14 Encapsulated Systems 133

3.7.15 Functionalized Polymers 133

3.7.16 Epoxy Resins as Compatibilizers 134

3.7.17 Surface Metallization 135

References 135

4. Phenol/Formaldehyde Resins 155

4.1 History 155

4.2 Monomers 155

4.2.1 Phenol 156

viii Contents

4.2.2 o-Cresol 156

4.2.3 Cardanol 156

4.2.4 Formaldehyde 156

4.2.5 Multihydroxymethylketones 157

4.2.6 Production Data of Important Monomers 157

4.2.7 Basic Resin Types 157

4.2.8 Specialities 158

4.2.9 Synthesis 158

4.2.10 Catalysts 159

4.2.11 Manufacture 161

4.3 Special Additives 161

4.3.1 Low Emission Types 161

4.3.2 Boric Acid-modified Types 162

4.3.3 Fillers 163


4.4 Curing 164

4.4.1 Model Studies 164

4.4.2 Experimental Design 165

4.4.3 Water Content 165

4.4.4 Influence of Pressure 165

4.4.5 Wood 165

4.4.6 Novolak Curing Agents 166

4.4.7 Resol Resin Hardeners 166

4.4.8 Ester-type Accelerators 167

4.4.9 Ashless Resol Resins 167

4.5 Properties 167

4.5.1 Mechanical Properties 167

4.5.2 Recycling 167


4.6.1 Binders for Glass Fibers 168

4.6.2 Molding 169

4.6.3 Novolak Photoresists 169

4.6.4 High-temperature Adhesives 169

4.6.5 Urethane-modified Types 169

4.6.6 Carbon Products 170


4.7.1 Chemical-resistant Types 171

4.7.2 Ion Exchange Resins 171

4.7.3 Ionic Liquids 171

4.7.4 Brakes 171

4.7.5 Waterborne Types 172

4.7.6 High-viscosity Novolak 172

4.7.7 Foams 172

4.7.8 Visbreaking of Petroleum 172

4.8 Testing Methods 172

4.8.1 Water Tolerance 172

4.8.2, Salt Tolerance 172

4.8.3' Free Phenol Content 172

4.8.4 Free Formaldehyde 172

4.8.5 pH 172

4.8.6 Solids Content 173

4.8.7 o-Cresol Contact Allergy 173

References 173

Contentsix

5. Urea/Formaldehyde Resins 1795.1 History 1795.2 Synthesis of Resin

1795.2.1 Formaldehyde 1795.2.2 Urea

1795.2.3 Ammonia

1795.2.4 Diketones

1795.2.5 Dimethoxy Ethanal

1795.2.6 Specialities 1805.2.7 Polymerization 1815.2.8 Manufacture

1825.3 Special Additives

1835.3.1 Modifiers 1835.3.2 Fillers

1835.3.3 Flame Retardants 1845.3.4 Production Data of Important Monomers 184

5.4 Curing 1845.5 Measurement of Curing 1855.6 Properties 185

5.6.1 Formaldehyde Release 1855.6.2 Storage 1865.6.3 Hydrolytic Stability 186

5.7 Applications and Uses 1865.7.1 Glue Resins 1865.7.2 Binders 1875.7.3 Emulsion Paints 1875.7.4 Foundry Sands 1875.7.5 Electrical Applications 1875.7.6 Formation of Nanopowders 1875.7.7 Waste Water Cleaning 188

5.8 Special Formulations 1885.8.1 Ready-use Powders 1885.8.2 Cyclic Urea Prepolymer in PF Laminating Resins 1885.8.3 Liquid Fertilizer 1885.8.4 Soil Amendment 1885.8.5 Microencapsulation 188

References189

6. Melamine Resins 1936.1 History 1936.2 Monomers 193

6.2.1 Melamine 1936.2.2 Other Modifiers 1936.2.3 Synthesis 1936.2.4 Manufacture 194

6.3 Special Additives 1946.3.1 Reinforcing Materials

1946.3.2 Flame Retardants 1946.3.3 Recycling 195

6.4 Properties 1956.5 Applications and Uses 196

6.5.1 Wood Impregnation 1966.5.2 Waste Water Cleaning 1976.5.3 Separation of Metal Ions 197

x Contents

6.6 Special Formulations 1976.6.1 Coatings 197

6.6.2 Encapsulated Dyes 1986.6.3 Porous Resins 1986.6.4 Resins with Increased Elasticity 198

6.6.5 Microspheres 198References 199

7. Furan Resins 2037.1 History 2037.2 Monomers 203

7.2.1 Furfural 2037.2.2 Furfuryl Alcohol 2037.2.3 Specialities 204

7.2.4 Synthesis 2047.3 Special Additives 204

7.3.1 Reinforcing Materials 2047.4 Curing 205

7.4.1 Acidic Curing 2057.4.2 Oxidative Curing 2057.4.3 Ultrasonic Curing 205

7.5 Properties 2067.5.1 Recycling 206

7.6 Applications and Uses 2067.6.1 Carbons 2067.6.2 Chromatography Support 2087.6.3 Composite Carbon Fiber Materials 2097.6.4 Foundry Binders 2097.6.5 Glass Fiber Binders 2107.6.6 Aluminum Electrolysis 2107.6.7 Panels and Fiberboards

2107.6.8 Oil Field Applications 2107.6.9 Photosensitive Polymer Electrolytes 211

7.6.10 Plant Growth Substrates211

References212

8. Silicones217

8.1 History 2178.2 Monomers

2178.2.1 Chlorosilanes 2178.2.2 Silsesquioxanes 2178.2.3 Hydrogen-silsesquioxane Resins 2178.2.4 Alkoxysiloxanes. 2188.2.5 Silphenylenes 2198.2.6 Epoxy-modified Siloxanes 2198.2.7 Sil aferrocenophanes 2198.2.8 Synthesis 2198.2.9 Manufacture 221

8.3 Modified Types 2218.3.1 Chemical Modifications 2218.3.2 Fillers


8.4 Curing 2228.4.1 Curing by Condensation 222

Contents xi

8.5 Crosslinking 2238.5.1 Condensation Crosslinking 2238.5.2 Peroxides 2238.5.3 Hydrosilylation Crosslinking 223

8.6 Properties 2248.6.1 Silicone Rubber 2248.6.2 Thermal Properties 2248.6.3 Electrical Properties 2258.6.4 Surface Tension Properties 2258.6.5 Antioxidants 2258.6.6 Gas Permeability 2258.6.7 Weathering 225

8.7 Applications and Uses 2258.7.1 Coatings 2268.7.2 Adhesives 2278.7.3 Antifoaming Agents 2278.7.4 Release Agents 2278.7.5 Sealing and Jointing Materials 2278.7.6 Electrical Industry 2278.7.7 Medical Applications 228

8.8 Special Formulations 2288.8.1 Polyimide Resins 2288.8.2 Thermal Transfer Ribbons 2288.8.3 Self-assembly Systems 2298.8.4 Plasma Grafting 2298.8.5 Antifouling Compositions 229

References 230

9. Acrylic Resins• 235

9.1 History 2359.2 Monomers 235

9.2.1 Specialities 2359.2.2 Synthesis 2359.2.3 Manufacture 237

9.3 Special Additives 2379.3.1 Ultraviolet Absorbers 2379.3.2 Flame Retardants 237

9.4 Curing 2399.4.1 Initiator Systems 2399.4.2 Promoters 239

9.5 Properties 2399.5.1 Electrical Properties 2399.5.2 Hydrolytic and Photochemical Stability 2409.5.3 Recycling 240

9.6 Applications and Uses-.240

9.6.1 Acrylic Premixes 2409.6.2 Epoxy Acrylates 2419.6.3 Urethane Acrylates 2419.6.4 High-performance Biocomposite 2429.6.5 Solid Polymer Electrolytes 242

9.7 Special Formulations243

9.7.1 Coatings 2439.7.2 Tackifier Resins 2449.7.3 Drug Release Membranes 244

x[[ Contents

9.7.4 Support Materials for Catalysts 245

9.7.5 Electron Microscopy 245

9.7.6 Stereolithography 245

9.7.7 Electronic Applications 245

9.7.8 Magnetic Applications 245

9.7.9 Nanocomposites 245

9.7.10 Laminated Films 246

9.7.11 Ink-jet Printing Media 246

References •247

10. Cyanate Ester Resins 251

10.1 History 251

10.2 Monomers 251


10.2.2 Synthesis 251


10.3.1 Fillers 252


10.4 Curing 254

10.4.1 Thermal Curing 254

10.4.2 Curing with Epoxy Groups 257

10.4.3 Curing with Unsaturated Compounds 257

10.4.4 Initiator Systems 258

10.5 Properties 258

10.5.1 Modeling 259


10.6.1 Fiber Composites 259

10.6.2 Electronic Industry 259

10.6.3 Spacecraft 259


10.7.1 Phenolic Triazine Compositions 259

10.7.2 Epoxy-containing Compositions 259

10.7.3 Bismaleimide Triazine Resins 261

10.7.4 Siloxane Crosslinked Resins 261

10.7.5 Alloys with Thermoplastics 262

10.7.6 Coupling Agents for Cyanate Ester Resins 263

References 263

11. Bismaleimide Resins 269

11.1 Monomers 269

11.1.1 4,4'-Bis(maleimido)diphenylmethane 269

11.1.2 Allyl Compounds 269

11.1.3 Poly(ethylene glycol) End Capped with Maleimide 270

11.1.4 Poly(phenylene oxide) 271

11.1.5 Bismaleimide Bisimides 271

11.1.6 Maleimide Silicone Monomers 271

11.1.7 Maleimide Epoxy Monomers 271

11.1.8 Phosphorus-containing Monomers 272

11.1.9 Multiring Monomers with Pendant Chains 273

11.1.10 Benzoxine Comonomers 274

11.1.11 Reactions of Maleimides 274



11.2.1 Tougheners and Modifiers 280

Contents xiii

11.2.2 Fillers 283

11.2.3 Titanium Dioxide 284



11.3 Curing 28511.3.1 Monitoring Curing Reactions 285

11.3.2 Polymerization 286

11.3.3 Interpenetrating Networks 288

11.4 Properties 289

11.4.1 Thermal Properties 289

11.4.2 Water Sorption 289

11.4.3 Tribological Properties 290

11.4.4 Recycling 291


11.5.1 Biochemical Reagents 291


11.6.1 Adhesives 291

11.6.2 Polyquinoline Polymers 292

11.6.3 Phosphazene-triazine Polymers 292

11.6.4 Porous Networks 292

11.6.5 Nonlinear Optical Systems 292

References 293

12. Terpene Resins 303

12.1 History 303

12.2 Monomers 303

12.2.1 Resin 303

12.2.2 Turpentine 304

12.2.3 Rosin 304

12.3 Curing 304

12.3.1 Homopolymers 304

12.3.2 Copolymers 305

12.3.3 Terpene Phenol Resins 305

12.3.4 Terpene Maleimide Resins 306

12.3.5 Poly(farnesene)s 306

12.4 Properties 307

12.4.1 Solubility 307

12.4.2 Adhesive Properties 307

12.4.3 Characterization 308

12.4.4 Recycling 308


12.5.1 Sealants 309

12.5.2 Pressure-sensitive Adhesives 309

12.5.3 Polyacrylate Hot-melt Pressure-sensitive Adhesives 309

12.5.4 Hot-melt Adhesives 310

12.5.5 Coatings 310

12.5.6 Sizing Agents 311

12.5.7 Toner Compositions 312

12.5.8 Chewing Gums 312

12.5.9 Tire Puncture Sealant 313


12.6.1 Toughener for Novolaks 313

12.6.2 Fluoro Copolymers 313

References• 313

xiv Contents

13. Cyanoacrylates 317

13.1 Monomers 317

13.1.1 Synthesis 317

13.1.2 Crosslinkers 317

13.1.3 Commercial Products 317


13.2.1 Plasticizers 318

13.2.2 Accelerators 319

13.2.3 Thickeners 320

13.2.4 Stabilizers 321

13.2.5 Primers 322

13.2.6 Diazabicyclo and Triazabicyclo Primers 322

13.2.7 Polyaminc Dendrimers 323

13.3 Curing 323

13.3.1 Photo Curing 324

13.4 Properties 324


13.5.1 Rapid Prototyping 324

13.5.2 High-resolution Lithography 325

13.5.3 Cosmetic and Medical Applications.. 325

References 327

14. Benzocyclobutene Resins 331

14.1 Modified Polymers 333

14.1.1 Thcrmotropic Copolymers 333

14.1.2 BCB-modified Aromatic Polyamides 333

14.1.3 BCB End Capped Polyimides 333

14.1.4 Flame-resistant Formulations 333

14.2 Crosslinkers 334

14.2.1 Modified Polyethylene terephthalate) 334


14.3.1 Applications in Microelectronics 334

14.3.2 Optical Applications 336

References 336

15. Reactive Extrusion 339

15.1 Extruder 339

15.1.1 Heat of Polymerization 341

15.1.2 Ceiling Temperature 342

15.1.3 Strategy of Reactive Extrusion 342

15.2 Compositions of Industrial Polymers 342

15.2.1 Polyolefins 343

15.2.2 Poly(styrene) 347

15.2.3 Poly(tetramethylene ether) and Poiy(caprolaclam) 347

15.2.4 Polyamides 348

15.2.5 Poly(butyl methacrylate) 348

15.2.6 Poiy(carbonate) 348

15.2.7 Polyesters 350

15.2.8 Thermoplastic Poly(urethane) 351

15.3 Biodegradable Compositions 351

15.3.1 Poly(lactide)s 353

15.3.2 Starch and Cellulose Derivatives 355

15.3.3 Biodegradable Fibers 357

15.3.4 Poly(e-caprolactone) 357

Contentsxv

15.3.5 Cationically Modified Starch 358

15.3.6 Blends of Starch and Polyesters 358

15.3.7 Blends of Starch and Poly(acrylamide) 359

15.3.8 Blends of Chitosan and Poly(acrylic acid) 360

15.3.9 Blends of Protein and Polyester 360

15.3.10 Modification of Protein with Monomers 360

15.4 Chain Extenders 361

15.4.1 Recycling of Poly(ethylene terephthalaLe) 361

15.4.2 Modified Poly(ethylene terephthalate) 361

15.4.3 Poly(butylene terephthalate) 362

15.5 Related Applications 36215.5.1 Transesterification 36215.5.2 Hydrolysis and Alcoholysis 362

15.5.3 Flame Retardant Master Batch 362

References 362

16. Compatibilization• 373

16.1 Equipment 37316.2 Basic Terms 373

16.2.1 Thermodynamic Compatibility 37316.2.2 Thermodynamic Models 37416.2.3 Particle Size 37416.2.4 Interfacial Slip 37416.2.5 Interpolymer Radical Coupling 37416.2.6 Technological Compatibility 374

16.3 Interpenetrating Polymer Networks 37516.4 Compatibilization by Additives 375

16.4.1 Poly(ethylene) Blended with Inorganic Fillers 37516.4.2 Filler Materials without Chemical Compatibilizers 37716.4.3 Modified Inorganic Fillers 37716.4.4 Clay Nanocomposites 37716.4.5 Graphene Oxide Sheets 37816.4.6 Thermoplastic Elastomers 37816.4.7 Polyamide 66 and Poly(butylene terephthalate) 37816.4.8 Poly(ethylene)AVood Flour Composites 37816.4.9 Recycled Polyolefins 379

16.4.10 Block Copolymers 37916.4.11 Impact Modification of Waste PET 38016.4.12 Starch 380

16.4.13 Blends of Cellulose and Chitosan 38116.5 Reactive Compatibilization 381

16.5.1 In Situ Generation of Compatibilizer 382

16.5.2 Coupling Agents for Compatibilization 38316.5.3 High-molecular-weight Peroxides 384

16.5.4 Vector Fluids 384

16.5.5 Poly(ethylene) and Polyamide 6 384

16.5.6 Polyolefins and Poly(butylene terephthalate) 38516.5.7 Poly(ethylene-octene) and Polyamide 6 386

16.5.8 Ethylene Acrylic Acid Polymers and Polyamide 6 386

16.5.9 PPO and Polyamide 6 38616.5.10 Wheat Straw 38616.5.11 Sisal Fibers 38616.5.12 Thermotropic Liquid Crystalline Polyesters 38716.5.13 Ionomers and Ionomeric Compatibilizers 387

xvi Contents

16.5.14 Solid Polymer Electrolytes 388

16.5.15 Polyvinyl chloride) 388

16.5.16 Poly(styrene) 388

16.5.17 Polyolefins/Poly(ethylene oxide) 392

16.5.18 Poly(phenylene sulfide) and Liquid Crystalline Polymers 392

16.5.19 LDPE/Thermoplastic Starch 392

16.5.20 PE and EVA 392

16.5.21 SBR and EVA 393

16.5.22 NBR and EPDM 393

16.5.23 NBR and PA6 393

16.5.24 Poly(carbonate) and Poly(vinylidene fluoride) 393

16.5.25 Bisphenol A-poly(carbonate) and ABS Copolymers 394

16.5.26 Kevlar 394

16.5.27 Polyamides 394

16.5.28 Polyethers 395

16.5.29 Polyolefins and Poly(ethylene terephthalate) 395

16.5.30 Poly(uretharie) and Polyethylene terephthalate) 396

16.6 Starch Polyester Blends 396

16.7 Functionalization of End Groups 396

16.7.1 Mechanisms 396

16.7.2 Amino-terminated Nitrile Rubber 398

16.7.3 Functionalization of Olefinic End Groups of Poly(propylene) 398

16.7.4 Muconic Acid-grafted Polyolefin Compatibilizers 399

16.7.5 Polyfunctional Polymers and Modified Polyolefin 399

References 400

17. Rheology Control 411

17.1 Melt Flow Rate 411

17.2 Rheology Control Techniques 411

17.2.1 Pellctizing 412

17.3 Peroxides for Rheology Control 412

17.3.1 Hydroperoxides 413

17.3.2 Peroxides 413

17.3.3 Diacyl Peroxides 414

17.3.4 Ketone Peroxides 414

17.3.5 Masterbatches of Peroxides 415

17.3.6 Pevestevs 415

17.3.7 Properties of Peroxides 415

17.3.8 Azo Compounds 417

17.4 Scavengers 418

17.4.1 Stable Nitroxyl Radicals 418

17.5 Mechanism of Degradation 418

17.5.1 Radiation-induced Degradation 418

17.6 High Melt Flow Poly(propylene) 420

17.7 Irregular Flow Improvement 420

17.8 Heterophasic Copolymers... 420

17.9 Poly(propylene) 421

17.9.1 Long-chain Branched Poly(propylene) 422

17.9.2 Effect of MFR on Temperature and Residence Time 423

References 423

18. Grafting 425

18.1 The Techniques in Grafting 425

18.1.1 Parameters that Influence Grafting 425

Contents xvii

18.1.2 Free-radical-induced Grafting 426

18.1.3 Grafting Using Stable Radicals 426

18.2 Polyolefins 427

18.2.1 Monomers for Grafting onto Polyolefins 427

18.2.2 Mechanism of Melt Grafting 427

18.2.3 Side Reactions 428

18.2.4 Viscosity 429

18.2.5 Ceiling Temperature 42918.2.6 Effect of Initiator Solubility 429

18.2.7 Distribution of the Grafted Groups 430

18.2.8 Effect of Stabilizers on Grafting 430

18.2.9 Radical Grafting of Polyolefins with Diethyl Maleate 430

18.2.10 Inhibitors of the Homopolymerization of Maleic Anhydride 431

18.2.11 Inhibitors of Crosslinking 431

18.2.12 Special Initiators 431

18.2.13 Maleic Anhydride 433

18.2.14 Polyolefins Grafted with Itaconic Acid Derivatives 434

18.2.15 Imidized Maleic Groups 435

18.2.16 Oxazoline-modified Polyolefins 435

18.2.17 Modification of Polyolefins with Vinylsilanes 435

18.2.18 Ethyl Diazoacetate-modified Polyolefins 435

18.2.19 Grafting Antioxidants 435

18.2.20 Comonomer-assisted Free-radical Grafting 436

18.2.21 Radiation-induced Grafting in Solution 438

18.2.22 Characterization of Polyolefin Graft Copolymers 438

18.2.23 PVC/LDPE Melt Blends 438

18.3 Other Polymers 439

18.3.1 Poly(styrene) Functionalized with Maleic Anhydride 439

18.3.2 Multifunctional Monomers for PP/PS Blends 439

18.3.3 Poly(methyl methacrylate) 439

18.3.4 Poly(ethylene-co-methyl acrylate) 439

18.3.5 n-Butyl Methacrylate Grafted onto Poly(vinyl chloride) 44018.3.6 Starch Esterification 440

18.3.7 Starch-grafted Acrylics 441

18.3.8 Cellulose-grafted Poly(caprolactone) 441

18.3.9 Thermoplastic Phenol/Formaldehyde Polymers 441

18.3.10 Polyesters and Poly(urethane)s 441

18.3.11 Polyacrylic Hot-melt Pressure-sensitive Adhesive 442

18.4 Terminal Functionalization 442

18.4.1 Ene Reaction with Poly(propylene) 44218.4.2 Styrene Butadiene Rubber 44318.4.3 Diels-Alder Reaction 443

18.5 Grafting onto Surfaces 44318.5.1 Grafting onto Poly(ethylene) 44318.5.2 Grafting onto Poly(vinylidene fluoride) 44518.5.3 Grafting onto Poly(tetrafluoroethylene) 445

References 446

19. Acrylic Dental Fillers 45319.1 History 45319.2 Methods of Development 45319.3 Polymeric Composite Filling Materials 45419.4 Monomers 454

19.4.1 Acrylics and Methacrylics 454

xviii Contents

19.4.2 Cyclic Monomers 457

19.4.3 Epoxy Monomers 458

19.4.4 Highly Loaded Composites 458

19.5 Radical Polymerization 458

19.5.1 Chemical Curing Systems 459

19.5.2 Photo Curing 461

19.5.3 Curing Techniques 462

19.5.4 Dual Initiator Systems 463

19.6 Inhibitors 463

19.7 Additives 463

19.7.1 Fillers and Reinforcing Materials 463

19.7.2 Pigments 466

19.7.3 Photostabilizers 466

19.7.4 Caries Inhibiting Agents 466

19.7.5 Coloring or Tint Agents 466

19.7.6 Adhesion Promoter 467

19.7.7 Thermochromic Dye 468

19.8 Properties 468

19.8.1 Optical Properties 469

19.8.2 Chemical Stability 469

19.8.3 Cytotoxicity 469

19.9 Applications 470

19.9.1 Filling Techniques 470

19.9.2 Primer Emulsions 470

References 470

20. Toners 475

20.1 Toner Components 47520.2 Toner Resins 476

20.3 Manufacture ofToner Resins 477

20.3.1 Suspension Polymerization 47720.3.2 Terephthalic Ester Resins 477

20.3.3 Toner Resins with Low Fix Temperature 47720.3.4 Toners for Textile Printing 478

20.4 Characterization of Toners 479

20.4.1 Consistency 47920.4.2 Health Aspects 480

References 480

Index483

Acronyms 483

Chemicals 493

General Index 524

Reactive polymers fundamentals and applications : a concise guide to industrial polymers ·...

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