THERMOPLASTIC MATERIALS Properties, Manufacturing Methods, and Applications Christopher С Ibeh ( r ojc) CRC Press NV* 1 Taylor &. Francis Group Boca Raton London NewYork CRC Press is an imprint of the Taylor & Francis Croup, an informa business
Contents Preface Author xix xxiii 1. Introduction and History of the Plastics Industry 1 1.1 Definition and Types 1 1.2 Overview of the Plastics Industry 3 1.3 Areas of Application of Plastics 7 1.3.1 Example Applications of Plastic Resins 8 1.4 Chronology of the Thermoplastics (Plastics) Industry: The Need Factor 10 1.5 Current Trends in the Plastics Industry 17 1.5.1 Electrically Conductive Plastics 18 1.5.2 Blending and Alloying 18 1.5.3 Polymer-Matrix Composites and Polymer-Matrix Nanocomposites 19 1.5.4 Recycling and Sustainability 19 1.5.5 Biodegradable Plastics 21 1.5.6 High-Temperature Plastics 21 References 22 2. Raw Materials and Their Sources: "The Plastics Tree" 27 2.1 Sources and Raw Materials of Polymers and Plastics 27 2.2 Compounding and Property Enhancement 29 2.3 Processing of Polymers and Plastics 34 References 39 3. Basic Structures and Characteristics of Polymers and Plastics 43 3.1 Chemical Bonding in Polymers and Plastics 43 3.2 Ionization Potential and Chemical Bonding 46 3.3 Major Types of Chemical Bonding in Polymers and Plastics 47 3.3.1 Secondary Bonds 48 3.4 Structural Units in Polymers (Plastics Resins) 51 3.4.1 Polymer Types 51 3.4.2 Stereoregularity 55 3.4.3 Copolymers 55 3.4.3.1 Homopolymers, Copolymers, and Terpolymers 56 References 59 v
vi Contents 4. Molecular Weight of Polymers 63 4.1 Introduction 63 4.2 Molecular Weight Distribution 64 4.3 Average Molecular Weight of Polymers 65 4.3.1 Determination of Average Molecular Weight 65 4.3.2 Nomenclature for Molecular Weight Calculations 65 4.3.3 Number Average Molecular Weight (M ) 66 4.3.3.1 Number Average Molecular Weight Degree of Polymerization (DP,,) 66 4.3.4 Weight Average Molecular Weight (M w ) 69 4.3.4.1 Molecular Weight Determination via the Light-Scattering Method 69 4.3.5 Viscosity Average Molecular Weight (M v ). 71 4.3.5.1 Viscosity Average Molecular Weight (M v ) via the Mark-Houwink Empirical Relation (Equation) 71 4.3.5.2 Fikentscher K-Value 72 4.3.5.3 The Margolies Equation: Viscosity Average Molecular Weight. 73 4.3.6 Z-Average Molecular Weight (M z ) 73 4.3.6.1 The Analytical Ultracentrifuge Sedimentation Equilibrium Method 74 4.3.7 The Melt Index 77 4.3.7.1 Correlation between Molecular Weight andmfr 78 References 78 5. Polymerization (Resinification) Methods 81 5.1 Chemistry of Reaction of Monomer(s) Involved with Respect to Toxicity, Flammability, and Odor 81 5.2 Heat of Polymerization Removal Capacity of System 83 5.3 Bulk Polymerization 83 5.4 Solution Polymerization 84 5.5 Emulsion Polymerization 86 5.6 Suspension Polymerization 87 References 88 6. Crystallinity and Crystallization in Polymers and Plastics 91 6.1 Definitions, Concepts, Etc 91 6.2 Specific Volume and Crystallinity 93 6.3 Crystallization Kinetics 99 6.3.1 Isothermal Crystallization Kinetics: Avrami Model 99 6.3.2 Non-Isothermal Crystallization Kinetics: Ozawa Model 102 6.3.3 Rate of Crystallization of Polymers 103
Contents Vll 6.4 Determination of Degree or Percentage Crystallinity DSC; XRD, etc 105 6.4.1 X-Ray Diffraction Determination of Percentage Crystallinity 108 6.5 Practical Applications of Crystallinity and Crystallization in the Polymers and Plastics Industries Ill 6.5.1 Annealing Ill 6.5.2 Plasticization 112 6.5.3 Drawing of Crystallites/Spherulites for Fibers and Films 112 6.5.4 Nucleation (Seeding)-Transparency via Reduction of Spherulite Size 112 References 112 7. Classification of Thermoplastics 117 7.1 Commodity or General Purpose Thermoplastics 117 7.2 Quasi-Commodity Thermoplastics 119 7.3 Engineering Thermoplastic Materials 120 7.4 Specialty Thermoplastic Materials 120 7.5 New and Emerging Materials 121 7.5.1 Thermoplastic Nanocomposites 121 7.5.2 Functionalized Thermoplastics 121 References 122 8. Permeability and Environmental-Stress-Cracking Resistance of Thermoplastics: Barrier Properties and Packaging Applications of Polymers 125 8.1 Permeability and Packaging '. 125 8.2 Modified-Atmosphere Packaging Technology 132 8.3 Permeability and ESCR of Thermoplastics 136 8.3.1 Testing Methods for ESCR 139 8.3.1.1 Slow-Crack-Propagation and Rapid- Crack-Propagation Testing of Polymeric (Polyethylene) Materials 142 8.3.2 Limitations of ESCR Testing Methods 142 8.3.2.1 The SABIC-ESCR Test Method 143 Problem 145 References 145 9. Polyolefins: Polyethylene, Polypropylene, and Their Copolymers 149 9.1 Chronology of Polyolefins Revisited 149 9.2 The Polyolefin Family 149
Contents 9.3 Raw Materials 151 9.4 Manufacturing (Polymerization) Methods for Polyethylenes 153 9.4.1 Low-Density Polyethylene: The High-Pressure Process 153 9.4.2 Production of High-Density Polyethylene 155 9.4.3 Production of Linear Low-Density Polyethylene: Modified Gas-Phase Method 157 9.5 Unique Properties of Polyethylene 159 9.5.1 Problems of Polyethylene 162 9.6 Materials Selection of Polyethylenes 166 9.6.1 Melt Index 166 9.6.2 Molecular-Weight Distribution 167 9.7 Processing and Applications of Polyethylenes 168 9.7.1 Blown-Film Polyethylene Products 168 9.7.2 Cast-Film Polyethylene Products 169 9.7.3 Extrusion Coating and Laminated Polyethylene Products 170 9.7.4 Blow-Molded Polyethylene Products 171 9.7.5 Injection-Molded PE Products 172 9.7.6 Pipes and Profile-Extruded Polyethylene Products 173 9.7.6.1 Wire and Cable Coating 174 9.7.6.2 Extruded Sheet/Vacuum Forming 176 9.7.6.3 Rotational Molding 178 9.7.7 Coextruded PE Products 178 9.7.8 Other Polyethylene Applications 180 9.7.8.1 Ultrahigh-Molecular-Weight Polyethylene 180 References 189 Polypropylene 193 10.1 Overview and Chronology 193 10.2 Raw Materials for Polypropylene 194 10.3 Manufacturing of Polypropylene 196 10.3.1 The Spheripol Process 199 10.3.2 The Unipol Process 202 10.3.3 The Novolen Process 204 10.3.4 The Spherizone Process 205 10.4 Unique Properties of Polypropylene 208 10.4.1 Problems of Polypropylene 213 10.5 Material Selection Parameters for Polypropylene 215 10.6 Applications of Polypropylene 215 10.6.1 Polypropylene Resins in Appliances and Consumer Products 219 10.6.2 Automotive Applications of Polypropylene 220 10.6.2.1 Polypropylene Agricultural Products 224
IX 10.6.3 Building and Construction Applications of Polypropylene 226 10.6.4 Leisure, Outdoors, and Sports 227 10.6.5 Medical and Healthcare Applications of Polypropylene 230 10.6.6 Polypropylene Types in Medical Applications 231 10.6.6.1 Polypropylene Homopolymers 232 10.6.6.2 Random Copolymers 232 10.6.6.3 Heterophasic Copolymers 233 10.6.7 Medical Polypropylene Products 233 10.6.8 Packaging Applications of Polypropylene 233 10.6.8.1 Rigid Packaging Applications 235 10.6.8.2 Flexible Packaging Products 236 10.6.8.3 Modified Atmosphere Packaging Technology 238 10.6.8.4 Other Packaging Innovations 244 10.6.8.5 Washers for All Segments of Society 244 10.7 Polypropylene Fibers 246 10.7.1 Production of Polypropylene Fiber/Filament 249 10.7.2 Unique Properties of Polypropylene Fibers 251 10.7.2.1 Crystallinity of Polypropylene 252 10.7.2.2 Mechanical Properties of Polypropylene Fibers 252 10.7.2.3 Thermal Properties of Polypropylene Fibers 254 10.7.2.4 Dyeability of Polypropylene Fibers 254 10.7.2.5 Applications of Polypropylene Fibers 256 References 256 11. Olefin Copolymers of Ethylene and Propylene 261 11.1 EPM: Ethylene-Propylene Monomer Rubber 261 11.2 EPDM: Ethylene-Propylene-Diene Monomer Rubber 261 11.2.1 Overview of EPM and EPDM Elastomers 261 11.2.2 Producing Companies 262 11.2.3 Raw Materials and Manufacturing of EP Copolymers 262 11.2.4 Unique Properties of EPM and EPDM Elastomers 264 11.2.5 Applications of EPM and EPDM Elastomers 265 11.3 Ethylene-Vinyl Acetate Copolymers 265 11.3.1 Raw Materials and Polymerization Methods 265 11.3.2 Formulations and Characteristics of EVA Copolymers 266 11.3.3 Applications of EVA Copolymers 267 11.4 lonomers: Copolymers and Terpolymers 267 11.4.1 Raw Materials and Manufacturing of lonomers 267
x Contents 11.4.2 Properties and Characteristics of lonomer Copolymers...269 11.4.3 Processing and Applications of lonomer Copolymers... 270 11.5 Ethylene-Ester Copolymers 271 11.5.1 Applications of Ethylene-Ester Copolymers 273 References 273 12. The Vinyls: PVC and Copolymers 275 12.1 Chronology of PVC Revisited 275 12.2 The Vinyl Family 275 12.2.1 Polyvinyl Chloride 276 12.3 Raw Materials for PVC, 277 12.4 Manufacturing (Polymerization) Methods for PVC 279 12.4.1 Suspension Polymerization of PVC 280 12.4.2 Emulsion Polymerization of PVC 283 12.4.3 Plastisol Manufacturing of PVC 286 12.5 Unique Properties of PVC 288 12.5.1 Commonly Used Plasticizers for PVC 291 12.5.2 Problems Associated with PVC 293 12.6 Material Selection of PVC 294 12.7 Processing and Applications of PVC 296 12.7.1 Typical Processes for PVC 297 12.7.1.1 Extruded PVC Products 297 12.7.1.2 PVC Calendering Products 302 12.7.1.3 PVC Injection Molding Products 304 12.7.1.4 PVC Rotational Molding Products 306 12.7.1.5 PVC Dip/Spray/Roll (Plastisol) Coating Applications 308 12.8 Common Copolymers of PVC 309 12.8.1 Copolymer of VCM and Vinyl Acetate 309 12.8.2 Copolymer of VCM and VDC 310 12.8.2.1 Manufacturing of VCM/VDC Copolymer 310 12.8.3 Chlorinated PVC (CPVC): (Cl 2 ± PVC) 312 12.9 Trends in PVC Formulations 312 12.9.1 Ultrahigh-Molecular-Weight PVC (UHMWPVC) 312 12.9.2 Cross-Linked PVC 313 12.9.3 Blending and Copolymerization 313 12.10 Susceptibility to PVC Exposure 315 12.11 Future Look: A Health Concern Addendum 316 References 317 13. Polystyrene and Copolymers 323 13.1 The Styrene Family 323 13.2 Polystyrene 323 13.3 Chronology of Polystyrene Revisited 325 13.4 Raw Materials for Polystyrene 326
Contents xi 13.5 Manufacturing (Polymerization) Methods for Polystyrene 328 13.5.1 Bulk Polymerization of Polystyrene 329 13.5.2 Solution Polymerization of Polystyrene 331 13.5.3 Suspension Polymerization of Polystyrene 331 13.5.3.1 Post-Impregnation Suspension Process 332 13.5.3.2 In Situ Suspension Process 333 13.6 Properties and Characteristics of Polystyrene 333 13.6.1 Problems of Polystyrene 336 13.7 Combustion of Polystyrene 338 13.8 Processing and Applications of Polystyrene 338 13.8.1 Injection-Molding Applications of Polystyrene 341 13.8.2 Extrusion-Based Applications of Polystyrene 343 13.8.3 Thermoformed Polystyrene Products 345 13.9 Styrene-Acrylonitrile 349 13.9.1 Production of SAN 351 13.9.2 Properties of SAN 351 13.9.3 Applications of SAN 352 13.10 Acrylonitrile-Butadiene-Styrene Terpolymer Resin 353 13.10.1 Raw Materials of ABS 353 13.10.2 Manufacturing of ABS 354 13.10.3 The Continuous Bulk (Mass or Batch) Polymerization Production of ABS 355 13.10.4 Emulsion Polymerization of ABS Resins 357 13.10.5 Hybrid Emulsion/Bulk Process for ABS 357 13.10.6 Expandable ABS Process 358 13.10.7 Unique Properties of ABS Terpolymer Resins 358 13.10.8 Problems of ABS 359 13.10.9 Processing of ABS 359 13.10.10 Applications of ABS 360 13.11 K-Resin (Styrene-Butadiene Copolymer) 366 13.11.1 K-Resin Overview 366 13.11.2 Composition and Raw Materials of K-Resin 367 13.11.3 K-Resin SBC Grades 367 13.11.4 Unique Characteristics of K-Resin 368 13.11.4.1 Ease of Processing of K-Resin 369 13.11.4.2 Recycling of K-Resin 370 13.11.4.3 Bonding and Heat Sealability of K-Resin 371 13.11.4.4 Limitations of K-Resin 371 13.12 Acrylonitrile Styrene Acrylate Terpolymer 376 13.12.1 Manufacturing of ASA Terpolymer 376 13.12.2 Unique Characteristics of ASA 377 13.12.3 Limitations of ASA 378 13.12.4 Applications of ASA 378 13.13 Styrene-Butadiene Rubber 382 References 383
xii Contents 14. Acrylic (Acrylate) Family 389 14.1 Chronology of PMMA Revisited 389 14.2 The Acrylic Family and Their Raw Materials 389 14.2.1 Polyacrylonitrile 390 14.2.2 НЕМА: Poly(2-Hydroxyethyl Methacrylate) 390 14.2.3 Polyacrylamide 391 14.2.4 Trimethylolpropane Triacrylate 391 14.3 Polymethyl Methacrylate 391 14.4 Manufacturing (Polymerization) Methods for PMMA 392 14.4.1 Suspension Polymerization of PMMA 394 14.5 Unique Properties of PMMA 395 14.6 Materials Selection of PMMA 397 14.7 Processing and Applications of PMMA 398 14.8 Common Copolymers of MMA 402 References 403 15. Polyester Family 405 15.1 The Thermoplastic Polyester Family 405 15.2 Polyethylene Terephthalate 405 15.3 Raw Materials and Manufacturing Method of PET 407 15.3.1 PET Synthetic Fiber Production 409 15.3.2 PET Film Production 409 15.4 Unique Properties and Characteristics of PET Resins 409 15.5 Processing and Applications of Polyethylene Terephthalate 410 15.5.1 Typical Injection Molding Profile for PET 411 15.5.2 Mold Temperatures 411 15.5.3 Pressures 411 15.5.4 Applications of PET Are in the Fiber and Film Forms 411 15.6 Polybutylene Terephthalate 414 15.6.1 Properties of PBT 414 15.6.2 Processing of PBT 414 15.6.3 Applications of PBT 416 15.7 Polyethylene Naphthalate 417 15.7.1 Properties of PEN Polyester Resins 417 15.7.2 Applications of PEN 417 15.8 New Thermoplastic Polyester Resins 418 15.8.1 PCT Polyester 419 15.8.2 Polytrimethylene Terephthalate 419 15.8.3 Glycol-Modified Copolyesters 420 15.9 The Extended Polyester Family: Biodegradable Polyester Material 420 References 420
xiii. Nylon (Polyamide) Family 423 16.1 Chronology of Nylon: Revisited 423 16.2 The Nylon (Polyamide) Family 424 16.3 Raw Materials and Manufacturing (Polymerization) Methods for Nylons 425 16.3.1 Nylon 6/6 (Nylon 6/12, Nylon 6/10 Series Are Also Produced via This Route) 425 16.3.2 Nylon 6 426 16.3.3 Nylon 11 426 16.3.4 Nylon Designation 426 16.3.5 Nylon Rope Trick: Interfacial Condensation 427 16.4 Unique Characteristics of Nylons 428 16.4.1 Problems of Nylon 430 16.5 Processing and Applications of Nylons 431 16.5.1 Applications of Nylons 433 16.6 The Extended Polyamide Family: Semi-Aromatic and Aromatic Polyamides 446 References 447. Polycarbonates 449 17.1 Polycarbonates: Overview 449 17.2 Raw Materials and Manufacturing Methods for Polycarbonates 451 17.3 Unique Properties of Polycarbonates 453 17.3.1 Problems of Polycarbonates 455 17.4 Processing of Polycarbonate Resins 455 17.5 Applications of Polycarbonate Resins 456 17.5.1 Optical Media Applications of Polycarbonate Resins 457 17.5.2 Glazing Applications of Polycarbonate Resins 457 17.5.3 Electrical and Electronics Applications of Polycarbonate Resins 458 17.5.4 Transportation and Automotive Applications of Polycarbonate Resins 458 17.5.5 Medical Applications of Polycarbonate Resins 462 17.5.6 Polycarbonate Resins in Computer and Business Machine Applications 462 17.5.7 Polycarbonate Resins' Usage in Appliances 462 17.5.8 Polycarbonate Resins in Recreation and Safety Applications 463 17.5.9 Polycarbonate Resins in Packaging Applications 465 17.5.10 Miscellaneous Applications of Polycarbonate Resins...466 17.6 Polycarbonate Resins Case Study: Environmental and Health Impact of Bisphenol A: An Ethical Perspective 466 17.6.1 Situational Statement 466
XIV Contents 17.6.2 Environmental Estrogen? 467 17.6.3 Bisphenol A 467 17.6.3.1 Applications of Bisphenol A 468 17.6.3.2 Research on the Environmental Impact ofbpa 469 17.6.4 Low Dose Effects 470 17.7 Conclusion 470 References 470 18. Polyacetals 473 18.1 Overview 473 18.2 Raw Materials and Manufacturing Method of Polyacetal 474 18.3 Unique Properties of Polyacetal 475 18.3.1 Problems of Polyacetal 476 18.4 Processing and Applications of Polyacetal 476 References 479 19. Polyphenylene Sulfides 481 19.1 Polyphenylene Sulfides 481 19.2 Raw Materials and Manufacture of PPS 482 19.3 Unique Properties 482 19.4 Processing and Applications of Polyphenylene Sulfides 484 19.4.1 Applications of PPS 485 References 490 20. Fluorocarbons (Teflon Family) 491 20.1 The Fluorocarbon Family (Teflon) 491 20.1.1 PTFCE (PCTFE) Polychlorotrifluoroethylene 491 20.1.2 PVF Polyvinyl Fluoride 492 20.1.3 PVDF Polyvinylidene Fluoride 492 20.1.4 FEP Fluorinated Ethylene-Propylene Copolymer 492 20.1.5 Teflon: AF Amorphous Fluoropolymers 492 20.1.6 New Teflon Materials 493 20.2 Polytetrafluoroethylene 494 20.2.1 Unique Properties of PTFE 495 20.2.2 PTFE Problems 496 20.2.3 Applications of PTFE 497 References 497 21. Liquid Crystalline Polymers 499 21.1 LCP Overview 499 21.2 LCP Types 501 21.3 Raw Materials and Manufacturing (Polymerization) Methods for LCP 503 21.3.1 Synthesis of TLCPs 503 21.3.2 Synthesis of LLCPs 504
Contents xv 21.4 Unique Properties of Liquid Crystalline Polymers 505 21.5 Processing and Applications of LCPs 508 21.5.1 Applications of Liquid Crystalline Polymers 510 21.5.1.1 Electrical/Electronic Applications of LCPs 510 21.5.1.2 Automotive Applications of LCPs 513 21.5.1.3 Aerospace Applications of LCPs 515 21.5.1.4 Fiber Applications of LCPs 516 21.5.1.5 Medical Applications of LCPs 517 21.5.1.6 LCPs in Blends 518 21.5.1.7 Consumer and Household Applications of LCPs 519 References 520 22. Polysulfones 523 22.1 Polysulfone Family 523 22.2 Raw Materials and Manufacturing (Polymerization) Methods for Polysulfones 523 22.3 Unique Properties of Polysulfones 525 22.3.1 Unique Properties of Polysulfones: Limitations 526 22.4 Processing and Applications of Polysulfones 526 References 528 23. Polyimide Family 529 23.1 Polyetherimide: Overview 529 23.2 Raw Materials and Manufacturing Method 530 23.3 Unique Properties of Polyetherimide 531 23.4 Processing of PEI 533 23.5 Applications of PEI 534 23.5.1 Membrane Applications of PEI 534 23.5.2 Electrical/Electronic Applications of PEI 534 23.5.3 Automotive/Transportation Applications of PEI 535 References 536 24. PEEK 539 24.1 PEEK: Overview 539 24.2 Raw Materials and Manufacturing (Polymerization) Methods for PEEK 540 24.3 Unique Properties 541 24.4 Processing and Applications of PEEK 543 24.4.1 Aerospace Applications of PEEK 543 24.4.2 Automotive Applications of PEEK 544 24.4.3 Electronic Applications of PEEK 546 24.4.4 Medical Applications of PEEK 547 References 550
xvi Contents 25. Polyphenylene Oxide 551 25.1 Polyphenylene Oxide 551 25.2 Raw Materials and Manufacturing (Polymerization) Methods for PPO 551 25.3 Unique Properties of PPOs 552 25.3.1 Unique Properties of PPOs: Limitations 553 25.4 Processing and Applications of PPO 553 References '.,.554 26. Cellulosics 555 26.1 Cellulosics: Overview 555 26.2 Raw Materials and Manufacturing (Polymerization) Methods for Cellulosics 556 26.3 Unique Properties 557 26.4 Processing and Applications of Cellulosics 558 References 560 27. Functionalized Thermoplastic and Elastomers 561 Andrey Beyle and Christopher С Ibeh 27.1 Terminology and Definitions 561 27.2 Chemical Reactions of Polymers 561 27.2.1 Classical Indirect Polymerization Case of Polyvinyl Alcohol 561 27.2.2 Crosslinking-Type Reactions 562 27.2.3 Reactions Involving End Groups 562 27.2.4 Concept of the Degree of Functionalization 562 27.3 Functionalizing of Inert Polymers and Fillers 563 27.4 Thermoplastic Elastomers 565 27.5 Blends and Alloys 568 27.5.1 Compatibilization 568 27.6 Functionalized Thermoplastics and Elastomers 569 27.6.1 Examples of Functionalized Thermoplastics and Elastomers 571 27.6.1.1 Ethylene-Propylene Rubbers 571 27.6.1.2 Ion-Exchange Polymers 573 27.6.1.3 Linear Triblock Polystyrene-b- Polyisobutylene-b-Polystyrene (SIBS) 576 27.6.1.4 Polyethylene-Polypropylene Rubber Reactive Blending with Polybutylene Terephthalate 577 References 577
Contents xvii 28. Plastics Nanocomposites 579 28.1 Introduction 579 28.2 Major Types of Nanocomposites 581 28.2.1 Isodimensional Nanoparticle-Based Nanocomposites 582 28.2.2 Carbon Nanotube/Polymer Nanocomposites 582 28.2.3 Nanoplatelet Polymer Nanocomposites 583 28.3 Processing Challenges of Nanocomposites 585 28.4 Process Optimization 587 References 589 29. Plastics and Sustainability: A Life Cycle Cost Analysis Approach 591 29.1 Introduction 591 29.2 Life Cycle Analysis Format 593 29.3 LCA Steps 593 29.4 Impact Assessment 595 29.5 LCA Interpretation 596 29.6 LCA Benefits 596 References 596 Index 599