THERMOPLASTIC MATERIALS Properties, Manufacturing Methods, and Applications

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1 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

2 Contents Preface Author xix xxiii 1. Introduction and History of the Plastics Industry Definition and Types Overview of the Plastics Industry Areas of Application of Plastics Example Applications of Plastic Resins Chronology of the Thermoplastics (Plastics) Industry: The Need Factor Current Trends in the Plastics Industry Electrically Conductive Plastics Blending and Alloying Polymer-Matrix Composites and Polymer-Matrix Nanocomposites Recycling and Sustainability Biodegradable Plastics High-Temperature Plastics 21 References Raw Materials and Their Sources: "The Plastics Tree" Sources and Raw Materials of Polymers and Plastics Compounding and Property Enhancement Processing of Polymers and Plastics 34 References Basic Structures and Characteristics of Polymers and Plastics Chemical Bonding in Polymers and Plastics Ionization Potential and Chemical Bonding Major Types of Chemical Bonding in Polymers and Plastics Secondary Bonds Structural Units in Polymers (Plastics Resins) Polymer Types Stereoregularity Copolymers 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 vi Contents 4. Molecular Weight of Polymers Introduction Molecular Weight Distribution Average Molecular Weight of Polymers Determination of Average Molecular Weight Nomenclature for Molecular Weight Calculations Number Average Molecular Weight (M ) Number Average Molecular Weight Degree of Polymerization (DP,,) Weight Average Molecular Weight (M w ) Molecular Weight Determination via the Light-Scattering Method Viscosity Average Molecular Weight (M v ) Viscosity Average Molecular Weight (M v ) via the Mark-Houwink Empirical Relation (Equation) Fikentscher K-Value The Margolies Equation: Viscosity Average Molecular Weight Z-Average Molecular Weight (M z ) The Analytical Ultracentrifuge Sedimentation Equilibrium Method The Melt Index Correlation between Molecular Weight andmfr 78 References Polymerization (Resinification) Methods Chemistry of Reaction of Monomer(s) Involved with Respect to Toxicity, Flammability, and Odor Heat of Polymerization Removal Capacity of System Bulk Polymerization Solution Polymerization Emulsion Polymerization Suspension Polymerization 87 References Crystallinity and Crystallization in Polymers and Plastics Definitions, Concepts, Etc Specific Volume and Crystallinity Crystallization Kinetics Isothermal Crystallization Kinetics: Avrami Model Non-Isothermal Crystallization Kinetics: Ozawa Model Rate of Crystallization of Polymers 103

$Contents Vll 6.4 Determination of Degree or Percentage Crystallinity DSC; XRD, etc 105 6.4.1 X-Ray Diffraction Determination of Percentage Crystallinity 108 6.$

4 Contents Vll 6.4 Determination of Degree or Percentage Crystallinity DSC; XRD, etc X-Ray Diffraction Determination of Percentage Crystallinity Practical Applications of Crystallinity and Crystallization in the Polymers and Plastics Industries Ill Annealing Ill Plasticization Drawing of Crystallites/Spherulites for Fibers and Films Nucleation (Seeding)-Transparency via Reduction of Spherulite Size 112 References Classification of Thermoplastics Commodity or General Purpose Thermoplastics Quasi-Commodity Thermoplastics Engineering Thermoplastic Materials Specialty Thermoplastic Materials New and Emerging Materials Thermoplastic Nanocomposites Functionalized Thermoplastics 121 References Permeability and Environmental-Stress-Cracking Resistance of Thermoplastics: Barrier Properties and Packaging Applications of Polymers Permeability and Packaging ' Modified-Atmosphere Packaging Technology Permeability and ESCR of Thermoplastics Testing Methods for ESCR Slow-Crack-Propagation and Rapid- Crack-Propagation Testing of Polymeric (Polyethylene) Materials Limitations of ESCR Testing Methods The SABIC-ESCR Test Method 143 Problem 145 References Polyolefins: Polyethylene, Polypropylene, and Their Copolymers Chronology of Polyolefins Revisited 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.

5 Contents 9.3 Raw Materials Manufacturing (Polymerization) Methods for Polyethylenes Low-Density Polyethylene: The High-Pressure Process Production of High-Density Polyethylene Production of Linear Low-Density Polyethylene: Modified Gas-Phase Method Unique Properties of Polyethylene Problems of Polyethylene Materials Selection of Polyethylenes Melt Index Molecular-Weight Distribution Processing and Applications of Polyethylenes Blown-Film Polyethylene Products Cast-Film Polyethylene Products Extrusion Coating and Laminated Polyethylene Products Blow-Molded Polyethylene Products Injection-Molded PE Products Pipes and Profile-Extruded Polyethylene Products Wire and Cable Coating Extruded Sheet/Vacuum Forming Rotational Molding Coextruded PE Products Other Polyethylene Applications Ultrahigh-Molecular-Weight Polyethylene 180 References 189 Polypropylene Overview and Chronology Raw Materials for Polypropylene Manufacturing of Polypropylene The Spheripol Process The Unipol Process The Novolen Process The Spherizone Process Unique Properties of Polypropylene Problems of Polypropylene Material Selection Parameters for Polypropylene Applications of Polypropylene Polypropylene Resins in Appliances and Consumer Products Automotive Applications of Polypropylene 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 IX Building and Construction Applications of Polypropylene Leisure, Outdoors, and Sports Medical and Healthcare Applications of Polypropylene Polypropylene Types in Medical Applications Polypropylene Homopolymers Random Copolymers Heterophasic Copolymers Medical Polypropylene Products Packaging Applications of Polypropylene Rigid Packaging Applications Flexible Packaging Products Modified Atmosphere Packaging Technology Other Packaging Innovations Washers for All Segments of Society Polypropylene Fibers Production of Polypropylene Fiber/Filament Unique Properties of Polypropylene Fibers Crystallinity of Polypropylene Mechanical Properties of Polypropylene Fibers Thermal Properties of Polypropylene Fibers Dyeability of Polypropylene Fibers Applications of Polypropylene Fibers 256 References Olefin Copolymers of Ethylene and Propylene EPM: Ethylene-Propylene Monomer Rubber EPDM: Ethylene-Propylene-Diene Monomer Rubber Overview of EPM and EPDM Elastomers Producing Companies Raw Materials and Manufacturing of EP Copolymers Unique Properties of EPM and EPDM Elastomers Applications of EPM and EPDM Elastomers Ethylene-Vinyl Acetate Copolymers Raw Materials and Polymerization Methods Formulations and Characteristics of EVA Copolymers Applications of EVA Copolymers lonomers: Copolymers and Terpolymers 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

7 x Contents Properties and Characteristics of lonomer Copolymers Processing and Applications of lonomer Copolymers Ethylene-Ester Copolymers Applications of Ethylene-Ester Copolymers 273 References The Vinyls: PVC and Copolymers Chronology of PVC Revisited The Vinyl Family Polyvinyl Chloride Raw Materials for PVC, Manufacturing (Polymerization) Methods for PVC Suspension Polymerization of PVC Emulsion Polymerization of PVC Plastisol Manufacturing of PVC Unique Properties of PVC Commonly Used Plasticizers for PVC Problems Associated with PVC Material Selection of PVC Processing and Applications of PVC Typical Processes for PVC Extruded PVC Products PVC Calendering Products PVC Injection Molding Products PVC Rotational Molding Products PVC Dip/Spray/Roll (Plastisol) Coating Applications Common Copolymers of PVC Copolymer of VCM and Vinyl Acetate Copolymer of VCM and VDC Manufacturing of VCM/VDC Copolymer Chlorinated PVC (CPVC): (Cl 2 ± PVC) Trends in PVC Formulations Ultrahigh-Molecular-Weight PVC (UHMWPVC) Cross-Linked PVC Blending and Copolymerization Susceptibility to PVC Exposure Future Look: A Health Concern Addendum 316 References Polystyrene and Copolymers The Styrene Family Polystyrene Chronology of Polystyrene Revisited 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.

8 Contents xi 13.5 Manufacturing (Polymerization) Methods for Polystyrene Bulk Polymerization of Polystyrene Solution Polymerization of Polystyrene Suspension Polymerization of Polystyrene Post-Impregnation Suspension Process In Situ Suspension Process Properties and Characteristics of Polystyrene Problems of Polystyrene Combustion of Polystyrene Processing and Applications of Polystyrene Injection-Molding Applications of Polystyrene Extrusion-Based Applications of Polystyrene Thermoformed Polystyrene Products Styrene-Acrylonitrile Production of SAN Properties of SAN Applications of SAN Acrylonitrile-Butadiene-Styrene Terpolymer Resin Raw Materials of ABS Manufacturing of ABS The Continuous Bulk (Mass or Batch) Polymerization Production of ABS Emulsion Polymerization of ABS Resins Hybrid Emulsion/Bulk Process for ABS Expandable ABS Process Unique Properties of ABS Terpolymer Resins Problems of ABS Processing of ABS Applications of ABS K-Resin (Styrene-Butadiene Copolymer) K-Resin Overview Composition and Raw Materials of K-Resin K-Resin SBC Grades Unique Characteristics of K-Resin Ease of Processing of K-Resin Recycling of K-Resin Bonding and Heat Sealability of K-Resin Limitations of K-Resin Acrylonitrile Styrene Acrylate Terpolymer Manufacturing of ASA Terpolymer Unique Characteristics of ASA Limitations of ASA Applications of ASA 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.

9 xii Contents 14. Acrylic (Acrylate) Family Chronology of PMMA Revisited The Acrylic Family and Their Raw Materials Polyacrylonitrile НЕМА: Poly(2-Hydroxyethyl Methacrylate) Polyacrylamide Trimethylolpropane Triacrylate Polymethyl Methacrylate Manufacturing (Polymerization) Methods for PMMA Suspension Polymerization of PMMA Unique Properties of PMMA Materials Selection of PMMA Processing and Applications of PMMA Common Copolymers of MMA 402 References Polyester Family The Thermoplastic Polyester Family Polyethylene Terephthalate Raw Materials and Manufacturing Method of PET PET Synthetic Fiber Production PET Film Production Unique Properties and Characteristics of PET Resins Processing and Applications of Polyethylene Terephthalate Typical Injection Molding Profile for PET Mold Temperatures Pressures Applications of PET Are in the Fiber and Film Forms Polybutylene Terephthalate Properties of PBT Processing of PBT Applications of PBT Polyethylene Naphthalate Properties of PEN Polyester Resins Applications of PEN New Thermoplastic Polyester Resins PCT Polyester Polytrimethylene Terephthalate Glycol-Modified Copolyesters 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.

10 xiii. Nylon (Polyamide) Family Chronology of Nylon: Revisited The Nylon (Polyamide) Family Raw Materials and Manufacturing (Polymerization) Methods for Nylons Nylon 6/6 (Nylon 6/12, Nylon 6/10 Series Are Also Produced via This Route) Nylon Nylon Nylon Designation Nylon Rope Trick: Interfacial Condensation Unique Characteristics of Nylons Problems of Nylon Processing and Applications of Nylons Applications of Nylons The Extended Polyamide Family: Semi-Aromatic and Aromatic Polyamides 446 References 447. Polycarbonates Polycarbonates: Overview Raw Materials and Manufacturing Methods for Polycarbonates Unique Properties of Polycarbonates Problems of Polycarbonates Processing of Polycarbonate Resins Applications of Polycarbonate Resins Optical Media Applications of Polycarbonate Resins Glazing Applications of Polycarbonate Resins Electrical and Electronics Applications of Polycarbonate Resins Transportation and Automotive Applications of Polycarbonate Resins Medical Applications of Polycarbonate Resins Polycarbonate Resins in Computer and Business Machine Applications Polycarbonate Resins' Usage in Appliances Polycarbonate Resins in Recreation and Safety Applications Polycarbonate Resins in Packaging Applications Miscellaneous Applications of Polycarbonate Resins Polycarbonate Resins Case Study: Environmental and Health Impact of Bisphenol A: An Ethical Perspective 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.

11 XIV Contents Environmental Estrogen? Bisphenol A Applications of Bisphenol A Research on the Environmental Impact ofbpa Low Dose Effects Conclusion 470 References Polyacetals Overview Raw Materials and Manufacturing Method of Polyacetal Unique Properties of Polyacetal Problems of Polyacetal Processing and Applications of Polyacetal 476 References Polyphenylene Sulfides Polyphenylene Sulfides Raw Materials and Manufacture of PPS Unique Properties Processing and Applications of Polyphenylene Sulfides Applications of PPS 485 References Fluorocarbons (Teflon Family) The Fluorocarbon Family (Teflon) PTFCE (PCTFE) Polychlorotrifluoroethylene PVF Polyvinyl Fluoride PVDF Polyvinylidene Fluoride FEP Fluorinated Ethylene-Propylene Copolymer Teflon: AF Amorphous Fluoropolymers New Teflon Materials Polytetrafluoroethylene Unique Properties of PTFE PTFE Problems Applications of PTFE 497 References Liquid Crystalline Polymers LCP Overview LCP Types Raw Materials and Manufacturing (Polymerization) Methods for LCP Synthesis of TLCPs 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.

12 Contents xv 21.4 Unique Properties of Liquid Crystalline Polymers Processing and Applications of LCPs Applications of Liquid Crystalline Polymers Electrical/Electronic Applications of LCPs Automotive Applications of LCPs Aerospace Applications of LCPs Fiber Applications of LCPs Medical Applications of LCPs LCPs in Blends Consumer and Household Applications of LCPs 519 References Polysulfones Polysulfone Family Raw Materials and Manufacturing (Polymerization) Methods for Polysulfones Unique Properties of Polysulfones Unique Properties of Polysulfones: Limitations Processing and Applications of Polysulfones 526 References Polyimide Family Polyetherimide: Overview Raw Materials and Manufacturing Method Unique Properties of Polyetherimide Processing of PEI Applications of PEI Membrane Applications of PEI Electrical/Electronic Applications of PEI Automotive/Transportation Applications of PEI 535 References PEEK PEEK: Overview Raw Materials and Manufacturing (Polymerization) Methods for PEEK Unique Properties Processing and Applications of PEEK Aerospace Applications of PEEK Automotive Applications of PEEK Electronic Applications of PEEK 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.

13 xvi Contents 25. Polyphenylene Oxide Polyphenylene Oxide Raw Materials and Manufacturing (Polymerization) Methods for PPO Unique Properties of PPOs Unique Properties of PPOs: Limitations Processing and Applications of PPO 553 References '., Cellulosics Cellulosics: Overview Raw Materials and Manufacturing (Polymerization) Methods for Cellulosics Unique Properties Processing and Applications of Cellulosics 558 References Functionalized Thermoplastic and Elastomers 561 Andrey Beyle and Christopher С Ibeh 27.1 Terminology and Definitions Chemical Reactions of Polymers Classical Indirect Polymerization Case of Polyvinyl Alcohol Crosslinking-Type Reactions Reactions Involving End Groups Concept of the Degree of Functionalization Functionalizing of Inert Polymers and Fillers Thermoplastic Elastomers Blends and Alloys Compatibilization Functionalized Thermoplastics and Elastomers Examples of Functionalized Thermoplastics and Elastomers Ethylene-Propylene Rubbers Ion-Exchange Polymers Linear Triblock Polystyrene-b- Polyisobutylene-b-Polystyrene (SIBS) 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.

14 Contents xvii 28. Plastics Nanocomposites Introduction Major Types of Nanocomposites Isodimensional Nanoparticle-Based Nanocomposites Carbon Nanotube/Polymer Nanocomposites Nanoplatelet Polymer Nanocomposites Processing Challenges of Nanocomposites Process Optimization 587 References Plastics and Sustainability: A Life Cycle Cost Analysis Approach Introduction Life Cycle Analysis Format LCA Steps Impact Assessment LCA Interpretation LCA Benefits 596 References 596 Index 599

Understanding the Basics of Plastic Materials and the IAPD Thermoplastics Rectangle. Prepared by the IAPD Education Committee (Module 2)

Understanding the Basics of Plastic Materials and the IAPD Rectangle Prepared by the IAPD Education Committee (Module 2) Key Characteristics: Very High Cost Per Pound Excellent Properties Above 400 F Excellent