Polyolefins

Preface

Contents

1 Origins of Polyolefins

1.1 Introduction and Prehistory

1.2 Polyethylene

1.2.1 Low Density Polyethylene

1.2.2 Karl Ziegler and High Density Polyethylene

1.2.3 Standard Oil of Indiana

1.2.4 Phillips Petroleum and High Density Polyethylene

1.2.5 Linear Low Density Polyethylene

1.3 Isotactic Polypropylene

1.3.1 Giulio Natta, Milan Politechnico and Montecatini

1.3.2 Standard Oil of Indiana and Phillips Petroleum

1.4 Isotactic Polybutene-1

1.5 Isotactic Polymers of Higher Olefins and Poly(4-Methyl Pentene-1)

1.6 Ethylene-Propylene Rubber

1.7 Metallocene Polymerization

1.8 Stereoregular Polystyrenes

1.8.1 Isotactic Polystyrene

1.8.2 Syndiotactic Polystyrene

1.9 Syndiotactic Polypropylene

1.10 Cyclopolyolefins

1.11 New Metallocene Polyolefin Copolymers

1.12 Current Production Levels

1.13 Bulk Polymer Properties and Chemical Stability

References

2 Characterization Methods

2.1 Introduction

2.2 Asymmetric Carbon Atoms and Tacticity

2.2.1 Low Molecular Weight Compounds

2.2.2 Polyolefins [5]

2.2.3 Tacticity Levels

2.3 Crystallinity

2.4 Crystal Structure [16, 17]

2.5 Chain Conformations in Crystals

2.6 Molecular Weight Distribution [7, 34, 35]

2.7 Orientation

2.7.1 Uniaxial Orientation

2.7.2 Biaxial Orientation

2.8 Superstructure

References

3 Crystallography of Polyolefins

3.1 Introduction

3.2 Early Investigations of Low Molecular Weight Paraffinic Compounds

3.3 Polyethylene

3.4 Isotactic Polypropylene

3.5 Syndiotactic Polypropylene

3.6 Isotactic Polybutene-1

3.7 Syndiotactic Polybutene-1

3.8 Isotactic Poly(4-Methyl Pentene-1)

3.9 Isotactic Polymers of Other a-Olefins

3.10 Isotactic Polystyrene

3.11 Syndiotactic Polystyrene

3.12 Summary and Trends

References

4 Single Crystals: Structural Hierarchy and Morphology

4.1 Introduction

4.2 Polyethylene

4.2.1 Single Crystals

4.2.2 Flow-Induced Structures from Solution

4.2.3 Bulk Structure

4.3 Isotactic Polypropylene

4.3.1 Single Crystals

4.3.2 Flow-Induced Structures from Solution

4.3.3 Bulk Structure

4.4 Syndiotactic Polypropylene

4.5 Isotactic Polybutene-1

4.5.1 Single Crystals

4.5.2 Bulk Structure

4.6 Isotactic Poly(4-Methyl Pentene-1)

4.6.1 Single Crystals

4.6.2 Flow-Induced Structures from Solution

4.6.3 Bulk Structures

4.7 Isotactic Polystyrene

4.7.1 Single Crystals

4.7.2 Flow-Induced Structures from Solution

4.7.3 Bulk Structure

4.8 Syndiotactic Polystyrene

4.8.1 Single Crystals

4.8.2 Bulk Structures

4.9 Summary

References

5 Spherulites and Quiescent Crystallization

5.1 Introduction

5.2 Spherulites

5.2.1 Quiescently Crystallized Polymers

5.2.2 Polyethylene

5.2.3 Isotactic Polypropylene

5.2.4 Syndiotactic Polypropylene

5.2.5 Isotactic Polybutene-1

5.2.6 Isotactic Poly(4-methyl pentene-1)

5.2.7 Isotactic Polystyrene

5.2.8 Syndiotactic Polystyrene

5.3 Quiescent Crystallization Kinetics

5.3.1 General

5.3.2 Polyethylene

5.3.3 Isotactic Polypropylene

5.3.4 Syndiotactic Polypropylene

5.3.5 Isotactic Polybutene-1

5.3.6 Isotactic Polystyrene

5.3.7 Syndiotactic Polystyrene

5.4 Time-Temperature Transformation and Continuous Cooling Transformation Plots

5.5 Summary and Perspectives

References

6 Polyolefin Copolymers and Blends

6.1 Introduction

6.2 Stereoblock Copolymers [1, 2]

6.3 Copolymers of Polyethylene

6.3.1 General

6.3.2 Ethylene-Propylene Copolymers (EPM)

6.3.3 Ethylene-Butene-1/Hexene-1 Copolymers

6.3.4 Ethylene-Octene Copolymers

6.3.5 Ethylene-Styrene Copolymers

6.3.6 Ethylene-Cyclopentene/Norbornene Copolymers

6.4 Copolymers of Polypropylene

6.4.1 Isotactic Polypropylene with Ethylene [53]

6.4.2 Isotactic Polypropylene with Other Monomers

6.4.3 Syndiotactic Polypropylene with Butene-1

6.5 Blends

6.5.1 Inter-Polyolefin Homopolymer Miscibility

6.5.2 Polypropylene-Ethylene Copolymer Blends

6.5.3 Polypropylene Dynamic Vulcanizates [68]

6.6 Perspective

References

7 Polymer Melt Processing, Rheological Properties, and Orientation in Flowing Polymer Melts

7.1 Introduction

7.2 Polymer Melt Processing Technology

7.2.1 Single Screw Extrusion [1, 2]

7.2.2 Twin Screw Extrusion and Polyolefin Modification/Grafting [2–4]

7.2.3 Die Extrusion [11]

7.3 Rheological Properties of Polymer Melts

7.4 Effects of Additives

7.5 Early Observations of Flow Birefringence

7.6 Flow Birefringence and Stress

7.7 Stress Optical Coefficients and Molecular Structure

7.8 Orientation Factors and Stress in Melts

7.9 Flow in Dies

7.9.1 Flow Patterns and Flow Birefringence

7.9.2 Unstable Flow

7.9.3 Flow Structuring of Polyolefins

7.10 Summary

References

8 Melt Spinning

8.1 Introduction

8.2 Melt Spinning Process

8.2.1 General

8.2.2 Continuous Filaments

8.2.3 Bulked Continuous Filament Yarns

8.2.4 Staple Fibers [15]

8.2.5 Spunbonded Fabrics [14, 18–21]

8.2.6 Melt-Blown Fabrics [14]

8.3 Dynamics, Heat Transfer, and Modeling in Melt Spinning

8.3.1 Dynamics and Heat Balance

8.3.2 Modeling of Melt Spinning

8.4 Melt Flow Instabilities

8.4.1 Die Flow (see also Section 7.9.2)

8.4.2 Spinline Disturbances/Instabilities

8.5 Melt Spinning of Vitrifying Polyhydrocarbons

8.5.1 Atactic Polystyrene

8.5.2 Cyclopolyolefins

8.5.3 Other Vitrifying Thermoplastics

8.5.4 Modeling of Orientation-Birefringence Development

8.6 Polyethylene

8.6.1 High-Density Polyethylene

8.6.2 Ultrahigh Modulus Polyethylene Fibers

8.6.3 Polyethylene Copolymers

8.6.4 Polyethylene-Polystyrene Blends

8.7 Isotactic Polypropylene

8.7.1 High Tacticity Polymers

8.7.2 Lower Tacticity Polymers

8.7.3 Isotactic Polypropylene-Particulate Compounds

8.7.4 Isotactic Polypropylene Blends

8.7.5 Isotactic Polypropylene Thermoplastic Dynamic Vulcanizates

8.8 Syndiotactic Polypropylene

8.9 Isotactic Polybutene-1

8.10 Isotactic Poly(4-Methyl Pentene-1)

8.11 Syndiotactic Polystyrene

8.12 Trends and Conclusions

References

9 Film Processing and Profile Extrusion

9.1 Introduction

9.2 Film Extrusion Processes

9.2.1 Cast Film Extrusion

9.2.2 Tubular Blown Film Extrusion

9.2.3 Tentering Frame for Biaxially Oriented Film [12]

9.2.4 Double Bubble Process for Biaxially Oriented Film [13]

9.3 Dynamics, Heat Transfer, and Modeling

9.3.1 Cast Film Extrusion [16–18]

9.3.2 Tubular Blown Film Extrusion

9.4 Melt Flow and Solidification Instabilities

9.4.1 Haze and Surface Roughness

9.4.2 Die Flow Produced Extrudate Distortion

9.4.3 Cast Film Instabilities

9.4.4 Bubble Instabilities

9.5 Profile Extrusion

9.6 Atactic Polystyrene Film

9.6.1 Tubular Blown Film

9.6.2 Biaxially Stretched Film

9.7 Polyethylene Film

9.8 Isotactic Polypropylene Film

9.8.1 Cast Film

9.8.2 Tubular Blown Film

9.8.3 Biaxially Oriented Film

9.9 Syndiotactic Polypropylene Film

9.10 Isotactic Polybutene-1 Film

9.11 Isotactic Poly(4-Methyl Pentene-1) Film

9.12 Syndiotactic Polystyrene Film

9.13 Summary and Conclusions

References

10 Molding

10.1 Introduction

10.2 Molding Processes

10.2.1 Compression Molding

10.2.2 Injection Molding

10.2.3 Blow Molding

10.2.4 Thermoforming [31]

10.2.5 Scrapless Forming [32]

10.2.6 Rotational Molding [33]

10.3 Dynamics, Heat Transfer, and Modeling

10.3.1 Injection Molding

10.3.2 Blow Molding

10.4 Atactic Polystyrene and Vitrifying Polyolefins

10.4.1 Injection Molding

10.4.2 Blow Molding

10.4.3 Modeling of Orientation-Birefringence Development

10.5 Polyethylene

10.5.1 Injection Molding

10.5.2 Blow Molding

10.5.3 Rotational Molding

10.6 Isotactic Polypropylene

10.7 Syndiotactic Polypropylene

10.8 Isotactic Poly(4-Methyl Pentene-1)

10.9 Isotactic Polystyrene

10.10 Syndiotactic Polystyrene

10.11 Trends and Conclusions

References

11 Mechanical Properties of Polyolefins

11.1 Introduction

11.2 Stress and Small Strain Elasticity

11.3 Influence of Molecular Weight

11.4 Influence of Temperature

11.5 Influence of Crystallinity and Comparisons to Other Materials

11.6 Uniaxial Large Strain Behavior [3, 4]

11.7 Mechanical Properties of Melt-Spun/Drawn Fibers

11.8 High Modulus Polyolefin Fibers

11.9 Mechanical Properties of Films

11.10 Mechanical Property Modification by Copolymerization and Blending

References

Subject Index

Author Index