Chemical Engineering @ChemengFiles.Com

In this single handbook the editors aim to give a diverse audience of readers a complete account of all aspects of PVC – from monomer manufacture to polymerization; the gamut of such additives as stabilizers, lubricants, plasticizers, impact modifiers, fillers and reinforcing agents; blends and alloys; compounding and processing; characterization; combustion resistance and weatherability; product engineering design; applications; environmental and safety; and finally the PVC industry dynamics. Jim Summers’ Introduction presents a good historical background on PVC and several of the individual chapters give a historical perspective to the technologies therein. The handbook contains both practical formulation information as well as a mechanistic view of why PVC behaves as it does. The authors are from both industry and academia. Not surprisingly, many of the industry authors are from the former BF Goodrich laboratories, where much of the industry’s technology was developed. Overall, however, about ten PVC and chemical- supplier companies are represented by the authors.

Content:

1 Introduction

1.1 Chemistry and Physical Structure .
1.1.1 Raw Materialds
1.1.2 Chlorine Content and Combustion Resistance
1.1.3 Polymerization Morphology
1.1.4 Vinyl’s Unique Melt Processing
1.1.5 Properties Depend
1.1.6 Vinyl as a Thermoplastic
1.1.7 PVC’s Solubility Parameter and Ease of Compounging
1.2 Vinyl’s Proud History

1.2.1 PVC Meeting Society’s Needs
1.2.2 The PVC Industry as a Responsible Citizen
1.2.3 Historic Events

1.2.3.1 Chlorine
1.2.3.2 Vinyl Chloride
1.2.3.3 Polymerization .
1.2.3.4 Early Processing
1.2.3.5 Plasticized PVC as a TPE
1.2.3.6 Wire and Cable
1.2.3.7 Pipe and Fittings
1.2.3.8 Siding,Windows, and Packaging
1.2.3.9 Society of Plastics Engineers, Vinyl Division
1.2.3.10 Weatherability
1.2.3.11 Vinyl Chloride Exposure and Responsible Care
1.2.3.12 Recycling .

1.3 Commercial Significance .

1.3.1 Growth of the Vinyl Industry
1.3.2 PVC as a Major Thermoplastic
1.3.3 PVC as a Thermoplastic Elastomer (TPE)
1.3.4 PVC as an Engineering Thermoplastic

2 Vinyl Chloride Monomer

2.1 Overview
2.2 Introduction
2.3 Physical Properties
2.4 Reactions
2.4.1 Polymerization .
2.4.2 Substitution at the Carbon-Chlorine Bond
2.4.3 Oxidation
2.4.4 Addition .
2.4.5 Photochemistry
2.4.6 Pyrolysis .

2.5 Manufacture .

2.5.2 Oxychlorination

2.6 Purification of Ethylene Dichloride for Pyrolysis
2.7 Ethylene Dichloride Pyrolysis to Vinyl Chloride .
2.9 Economic Aspects .
2.10 Environmental Considerations
2.11 Technology Trends
2.12 Specifications
2.13 Health and Safety Factors
2.14 Uses

3 Polymerization

3.1 Basic Considerations
3.2 Suspension Process Overview .
3.2.1 Polymerization
3.2.3 Centrifugation
3.2.4 Drying and Screening

3.4 Special Considerations

3.4.1 Polymerization Kinetics
3.4.2 Resin Particle Structure and Formations
3.4.3 Agitation and Dispersants
3.4.4 Vinyl Chloride Recovery
3.4.5 Increasing Reactor Productivity
3.4.6 Chain Defects and Heat Stability
3.4.7 Molecular Weight Extension
3.4.8 Co-Polymerization

3.6 Microsuspension and Emulsion Polymerization

3.6.1 Microsuspension Polymerization of Vinyl Chloride
Compared to Emulsion and Suspension Polymerization
3.6.2 Procedure and Variations
3.6.3 Emulsion Polymerization of Vinyl Chloride Compared to
Microsuspension and Suspension PVC Polymerization
3.7 Procedure for Batch Polymerization
3.8 Other Considerations for Microsuspension and Emulsion Polymerization of PVC
3.8.1 Surfactant System
3.8.2 Initiators
3.8.4 Copolymers
3.9 Primary Particle Size Microsuspension
3.9.1 Primary Particle Size Emulsions
3.10 Molecular Weight
3.11 Polymerization Equipment Operation
3.11.1 Homogenizers
3.11.3 Agitation
3.11.4 Heat Removal

3.12 Downstream Equipment .

3.12.1 Residual Vinyl Chloride Removal (Stripping)
3.12.2 Drying
3.12.3 Grinding
3.12.4 Packaging

3.13 Product Quality
3.14 Safety and Environment

4 PVC Stabilizers and Lubricanta

4.1 Introductions
4.2 World PVC Stabilizer and Lubricant Markets
4.3 Structure and Degradation of PVC
4.4 The General Stabilization of PVC
4.5 The General Lubrication of PVC
4.6 Lead Stabilizers
4.6.1 Lead Stabilizer Chronology
4.6.2 Lead Stabilizer Manufacturing
4.6.3 Lead Stabilization Mechanisms
4.6.4 Lead Stabilizers of Commercial Importance
4.6.5 Lead Stabilizer Strengths and Weaknesses
4.6.6 Lead Stabilizer/Lubricant Use Levels .

4.7 Organotin Stabilizers

4.7.1 Organotin Stabilizer Chronology
4.7.2 Organotin Stabilizer Manufacturing
4.7.3 Organotin Stabilizer Mechanism
4.7.4 Organotin Stabilizers of Commercial Importance
4.7.5 Organotin Stabilizer Synergists
4.7.6 Lubrication of Organotin Stabilizers
4.7.7 Organotin Stabilizer Strengths and Weakness
4.7.8 Organotin Stabilizer/Lubricant Use Levels

4.8 Mixed Metal Stabilizers
4.8.1 Mixed Metal Chronology

4.8.2 Mixed Metal Manufacturing
4.8.3 Mixed Metal Stabilizer Mechanisms
4.8.4 Mixed Metal Stabilizer Synergists

4.8.4.1 Epoxy Esters
4.8.4.2 Phosphite Esters
4.8.4.3 Minor Organic Synergists
4.8.4.4 Inorganic Acid Scavengers

4.8.5 Mixed Metal Strengths and Weaknesses
4.8.6 Mixed Metal Stabilizer/Lubricant Use Levels

4.9 PVC Lubricants

4.9.1 Internal and External Lubricants
4.9.2 Three Category Lubricant Classification
4.9.3 Lubricant-Lubricant Interactions
4.9.4 Stabilizer Lubricant Interactions
4.9.5 Lubricating Stabilizers
4.9.7 Stabilizer Lubricant One-Packs
4.9.8 Lubricant Sources
4.9.8.1 Petroleum Waxes
4.9.8.2 Synthetic Hydrocarbon Waxes
4.9.8.3 Mineral Waxes
4.9.8.4 Natural Triglycerides

4.10 Testing of Stabilizers and Lubricants

4.10.1 Oven Stability Tests
4.10.2 Press Clarity and Color
4.10.3 Dynamic Milling
4.10.4 Torque Rheometer Testing
4.10.5 Plate-Out Test
4.10.6 Volatility Tests
4.10.7 Compatibility Tests
4.10.8 Stabilizer-Stabilizer-Incompatibilities

4.11 Suppliers of PVC Stabilizers and Lubricants
4.12 PVC Stabilizer Environmental Concerns

4.12.1 General Environmental Concerns
4.12.2 Lead Environmental Concerns
4.12.3 Cadmium Environmental Concerns
4.12.4 Barium Environmental Concerns
4.12.5 Organotin Environmental Concerns
4.12.6 Stabilizers Based Upon Food Additives

4.13 Chemistry of Degradation and Stabilization
4.14 Mechanism of Thermal Dehydrochlorination

4.14.1 Thermally Labile Structural Defects
4.14.2 Hypothetical Labile Structures
4.14.3 Polyene Elongation
4.14.3.1 Ion-Pair/Quasiionic Mechanism
4.14.3.2 Other Proposed Mechanisms
4.14.3.3 Autocatalysis

4.15 Thermal Stabilization

4.15.1 General Mechanisms
4.15.2 Stabilizers Containing Metals
4.15.3 Organic Stabilizers
4.15.3.1 Costabilizers
4.15.3.2 Principal Stabilizers (Ester Thiols)

4.16 Acknowledgments

5 Plasticizers

5.1 Introduction
5.2 Historical Developments
5.3 Mechanisms of Plasticization
5.4 Types of Plasticizers
5.5 Plasticizer Performance
5.6 Plasticizer Efficiency
5.7 Low Temperature
5.8 Permanence (Transience) of Plasticizers
5.9 Solvency, Miscibility, or Compatibility
5.10 Processability
5.11 Plasticizer Markets
5.12 Health Aspects of Plasticizers
5.13 Future of Plasticizers

6 Processing Aids and Impact Modifiers

6.1 Processing Aids
6.1.1 Introduction
6.1.2 Development
6.1.3 Role of Processing Aids in PVC
6.1.3.1 Promotion of Homogeneous Melt
6.1.3.2 Melt Homogeneity
6.1.3.3 Melt Strength, Extensibility, and Elasticity

6.1.4 Benefits of Processing Aids in PVC

6.1.4.1 Extrusion
6.1.4.2 Foam Extrusion
6.1.4.3 Calendering/Thermoforming
6.1.4.4 Injection Molding
6.1.4.5 Blow Molding

6.1.5 Commercial Sources of Processing Ads

6.2 Impact Modifiers

6.2.1 Introduction
6.2.2 Development
6.2.3 Impact and Toughness Testing
6.2.3.1 Methodology
6.2.3.2 Role of Fusion (Gelation)

6.2.4 Impact Modification Theory
6.2.5 Impact Modifiers – Function, Features, and Types

6.2.5.1 Predefined Particle Size Modifiers
6.2.5.2 Intermediate Modifiers
6.2.5.3 Modifiers with Non-Predefined Particle Size
6.2.5.4 Other Types of Modification

6.2.6 Impact Modifier Selection
6.2.7 Commercial Sources

7 Fillers and Reinforcing Agents

7.1 Mineral Fillers in PVC Matrix
7.1.1 Introduction
7.1.2 Mineral Properties
7.1.3 Particle Properties
7.1.3.1 Particle Size Distribution
7.1.3.2 Surface Area
7.1.3.3 Optical Characteristics
7.1.3.4 Color
7.1.3.5 Aspect Ratio
7.1.3.6 Specific Gravity/Density
7.1.3.7 Mohs Hardness
7.1.3.8 Particle Packing Fraction

7.1.4 Commercial Mineral Fillers and Reinforcing Agents

7.1.4.1 Calcium Carbonate (CaCO3)
7.1.4.2 Kaolin (Al2O3 2 SiO2 2 H2O)
7.1.4.3 Talc (Mg3SiO10(OH)2)
7.1.4.4 Mica (K2M(Al2Si6O20)(OH)4)
7.1.4.5 Barite (BaSO4)
7.1.4.6 Wollastonite (CaSiO3)
7.1.4.7 Calcium Sulfate (CaSO2 2 H2O)
7.1.4.8 Nepheline Syenite/Feldspar
7.1.4.9 Glass Microspheres

7.1.5 Applications and Development in PVC Compounds
7.1.6 Surface Treatment and Coupling Agent Technology

7.1.6.1 Stearates
7.1.6.2 Zirconates, Titanates, and Zirco-Aluminates
7.1.6.3 Silanes

7.2 Natural Fillers in PVC Matrix

7.2.1 Introduction
7.2.2 Characteristics of Natural Fibers
7.2.2.1 Wood Structure
7.2.2.2 Chemical Composition of Wood

7.2.3 PVC/Natural-Fiber Composites

7.2.3.1 Influence of Processing Conditions
7.2.3.2 Effects of Additives Used in the Formulations
7.2.3.3 Foaming of PVC/Natural-Fiber Composites
7.2.3.4 Durability of PVC/Natural-Fiber Composites

8 PVC Blends and Alloys

8.1 Introductions
8.2 High Heat Distortion Temperature PVC Blends
8.2.1 Glutarimide Copolymers
8.2.2 ABS Blends
8.2.3 Suprel
8.2.4 Styrene/Maleic Anhydride (SMA) Copolymer Blends

8.3 Flexible PVC Blends

8.3.1 Butadiene Acrylonitrile Copolymer Blends
8.3.2 Polyketone Blends

8.4 Compatibilizers

9 Compounding Processes

9.1 Introduction
9.2 Connection Between Polymerization and Compounding
9.3 Powder Mixing of PVC
9.3.1 Role of High Speed Mixing
9.3.2 Agglomeration Problems with High Speed Mixing
9.3.3 Solutions to the Agglomeration Problems in High Speed Mixing
9.3.4 Powder Flow and Packing
9.3.5 Vinyl Chloride Monomer Removal
9.3.6 Plasticizer Addition

9.4 Distribution and Dispersion of Ingredients

9.4.1 Effective Dispersions
9.4.1.1 Interfacial Tension on Dispersion
9.4.1.2 Compatibility of Materials for Dispersion
9.4.1.3 Elongational Work for Dispersion

9.4.2 Temperature Requirements
9.4.3 Avoiding Shear Heating

9.5 Powder to Product by Twin Screw Extrusion
9.6 Powder to Compound with an Internal Batch Mixer (Banbury) and Mill
9.7 Powder to Compound in an Internal Continuous Mixer and Mill
9.8 Powder to Compound by Single Screw Compounding
9.9 Powder to Compound by Reciprocating Single Screw Compounding
9.10 Powder to Compound by Twin Screw Compounding

10 Flexible PVC

10.1 Origins
10.2 Types of PVC Resins Used in Flexible Applications
10.3 Particulate Architecture of PVC Resins Used in Flexible Products
10.4 Favored Processing Methods for Flexible PVC
10.5 Designing Flexible PVC Compounds
10.5.1 Formulation Development
10.5.2 General Problems in Formulation Development
10.5.3 Properties Often Specified for Semi-Rigid and Flexible PVC Products

10.6 Additives Used in Flexible PVC Compounds

10.6.1 Liquid Plasticizers and Solid Flexibilizers
10.6.2 Lead-Based Stabilizers
10.6.3 Mixed Metal Stabilizers
10.6.4 Fillers
10.6.5 Lubricants
10.6.6 Light Stabilizers
10.6.7 Flame Retardants and Smoke Suppressants
10.6.8 Other Additives

10.7 Markets for Flexible and Semi-Rigid PVC
10.8 Specifications for and Quality Control Testing on Flexible PVC Products

10.8.1 Tensile Properties after Oven Aging
10.8.2 Thermal Stability by Torque Rheometer
10.8.3 Melt Viscosity
10.8.4 Hardness
10.8.5 Low Temperature Brittleness
10.8.6 Plasticizer Compatibility
10.8.7 Moisture
10.8.8 Poor Dispersion, Contamination, and Resin Gels
10.8.9 Small-Scale Defects and Surface Phenomena

10.9 Regulatory Issues
10.10Future Projections

11 Specialty Grade PVC Resins

11.1 Dispersion and Blending Resins
11.2 Powder Process Resins
11.2.1 PVC for Powder Coating and Powder Molding Systems

11.3 Specialty Suspension PVC Resins

11.3.1 Ultra High Molecular Weight Resins
11.3.2 Ultra High Absorptive Resin
11.3.3 Deglossing or Dulling Resins
11.3.4 Specialty Grade Emulsion Resins

11.4 Copolymer Resins

11.4.1 Conventional VCl/VAc Copolymers
11.4.2 Solution Polymers
11.4.3 Elastomeric Resins

11.5 Overview of Chlorinated Polyvinyl Chloride Materials, Products, and
Applications

11.5.1 Introduction
11.5.2 The Chlorination Process
11.5.3 Chlorinated Polyvinyl Chloride Compounds
11.5.4 End Use Applications for Chlorinated Polyvinyl Chloride Compounds
11.5.4.1 Potable Water Distribution at Elevated Temperatures
11.5.4.2 Industrial Handling of Corrosive Fluids at Elevated
Temperatures
11.5.4.3 CPVC-Based Fire Sprinkler Systems
11.5.4.4 CPVC Based Non-Pipe Products that Offer Alternatives to Other
High Temperature Thermoplastics

11.5.5 Summary

12 Physical Properties and Characterization of PVC

12.1 Introduction
12.2 Characterization at the Molecular Level
12.3 Characterization at the Particulate Level
12.4 Characterization of Vinyl Compounds
12.5 Typical Characterization Requirements in the Laboratory
12.6 Miscellaneous Properties
12.7 Summary

13 Flammability and Fire Performance

13.1 Introduction
13.2 Thermal Degradation and Thermal Decomposition
13.3 Thermal Decomposition and Fire Properties
13.4 Fire Performance: General
13.5 Individual Fire Properties and Associated Test Methods
13.5.1 Ignitability
13.5.1 Ease of Extinction
13.5.2 Flammability
13.5.3 Flame Spread
13.5.4 Heat Release
13.5.5 Smoke Obscuration

13.6 Fire Retardance and Smoke Suppression

13.6.1 Smoke Toxicity
13.6.2 Fire Modeling and Fire Hazard Assessment

14 Weathering of PVC Compounds

14.1 Introduction
14.2 Weathering Mechanism
14.3 Weatherability Comparison Between PVC and Other Polymers
14.4 Weathering Testing Methods
14.4.1 Outdoor Exposure
14.4.2 Accelerated Laboratory Exposure
14.4.3 Outdoor Exposure Standards

14.5 Factors Affecting Outdoor Performance of PVC

14.5.1 Color Stability
14.5.1.1 Stabilizers
14.5.1.2 Pigments
14.5.1.3 Effect of Calcium Carbonate on PVC Weatherability
14.5.1.4 Effect of Process Conditions on Color Weatherability

14.5.2 Impact Retention

14.5.2.1 PVC Resin
14.5.2.2 Impact Modifier
14.5.2.3 Stabilizer
14.5.2.4 Filler
14.5.2.5 Compound Processing Conditions

14.5.3 Dimensional Stability

14.5.3.1 Material Properties
14.5.3.2 Product Design Considerations
14.5.3.3 Internal Stresses in the Profile

14.6 Industry Trends and Recommendations
14.7 US Industry Standards
14.8 Conclusions

15 Fabrication Processes

15.1 Introduction
15.2 Rigid PVC Processes
15.2.1 Extrusion
15.2.1.1 Single-Screw Extruder
15.2.1.2 Twin-Screw Extruder
15.2.1.3 Cylindrical versus Conical Twin-Screw Extruders
15.2.1.4 Melt Flow Path to the Die
15.2.1.5 Gear Pump
15.2.1.6 General Die Design
15.2.1.7 Foam Extrusion
15.2.1.8 Downstream Calibration and Take-Off

15.2.2 Calendering
15.2.3 Injection Molding

15.2.3.1 Screw Injection Molding Machine
15.2.3.2 Injection Mold Design2539

15.2.4 Blow Molding

15.2.4.1 Extrusion Blow Molding
15.2.4.2 Injection Blow Molding

15.2.5 Thermoforming

15.2.5.1 Thin-Gauge Thermoforming
15.2.5.2 Heavy-Gauge Thermoforming
15.2.5.3 Other Heavy-Gauge PVC-Type Sheet Forming

15.2.6 Compression Molding with Radio-Frequency Heating

15.3 Composite Processing

15.3.1 Fillers
15.3.3 Foams
15.3.4 Effect of Fillers and Reinforcements on Viscosity
15.3.5 Effect of Dissolved Gases on Viscosity
15.3.6 Filled and Reinforced Foams – A Comment
15.3.7 The Role of Additives

15.4 Processing PVC-Containing Polymers

15.4.1 Processing Chlorinated PVC
15.4.2 PVC-ABS
15.4.3 PVC-PMMA

15.5 Plasticized PVC Processes

15.5.1 Liquid Processing

15.5.1.1 Coating
15.5.1.2 Slush Molding
15.5.1.3 Rotational Molding

15.5.2 Soft Processing

15.5.2.1 Flow Molding
15.5.2.2 Drysol Rotational Molding

15.5.3 Lower-Durometer or Semi-Rigid Processing

15.5.3.1 Extrusion
15.5.3.2 Blow Molding
15.5.3.3 Injection Molding
15.5.3.4 Blown Film

15.6 Joining and Assembly

15.6.1 Dielectric Welding
15.6.2 Solvent Welding
15.6.3 Thermal Welding
15.6.4 Heat Staking
15.6.5 Mechanical Fastening
15.6.6 Electromagnetic Welding

16 Product Engineering Design

16.1 Introduction
16.2 Making a Good Product
16.3 Designing a Good Injection Molding Product
16.4 Processing Effect on PVC Products
16.5 Material Properties of PVC Molded Products
16.6 End-Use Effects on PVC Molded Products
16.7 Concluding Remarks

17 PVC Applications, their Standards and Regulations, and Starting Formulations

17.1 Introduction
17.1.1 Applications Information Sources
17.1.1.1 Organizations
17.1.1.2 Standards and Codes

17.2 Pipe

17.2.1 Organizations
17.2.2 Water Service Distribution
17.2.3 Drain,Waste, and Vent
17.2.4 Starting Point Formulations

17.3 Construction

17.3.1 Siding
17.3.2 Windows and Doors

17.3.3.1 Fencing and Railing
17.3.3.2 Decking

17.3.4 Flooring
17.3.5 Single Ply Roofing
17.3.6 Other Construction

17.3.6.1 Wallcovering
17.3.6.2 Landfill Liners
17.3.6.3 Expansion Joints

17.4 Consumer Goods and Home Furnishings

17.4.1 Flexibles

17.5 Packaging

17.6 Electrical/Electronic

17.6.1 Conduit

17.7 Transportation/Automotive
17.8 Other Applications

17.8.1 Medical
17.8.2 Coatings

17.9 Organizations

18 PVC Environmental, Health, Safety

18.1 Introduction
18.1.1 Industry Size and Safety Record

18.2 Overview of Monomer and Polymer Regulatory Issues (EDC/VCM/PVC)

18.2.1 U.S. Environmental Releases
18.2.2 Ambient Air Concentrations in Communities Near Manufacturing
Facilities
18.2.3 Workplace Exposure
18.2.4 Dioxins

18.3 Compounding Processes

18.3.1 Raw Materials
18.3.1.1 PVC Resins – Safe Handling of PVC Resins
18.3.1.2 CPVC
18.3.1.3 Stabilizers
18.3.1.4 Plasticizers

18.3.2 Operations

18.3.2.1 Processing and Materials Handling –Resin and Compounding
18.3.2.2 Workplace Exposure and Emissions
18.3.2.3 Safety
18.3.2.4 PVC Dust

18.3.3 Fabrication

18.3.3.1 General
18.3.3.2 Equipment Hazards

18.4 Product Applications

18.4.1 Building and Construction
18.4.1.1 Pipe and Fittings
18.4.1.2 Siding, Windows, and Fencing/Decking/Railing

18.4.2 Packaging
18.4.3 Medical Products
18.4.4 Automotive
18.4.5 Toys
18.4.6 Combustion Safety and Toxicity

18.5 End of Life

18.5.1 Reduce, Reuse, Recycle
18.5.2 Incineration
18.5.3 Landfill

19 PVC Industry Structure and Dynamics

19.1 Supply and Producers
19.1.1 Global Regional Supply
19.1.2 Leading Producers
19.1.3 Producer Back Integration
19.1.4 Producer Forward Integration
19.1.5 Industry Restructuring

19.2 Demand

19.2.1 Global Regional Demand
19.2.2 Per Capita Consumption
19.2.3 Demand by End Use
19.2.4 Market Status of Specialty Resins
19.2.5 Merchant Resin vs. Compound Sales
19.2.6 Impact of Regulations
19.2.7 Interregional Trade
19.2.8 Growth Forecast until 2010
19.2.9 Capacity Needs

19.3 Pricing and Economics

19.3.1 Resin Price Structure
19.3.2 Price Cyclicality
19.3.3 Price Determinants
19.3.4 PVC Resin Cost Components
19.3.5 New Plant Capital Investment

Download Link:
Table of Content of PVC Handbook
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Preface of PVC Handbook
(3 pages of pdf files, 111 Kb)

Chapter 5 Plasticizers of PVC Handbook
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Flexible PVC of PVC Handbook
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