Report No by ROBERT H. SCHWAAR. November A private report by the PROCESS ECONOMICS PROGRAM PARK, CALIFORNIA STANFORD RESEARCH INSTITUTE I

Transcription

1 Report No. 104 THERMOPLASTIC ELASTOMERS by ROBERT H. SCHWAAR with oontxibutions by James J. L. Ma November 1976 A private report by the PROCESS ECONOMICS PROGRAM STANFORD RESEARCH INSTITUTE I MENLO PARK, CALIFORNIA

2 3 CONTENTS INTRODUCTION s-r General Aspects... Econmic Aspects.... Technical Aspects... Styrenic Thermoplastic Elastomers... Hydrogenated Styrenic Block Copolymers.... Blends of Rubber and Thermoplastics... Thermoplastic Copolyester Elastomers.... INDUSTRY STATUS... Production.... Producers... Prices... Markets PROPERTIES OF THERMOPLASTIC ELASTOMERS STYRENIC BLOCK COPOLYMERS... Chemistry... Effect of Structure on Product Properties... Review of Processes... Initiators.... Solvent... Raw Materials Purity.... Polymerization Procedures... Reactors... MUDistribution.... Additives... Polymerization Monitoring... Coupling Living Diblock Polymers.... Linear Triblock Copolymers.... Star-Block Copolymers... Conversion of Polymer Solution to Dry Product... Process Description... Feed Purification... Preparation of Coupled Block Copolymer.... Polymer Recovery and Finishing.... Conversion of Crumb to Pellets.... Solvent Recovery Vii

3 CONTENTS 5 (Continued) Process Discussion.... Feed Purification... Polymerization and Coupling... Additives... Stripping and Coagulating... Polymer Crumb Drying.... Solvent Recovery.... Final Processing.... '.... Materials of Construction... Waste Treatment... Cost Estimates.... Capital Costs... Production Costs HYDROGENATED STYRENIC BLOCK COPOLYMERS.... Chemistry Review of Procesiei... Control of Diene Polymer Configuration.... Hydrogenation Selectivity... Hydrogenation Conditions.... :... Removal of Hydrogenation Catalyst... Conversion of Polymer Solution to Dry Polymer Powder.... Process Description... Purification of Monomer and Solvent Feeds... Preparation of Coupled Block Copolymer.... Hydrogenation.... Coagulation of Polymer Cement... c... Conversion of Crumb to Pellets.... Solvent Recovery.... Process Discussion.... Impurities in the Butadiene... Reaction Temperature.... Diene Polymerization Control Agent.... Coupling Agent.... Catalyst Deactivation... Hydrogen Consumption.... Catalyst Removal.... Polymer Recovery.... Waste Treatment... CostEstimates... Capital Costs... Production Costs.....i :: Viii

4 CONCERTS 7 BLENDS OF RUBBER AND THERMOPLASTICS Review of Processes Polyolefin Blends With Partial Curing Polyolefin Blends Without Partial Curing Other Polyolefin Blends Process Description Mixing Section Operations Product Finishing Section Operation Extruding and Pelletizing Pellet Dewatering and Drying Pellet Blending Product Packaging Process Discussion Plant Capacity Design Basis Batch Versus Continuous Mixing Extruding and Pelletizing Additives Materials of Construction Cost Estimates Capital Costs Production Costs THERMOPLASTIC COPOLYESTER ELASTOMERS Chemistry Reactions Kinetics.... ;$ Review of Processes Development Catalysts :.fi Additives... Processing Sequence Ester Interchange and Polycondensation Recovery of Methanol and 1,4-Butanediol Final Polymerization in Solid Phase Continuous Polymerization Process Description Polymerization Section Charging Catalyst Preparation Ester Interchange and Polycondensation Solvent Recovery Section Product Finishing Section

5 CONTENTS 8 (Continued) Process Discussion Plant Capacity Design Basis Raw Materials Materials of Construction Cost Estimates Capital Costs Production Costs OTHER THERMOPLASTIC ELASTOMERS Modified EPDM Modified Polybutadiene Propylene-Hexene-1 Random Copclymer Other Olefin Copolymers Modification of Thermoplastics Ionic Thermoplastic Elastomers Polyimidothioether-Polysulfide Block Copolymers Other Sulfur-Containing Block Copolymers Thiourea Copolymers Silicone-Based Thermoplastic Elastomers APPENDIX A DESIGN AND COST BASES APPENDIX B RAW MATERIAIS SPECIFICATIONS CITED REFERENCES PATENTREFERENCESBYCOMPANY X

6 ILLUSTRATIONS 4.1 Hardness of Thermoplastic Elastomers, Rubbers and Plastics , Flexural Elastic Modulus of Thermoplastic Elastomers, Rubbers, and Plastics..... ' Diagrammatic Representation of a Linear Styrene-Diene Triblock Thermoplastic Elastomer Effect of Structure of Block Copolymers on Solution Viscosity Star-Block Butadiene-Styrene Copolymer Process Flow Diagram Star-Block Butadiene-Styrene Copolymer Effect of Plant Capacity on Total Fixed Capital Star-Block Butadiene-Styrene Copolymer Effect of Operating Level and Plant Capacity on Production Cost Star-Block Butadiene-Styrene Copolymer Effect of Butadiene and Styrene Prices on Total Production Cost Hydrogenated SBS Copolymer, Production Process Flow Diagram Hydrogenated SBS Copolymer Production Effect of Plant Capacity on Total Fixed Capital Hydrogenated SBS Copolymer Production Effect of Operating Level and Plant Capacity on Production Cost , Hydrogenated SBS Copolymer Production Effect of Butadiene and Styrene Prices on Total Production Cost Blends of Rubber and Thermoplastics Process Flow Diagram Blends of Rubber and Thermoplastics Effect of Polypropylene and Peroxide Contents on Hardness Blends of Rubber and Thermoplastics Effect of Plant Capacity on Total Fixed Capital Xi

7 ILLUSTRATIONS 7.4 Blends of Rubber and Thermoplastics Effect of Operating Level and Plant Capacity on Production Cost Blends of Rubber and Thermoplastics Effect of Raw Material Costs on Total Production Cost Thermoplastic Copolyester Elastomers Effect of Time and Temperature on Inherent Viscosity of Melt Thermoplastic Copolyester Elastomers Process Flow Diagram Thermoplastic Copolyester Elastomers Effect of Plant Capacity on Total Fixed Capital Thermoplastic Copolyester Elastomers Effect of Operating Level and Plant Cost on ProductionCost Thermoplastic Copolyester Elastomers Effect of Raw Material Costs on Total Production Cost Xii

8 TABLES 2.1 Suxmnary of Cost Estimates for Thermoplastic Elastomers Producers of Thermoplastic Elastomers (Other than Polyurethanes) End-Use Applications of Thermoplastic Elastomers (United States, 1973) Properties of Thermoplastic Elastomer Gums and Compounds Styrenic Block Copolymers PatentSumnary Coupling Agents for Lithium-Initiated Block Copolymers Patent Sunmary Properties of Linear- and Star-Block Copolymers Star-Block Styrene-Butadiene Copolymer Design Bases and Assumptions Star-Block Styrene-Butadiene Copolymer Major Equipment and Utilities Summary Star-Block Styrene-Butadiene Copolymer StreamFlows Star-Block Styrene-Butadiene Copolymer Sumnary of Waste Products i8 Star-Block Styrene-Butadiene Copolymer Production Major Capital Equipment Cost Star-Block Styrene-Butadiene Copolymer Total Capital Investment Star-Block Styrene-Butadiene Copolymer Production Costs Hydrogenated Styrenic Block Copolymers PatentSummary Hydrogenated SBS Copolymer Design Bases and Assumptions Hydrogenated SBS Copolymer Production Typical Batch Cycles Hydrogenated SBS Copolymer Production Major Equipment and Utilities Summary Xiii

9 TABLES 6.5 Hydrogenated SBS Copolymer Production Stream Flows Hydrogenated SBS Copolymer Production Summary of Waste Products Hydrogenated SBS Copolymer Production Major Capital Equipment Cost Hydrogenated SBS Copolymer Production Total Capital Investment Hydrogenated SBS Copolymer Production Production Costs Blends of Rubber and Thermoplastics Patents-r-y Blends of Rubber and Thermoplastics Major Equipment and Utilities Summary Blends of Rubber and Thermoplastics Stream Flows Based on Durometer 77A Blend Blends of Rubber and Thermoplastics Total Capital Investment Blends of Rubber and Thermoplastics Major Capital Equipment Cost Blends of Rubber and Thermoplastics Production Cost for Durometer 77A Blend Thermoplastic Copolyester Elastomers PatentS-r-y Thermoplastic Copolyester Elastomers Design Bases and Assumptions Thermoplastic Copolyester Elastomers Major Equipment and Utilities Sunnnary Thermoplastic Copolyester Elastomers Stream Flows for 55D Copolymer Thermoplastic Copolyester Elastomers Total Capital Investment Thermoplastic Copolyester Elastomers Major Capital Equipment Cost Thermoplastic Copolyester Elastomers Production Costs for Durometer 55D Copolymer XiV

10 TABLES B.l Butadiene Specifications (Commercial Grade) B.2 Styrene Specifications B.3 Dimethyl Terephthalate Properties B.4 Polytetramethylene Ether Glycol Specifications B.5 1,4-Butanediol Properties Agerite White Antioxidant Properties B.7 Tetrabutyl Titanate Properties and Specifications xv