Report No. 78 ACRYLONITRILE THERMOPLASTICS by ROBERT H. SCHWAAB August 1972 A private report by the PROCESS ECONOMICS PROGRAM STANFORD RESEARCH INSTITUTE I MENLO PARK, CALIFORNIA
CONTENTS 1 INTRODUCTION,........................ 1 2 SUMMARY... General Aspects... Technical Aspects... 3 3 a 3 INDUSTRY STATUS... High-Nitrile Resins... Standard Oil (Ohio)... Monsanto... DuPont......... Other Producers s' 13 13 13 15 16... 16... 17 and Acrylic Competition Between High-kirili Rekk Multipolymers... 19 Opportunities for Barrier Resins in Bottles... 19 Opportunities for Barrier Resins in Films... 21 4 CBARACTERISTICS AND PROPERTIES OF ACRYLONITRILE THERMOPLASTICS.... Barrier Properties... Impact Strength... Transparency... Heat Deflection Temperature... Creep Strength... Waste Disposal Considerations... 5 CHEMISTRY... Ungrafted Resins... Kinetics of Interpolymerization... Azeotrope Formation in Copolymerization... Mechanism of Graft Polymerization... 6 BARRIER RESIN FROM ACRYLONITRILE... Review of Processes... Process Development... Processing Sequence... Rubbery Substrate... Graft Polymerization... Polymer Latex Finishing... Polymer Finishing... 23 23 30 32 37 38 39 43 44 44 46 49 55 55 56 59 60 64 71 74 V
CONTENTS 6 (continued) Process Description... Preparation of Nitrile Rubber Latex... Preparation of Blending Resin Latex or Graft Resin Latex,, Continuous Production of Dry Crumb from Mixed Latex... Polymer Blending and Finishing Section... Process Discussion... Plant Capacity... Design Basis... Production of Rubbery Substrate... Graft Latex Production and Blend Latex Production.,..,. Continuous Production of Dry Polymer Crumb... Additives... Extrusion... Packaging... Materials of Construction... Cost Estimates... Capital Costs... Production Costs... 7 BARRIER RESIN FROM METHACRYLONITRILE... Review of Processes... Process Development... Processing Sequence... Rubbery Substrate... Graft Polymerization... Polymer Latex Finishing... Matrix Resin Copolymerization... Polymer Blending and Finishing... Process Description... Preparation of Acrylate Rubber Latex... Preparation of Graft Resin Latex.,.,..,.,..,,, Continuous Production of Dry Polymer Crumb from Latex... Preparation of Matrix Copolymer by Suspension Polymerization... Polymer Blending and Finishing Section... Process Discussion... Plant Capacity... Design Basis... Production of Rubbery Substrate... Graft Resin Production... Matrix Copolymer Production... 79 81 82 82 84 93 93 93 94 94 97 97 98 99 99 100 100 100 111 111 115 116 117 118 124 125 131 132 134 134 136 137 138 155 vi
CONTENTS 7 (continued) Additives... 155 Extrusion... 156 Packaging.,... 157 Materials of Construction... 158 Cost Estimates... 158 Capital Costs... 158 Production Costs... 159 8 ACRYLIC MULTIPOLYMER... 169 Review of Processes... 169 Other Processes... 173 Graft Polymer... 173 Terpolymer... 178 Polymer Blending and Finishing... 181 Process Description.......... 186 Continuous Production of Terpolymer Solution 186 Preparation of Graft Resin Latex... 187 Polymer Blending and Finishing Section... 189 Process Discussion... 196 Graft Latex Production 196 Solvent... 1 197 Extruder 197 Packaging... : 197 Cost Estimates... 198 Capital Costs... 198 Production Costs... 199 9 CONVERSION OF BARRIER RESIN TO FINISHED ARTICLES... Continuous-Extrusion Blow-Molding... Review of Processes... Process Description... Injection Blow-Molding... Review of Processes... Process Description... Cold-Parison Blow-Molding... Review of Processes... Process Description... Process Discussion... Thermoforming... Review of Processes... Process Description... 209 211 211 217 221 221 225 229 229 231 238 243 243 246 vii
CONTENTS 9 (continued) Cost Estimates.................,...... Capital Costs...,...,,........,...,.. Production Costs.,.,,,,...,.,,....,... 251 251 252 APPENDIX A DESIGN AND COST BASIS,....,.,,,,..... 255 APPENDIXB THE MARKET FOR CARBONATED BEVERAGE CONTAINERS,,.. 259 APPENDIXC DESIGN OF A PLASTIC BO'ITLE FOR CARBONATED BEVERAGES. 267 APPENDIXD MOLECULAR ORIENTATION OF FILMS AND BOTTLES,.,... 271 APPENDIX E APPENDIX F MEASUREMENT OF BARRIER PROPERTIES,.....,... GENERAL REVIEW OF EMULSION POLYMERIZATION..,... 275 277 APPENDIX G EQUIPMENT SUPPLIERS.,..,.,......,.,. 283 CITED REFERENCES... 285 PATENT REFERENCES BY COMPANY... 319 Viii
ILLUSTRATIONS 6.1 6.2 6.3 7.1 7.2 7.3 7.4 8.1 8.2 8.3 8.4 9.1 9.2 9.3 9.4 9.5 9.6,...........,. Effect of Plant Capacity on Total Fixed Capital....,, Effect of Operating Level and Plant Capacity on Production Cost.,........,....,.............,.... Effect of Plant Capacity on Total Fixed Capital.,..,. Effect of Methacrylonitrile Monomer Cost on Production Cost............,......... Effect of Operating Level and Plant Capacity on Production Cost...................... s Compositions........,.......,......, Production of..,..,.....,, Effect of Plant Capacity on Total Fixed Capital..,,,. Effect of Operating Level and Plant Capacity on Production Cost....,... ;..,.,.,..,... Bottle Production by Continuous-Extrusion Blow Molding... Bottle Production by Injection Blow-Molding......,. Bottle Production from Cold Parisons by Corpoplast Process. Corpoplast Cold-Parison Blow-Molding.........,,. Packaging of Parisons.,..............,.. Bottle Production from Sheet by Thermoforming and Spin Welding........................ 249 85 105 109 141 163 167 168 175 191 203 207 219 227 235 237 241 IX
TABLES 2.1 2.2 2.3 3.1 4.1 4.2 4.3 4.4 5.1 6.1 6.2 6.3 6.4 6.5 6.6 7.1 7.2 7.3 7.4 High-Nitrile Thermoplastics and Comparison of Processes,............,..... 5 High-Nitrile Thermoplastics and Comparison of Estimated Capital and Manufacturing Costs,.. 6 Production of Bottles from Barrier Resin Comparison of Estimated Costs....,.,......,.. 7 and Clear ABS Comparison of Properties...........,...,.. 18 Comparison of Physical Properties of Acrylonitrile Thermoplastics...........,...,......, 24 Gas Permeation Rates of High-Barrier Polymers..,...,, 25 Properties of Transparent Polymers.........,.., 33 Heat Distortion Temperatures of Typical Bottle Resins..,. 38 Reactivity Ratios of Acrylonitrile in Copolymerization... 46 Barrier Resins from Acrylonitrile Patent Summary.............,......... 57 Major Process Equipment and Utilities Summary,..,.,.. 85 Stream Flows........................ 91 Total Capital Investment.........,......., 103 Major Capital Equipment................... 106 Production Costs,......,.,,...,....,.. 107 Barrier Resins from Methacrylonitrile PatentSummary....................... 113 Major Process Equipment and Utilities Summary......,. 141 Stream Flows....,..,.......,.....,.. 147 Total Capital Investment,................. 161 Xi
TABLES 7.5 7.6 8.1 8.2 8.3 8.4 8.5 8.6 9.1 9.2 9.3 9.4 9.5 9.6 9.7 9.8 9.9 Major Capital Equipment,..,.....,.,....,.. 164 Production Costs...........,....,,,,,. 165 s PatentSummary..........,............ 171 Major Process Equipment and Utilities Summary.,,,,.., 191 Stream Flows..,...,,......,......... 195 Total Capital Investment....,.,..,,..,.,.. 201 Major Capital Equipment..,.,.........,,,, 204 Production Costs...,..,....,,,.,..,... 205 Bottle Production by Continuous-Extrusion Blow-Molding Selected List of Equipment Manufacturers.,..,,,,,,, 213 Bottle Production by Continuous-Extrusion Blow-Molding Major Process Equipment and Utilities Summary..,,..,. 219 Bottle Production by Injection Blow-Molding Selected List of Equipment Manufacturers,...,..... 223 Bottle Production by Injection Blow-Molding Major Process Equipment and Utilities Summary..,,.... 227 Bottle Production by Cold-Parison Blow-Molding Effect of Molecular Orientation on Physical Properties... 230 Bottle Production from Cold Parisons by Corpoplast Process Major Process Equipment and Utilities Summary.,.,.., 235 Bottle Production from Sheet by Thermoforming and Spin Welding Major Process Equipment and Utilities Summary..,..... 249 Bottle Production Total Fixed Capital......,.............. 253 Bottle Production Conversion Costs........,.......,.,,., 253 xii