Fluorinated Polymers
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PROCESS ECONOMICS PROGRAM SRI INTERNATIONAL Menlo Park, California Abstract 94025 Process Economics Program Report No. 166 FLUORINATED POLYMERS (September 1983) This report deals with polytetrafluoroethylene (PTFE), and copolymers of tetrafluoroethylene with hexafluoropropylene, perfluoro- propylperfluorovinyl ether, and ethylene. For PTFE, both the suspen- sion process for making three grades (finely divided resin, presintered resin, and agglomerated resin), and the emulsion process for making coagulated resin and concentrated emulsion, are evaluated. SRI also evaluates the manufacture of the monomers for the above, viz., tetrafluoroethylene,hexafluoropropylene, perfluoropropylper- fluorovinyl ether. The last named monomer is made from perfluoro- .propionyl fluoride and hexafluoropropylene oxide; their manufacture is evaluated too. Also included in this report is a systematic study of fluorinated ion-exchange membranes which are made from a copolymer of tetrafluoro- ethylene and a perfluorinated vinyl ether with a carboxylic or sulfonic acid end group. The manufacture of perfluorinated vinyl ether, its copolymerization with tetrafluoroethylene to form an ion-exchange resin, and the processing of this resin to form a membrane, are all evaluated. PEP'83 YCY/CN Report No. 166 FLUORINATED POLYMERS by YEN-CHEN YEN with contributions by CHIEN NIEH and LIN CHAIO HSU I 0 1 September 1963 0E A private report by the m PROCESS ECONOMICS PROGRAM Menlo Park, California 94025 For detailed marketing data and information, the reader is referred to one of the SRI programs specializing in marketing research. The CHEMICAL ECONOMICS HANDBOOK Program covers most major chemicals and chemical products produced in the United States and the WORLD PETROCHEMICALS Program covers major hydrocarbons and their derivatives on a worldwide basis. In addition, the SRI DIRECTORY OF CHEMICAL PRODUCERS services provide detailed lists of chemical producers by company, prod- y uct, and plant for the United States and Western Europe. I ii CONTENTS 1 INTRODUCTION......................... 1 2 SUMMARY ........................... 3 General Aspects ....................... 3 Technical Aspects ...................... 8 Tetrafluoroethylene from Chlorodifluoromethane ....... 8 Polytetrafluoroethyleneby Suspension Process ....... 8 Polytetrafluoroethyleneby Emulsion Process ........ 9 Hexafluoropropylene from Tetrafluoroethylene ........ 9 Copolymerization of Tetrafluoroethylene and Hexafluoropropylene ..................... 10 Hexafluoropropylene Oxide from Hexafluoropropylene ..... 10 Perfluoropropionyl Fluoride from Propionyl Chloride .... 10 Perfluoropropyl Perfluorovinyl Ether ............ 11 Copolymer of TFE and Perfluoropropyl Perfluorovinyl Ether. 11 Copolymer of TFE and Ethylene ............... 11 Perfluoro-4-oxa-5-HexenesulfonylFluoride ......... 12 Fluorinated Ion-Exchange Resin ............... 12 Fluorinated Ion-Exchange Membrane ............. 12 3 INDUSTRY STATUS ....................... 15 Products, Properties, and Applications ............ 15 Producers and Production ................... 18 4 TETRAFLUOROETHYLENE ..................... 23 Chemistry .......................... 23 Review of Processes ..................... 26 Process Description ..................... 27 Process Discussion ...................... 37 Cost Estimates. ....................... 37 5 POLYTETRAFLUOROETHYLENE ................... 45 Chemistry .......................... 45 Review of Processes ..................... 46 A Process for Making Polytetrafluoroethylene by Suspension Polymerization ................. 50 Process Description .................... 50 Process Discussion ..................... 59 Cost Estimates ....................... 59 iii CONTENTS 5 POLYTETRAFLUOROETHYLENE (continued) A process for Making Polytetrafluoroethylene by Emulsion Polymerization . 65 Process Description . 65 Process Discussion . 72 Cost Estimates. 72 Integrated Production Tetrafluoroethylene and the Polymer . 77 6 HEXAFLUOROPROPYLENE (HFP) ................. 79 Chemistry ......................... 79 Review of Processes .................... 80 Process Description .................... 81 Process Discussion ..................... 86 Cost Estimates. ...................... 86 7 COPOLYMER OF TETRAFLUOROETHYLENE AND HEXAFLUOROPROPYLENE . 91 Chemistry ......................... 91 Review of Processes .................... 92 Process Description .................... 93 Process Discussion ..................... 100 Cost Estimates ....................... 100 8 PERFLUOROALKYL PERFLUOROVINYL ETHER ............ 105 Chemistry ......................... 105 Review of Processes .................... 107 A Process for Making Hexafluoropropylene Oxide ....... 107 Process Description ................... 107 Process Discussion .................... 113 Cost Estimates ...................... 113 A Process for Making Perfluoropropionyl Fluoride ...... 118 Process Description ................... 118 Process Discussion .................... 122 Cost Estimates ...................... 122 A Process for Making Perfluoropropyl Perfluorovinyl Ether. 126 Process Description ................... 126 Process Discussion .................... 133 Cost Estimates ...................... 133 IV CONTENTS 9 COPOLYMER OF TETRAFLUOROETHYLENE AND PERFLUOROALXYL PERFLUOROVINYL ETHER . 139 Review of Processes ..................... 139 Process Description ..................... 140 Process Discussion ..................... 146 Cost Estimates ....................... 146 10 COPOLYMER OF TETRAFLUOROETHYLENE AND ETHYLENE . 151 Chemistry .......................... 151 Review of Processes ..................... 152 Process Description ..................... 152 Process Discussion ..................... 158 Cost Estimates ....................... 158 11 FLUORINATED COPOLYMERS CONTAINING ION-EXCHANGE GROUPS . 163 Chemistry and Review of Processes .............. 163 Du Pont's Process for Making a Monomer with Sulfonyl Groups ................... 165 Asahi Chemical's Process for Making a Monomer with Sulfonyl Groups ................... 166 Asahi Glass Process for Making a Monomer with Carboxylic Groups .................. 169 Other Processes for Making Monomers ............ 170 Copolymerization ...................... 171 Membrane Formation ..... ... ............ 171 Treatment of Membrane 172 Other Ion-Exchange Membranes ..............................173 A Process for Making a Perfluorinated Vinyl Ether with Sulfonyl Fluoride Groups ................ 173 Process Description .................... 173 Process Discussion .................... 185 Cost Estimates ...................... 185 A Process for Making Ion-Exchange Resin ........... 190 Process Description .................... 190 Cost Estimates ...................... 197 A Process for Making Ion-Exchange Membrane ......... 202 Process Description .................... 202 Process Discussion .................... 206 Cost Estimates ...................... 206 CONTENTS APPENDIX A PHYSICAL DATA .................. 213 APPENDIX B TOXICITY .................... 215 PATENT SUMMARY TABLES ...................... 217 CITED REFERENCES ........................ 287 PATENT REFERENCES ........................ 321 Vi ILLUSTRATIONS 4.1 Tetrafluoroethylene from Chlorodifluoromethane Flow sheet........................ 331 4.2 Tetrafluoroethylene from Chlorodifluoromethane Effect of Operating Level and Plant Capacity on Production Cost and Product Value . 43 5.1 Polymerization of Tetrafluoroethylene by Suspension Process Flow sheet........................ 335 5.2 Polymerization of Tetrafluoroethylene by Emulsion Process Flow Sheet........ , . 337 6.1 Hexafluoropropylene from Tetrafluoroethylene Flow Sheet........................ 339 7.1 Copolymerization of Tetrafluoroethylene and Hexafluoropropylene Flow sheet........................ 341 8.1 Hexafluoropropylene Oxide from Hexafluoropropylene Flow Sheet........................ 345 8.2 Perfluoropropionyl Fluoride from Propionyl Chloride Flow Sheet........................ 347 8.3 Perfluoropropyl Perfluorovinyl Ether from Perfluoropropionyl Fluoride and HFPO Flow Sheet........................ 349 9.1 Copolymerization of Tetrafluoroethylene and Perfluoropropyl Perfluorovinyl Ether Flow Sheet........................ 351 10.1 Copolymerization of Tetrafluoroethylene and Ethylene 0- Flow Sheet........................ 353 11.1 Perfluoro-4-Oxa-5-HexenesulfonylFluoride for Ion-Exchange Resin Flow Sheet........................ 355 11.2 Manufacture of Ion-Exchange Resin 0- Flow sheet........................ 359 11.3 Manufacture of Ion-Exchange Membrane Flow sheet........................ 361 0 Vii TABLES 2.1 Cost Features of Polytetrafluoroethylene and Copolymers of Tetrafluoroethylene . 5 2.2 Cost Features of Monomers of Fluorinated Polymers and Precursors . 6 2.3 Cost Features of Fluorinated Ion-Exchange Membrane, Resin, and Monomer . 7 3.1 Comparison of Polytetrafluoroethylene and Copolymers of Tetrafluoroethylene . 17 3.2 World Producers of Polytetrafluoroethylene . 19 3.3 World Producers of Copolymers of Tetrafluoroethylene . 20 3.4 U.S. Production of Fluoropolymers . 21 4.1 Tetrafluoroethylene from Chlorodifluoromethane Patent Summary . ...219 4.2 Separation, Recovery, and Purification of Tetrafluoroethylene Patent Summary . ...221 4.3 Other Processes for Making Tetrafluoroethylene Patent Summary . ...224 4.4 Tetrafluoroethylene from Chlorodifluoromethane Design Bases and Assumptions . 28 4.5 Tetraflwroethylene from Chlorodifluoromethane Stream Flows . 31 4.6 Tetrafluoroethylene from Chlorodifluoromethane Major Equipment.