PROCESS ECONOMICS PROGRAM

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1 PROCESS ECONOMICS PROGRAM SRI INTERNATIONAL Abstract Menlo Park, California Economics Program Report No. 166 FLUORINATED POLYMERS (September 1983) This report deals with polytetrafluoroethylene (PTFE), and copolymers of tetrafluoroethylene with hexafluoropropylene, perfluoropropylperfluorovinyl ether, and ethylene. For PTFE, both the suspension 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, perfluoropropylperfluorovinyl 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 tetrafluoroethylene 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

2 Report No. 166 FLUORINATED POLYMERS by YEN-CHEN YEN with contributions by CHIEN NIEH and LIN CHAIO HSU E 0 I 1 m A private report by the September 1963 PROCESS ECONOMICS PROGRAM Menlo Park, California 94025

3 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, product, and plant for the United States and Western Europe. y I ii

4 CONTENTS 1 INTRODUCTION SUMMARY... 3 General Aspects... 3 Technical Aspects... 8 Tetrafluoroethylene from Chlorodifluoromethane... 8 Polytetrafluoroethylene by Suspension... 8 Polytetrafluoroethylene by Emulsion... 9 Hexafluoropropylene from Tetrafluoroethylene... 9 and Hexafluoropropylene Hexafluoropropylene Oxide from Hexafluoropropylene Perfluoropropionyl Fluoride from Propionyl Chloride Perfluoropropyl Perfluorovinyl Ether Copolymer of TFE and Perfluoropropyl Perfluorovinyl Ether.. 11 Copolymer of TFE and Ethylene Perfluoro-4-oxa-5-Hexenesulfonyl Fluoride Fluorinated Ion-Exchange Resin Fluorinated Ion-Exchange Membrane INDUSTRY STATUS Products, Properties, and Applications Producers and Production TETRAFLUOROETHYLENE Chemistry Review of es Description Discussion Cost Estimates POLYTETRAFLUOROETHYLENE Chemistry Review of es A for Making Polytetrafluoroethylene by Suspension Polymerization Description Discussion Cost Estimates iii

5 CONTENTS 5 POLYTETRAFLUOROETHYLENE (continued) A process for Making Polytetrafluoroethylene by Emulsion Polymerization Description Discussion Cost Estimates Integrated Production Tetrafluoroethylene and the Polymer HEXAFLUOROPROPYLENE (HFP) Chemistry Review of es Description Discussion Cost Estimates COPOLYMER OF TETRAFLUOROETHYLENE AND HEXAFLUOROPROPYLENE.. 91 Chemistry Review of es Description Discussion Cost Estimates PERFLUOROALKYL PERFLUOROVINYL ETHER Chemistry Review of es A for Making Hexafluoropropylene Oxide Description Discussion Cost Estimates A for Making Perfluoropropionyl Fluoride Description Discussion Cost Estimates A for Making Perfluoropropyl Perfluorovinyl Ether Description Discussion Cost Estimates IV

6 CONTENTS 9 COPOLYMER OF TETRAFLUOROETHYLENE AND PERFLUOROALXYL PERFLUOROVINYL ETHER Review of es Description Discussion Cost Estimates COPOLYMER OF TETRAFLUOROETHYLENE AND ETHYLENE Chemistry Review of es Description Discussion Cost Estimates FLUORINATED COPOLYMERS CONTAINING ION-EXCHANGE GROUPS Chemistry and Review of es Du Pont's for Making a Monomer with Sulfonyl Groups Asahi Chemical's for Making a Monomer with Sulfonyl Groups Asahi Glass for Making a Monomer with Carboxylic Groups Other es for Making Monomers Copolymerization Membrane Formation Treatment of Membrane 172 Other Ion-Exchange Membranes A for Making a Perfluorinated Vinyl Ether with Sulfonyl Fluoride Groups Description Discussion Cost Estimates A for Making Ion-Exchange Resin Description Cost Estimates A for Making Ion-Exchange Membrane Description Discussion Cost Estimates

7 CONTENTS APPENDIX A PHYSICAL DATA APPENDIX B TOXICITY PATENT SUMMARY TABLES CITED REFERENCES PATENT REFERENCES Vi

8 ILLUSTRATIONS Tetrafluoroethylene from Chlorodifluoromethane Flow sheet... Tetrafluoroethylene from Chlorodifluoromethane Effect of Operating Level and Plant Capacity on Production Cost and Product Value Polymerization of Tetrafluoroethylene by Suspension Flow sheet... Polymerization of Tetrafluoroethylene by Emulsion Flow Sheet..., Hexafluoropropylene from Tetrafluoroethylene Flow Sheet... and Hexafluoropropylene Flow sheet... Hexafluoropropylene Oxide from Hexafluoropropylene Flow Sheet... Perfluoropropionyl Fluoride from Propionyl Chloride Flow Sheet... Perfluoropropyl Perfluorovinyl Ether from Perfluoropropionyl Fluoride and HFPO Flow Sheet... and Perfluoropropyl Perfluorovinyl Ether Flow Sheet... and Ethylene Flow Sheet... Perfluoro-4-Oxa-5-Hexenesulfonyl Fluoride for Ion-Exchange Resin Flow Sheet... Manufacture of Ion-Exchange Resin Flow sheet... Manufacture of Ion-Exchange Membrane Flow sheet Vii

9 TABLES 2.1 Cost Features of Polytetrafluoroethylene and Copolymers of Tetrafluoroethylene Cost Features of Monomers of Fluorinated Polymers and Precursors Cost Features of Fluorinated Ion-Exchange Membrane, Resin, and Monomer Comparison of Polytetrafluoroethylene and Copolymers of Tetrafluoroethylene World Producers of Polytetrafluoroethylene World Producers of Copolymers of Tetrafluoroethylene U.S. Production of Fluoropolymers Tetrafluoroethylene from Chlorodifluoromethane Patent Summary Separation, Recovery, and Purification of Tetrafluoroethylene Patent Summary Other es for Making Tetrafluoroethylene Patent Summary Tetrafluoroethylene from Chlorodifluoromethane Design Bases and Assumptions Tetraflwroethylene from Chlorodifluoromethane Stream Flows Tetrafluoroethylene from Chlorodifluoromethane Major Equipment Tetrafluoroethylene from Chlorodiflwromethane Utilities Summary Tetrafluoroethylene from Chlorodifluoromethane Total Capital Investment Tetraflwroethylene from Chlorodifluoromethane Production Costs Polytetrafluoroethylene by Aqueous Suspension Polymerization Patent Summary IX

10 TABLES ,5.15 Polytetrafluoroethylene by Aqueous Emulsion Polymerization Patent Summary Polytetrafluoroethylene by Solution Polymerization Patent Summary Polytetrafluoroethylene by Polymerization Without a Diluent or Solvent Patent summary Grades of PTFE Coagulation of Polytetrafluoroethylene from a Dispersion Patent summary Concentration of Polytetrafluoroethylene Dispersion Patent summary Dispersion of Polytetrafluoroethylene in Medium Other than Water Patent summary Polytetrafluoroethylene Powder-ing Patent summary Reclaiming of Polytetrafluoroethylene Waste Patent summary Polymerization of Tetrafluoroethylene by Suspension Design Bases and Assumptions Polymerization of Tetrafluoroethylene by Suspension Stream Flows Polymerization of Tetrafluoroethylene by Suspension Major Equipment Polymerization of Tetrafluoroethylene by Suspension Utilities Summary Polymerization of Tetrafluoroethylene by Suspension Total Capital Investment X

11 TABLES Polymerization of Tetrafluoroethylene by Suspension Production Costs Polymerization of Tetrafluoroethylene by Emulsion Polymerization Design Bases and Assumptions Polymerization of Tetrafluoroethylene by Emulsion Stream Flows Polymerization of Tetrafluoroethylene by Emulsion Major Equipment Polymerization of Tetrafluoroethylene by Emulsion Utilities Summary......, Polymerization of Tetrafluoroethylene by Emulsion Total Capital Investment Polymerization of Tetrafluoroethylene by Emulsion Production Costs Integrated TFE and PTFE Production Production Costs Hexafluoropropylene Preparation Patent Summary... Hexaflwropropylene from Tetrafluoroethylene Design Bases and Assumptions Hexaflwropropylene from Tetrafluoroethylene Stream Flows Hexaflwropropylene from Tetrafluoroethylene Major Equipment Hexafluoropropylene from Tetrafluoroethylene Utilities Summary Hexafluoropropylene from Tetraflwroethylene Total Capital Investment Xi

12 TABLES Hexafluoropropylene from Tetrafluoroethylene Production Costs Polymers of Tetrafluoroethylene Containing Small Amounts of Hexafluoropropylene Patent summary Copolymers of Tetrafluoroethylene and Hexaflwropropylene Patent summary Fabrication and Application of Tetrafluoroethylene-Hexafluoropropylene Patent summary Polymers Containing Hexaflwropropylene and Another Monomer Other than Tetrafluoroethylene Patent summary and Hexaflwropropylene Design Bases and Assumptions and Hexafluoropropylene Stream Flows and Hexafluoropropylene Major Equipment , and Hexafluoropropylene Utilities Summary and Hexaflwropropylene Total Capital Investment and Hexafluoropropylene Production Costs Hexafluoropropylene Oxide from Hexafluoropropylene Patent summary Separation of Hexaflwropropylene and Hexaflwropropylene Oxide Patent Summary Xii

13 TABLES Preparation of Perfluorinated Acyl Fluoride Patent summary... Perflwroalkyl Perfluorovinyl Ethers and Other Similar Ethers Patent summary... Hexafluoropropylene Oxide from Hexafluoropropylene Design Bases and Assumptions Hexafluoropropylene Oxide from Hexafluoropropylene Stream Flows Hexafluoropropylene Oxide from Hexafluoropropylene Major Equipment Hexaflwropropylene Oxide from Hexafluoropropylene Utilities Summary Hexafluoropropylene Oxide from Hexafluoropropylene Total Capital Investment..., Hexafluoropropylene Oxide from Hexafluoropropylene Production Costs Perfluoropropionyl Fluoride from Propionyl Chloride Design Bases and Assumptions Perfluoropropionyl Fluoride from Propionyl Chloride Stream Flows Perflwropropionyl Fluoride from Propionyl Chloride Major Equipment Perflwropropionyl Fluoride from Propionyl Chloride Utilities Summary Perfluoropropionyl Fluoride from Propionyl Chloride Total Capital Investment Perfluoropropionyl Fluoride from Propionyl Chloride Production Costs Perflwropropyl Perfluorovinyl Ether from Perflwropropionyl Fluoride and HFPO Design Bases and Assumptions Perflwropropyl Perfluorovinyl Ether from Perfluoropropionyl Fluoride and HFPO Stream Flows Xiii

14 TABLES Perfluoropropyl Perfluorovinyl Ether from Perfluoropropionyl Fluoride and HFPO Major Equipment Perfluoropropyl Perfluorovinyl Ether from Perfluoropropionyl Fluoride and HFPO Utilities Summary Perfluoropropyl Perfluorovinyl Ether from Perfluoropropionyl Fluoride and HFPO Total Capital Investment Perfluoropropyl Perfluorovinyl Ether from Perfluoropropionyl Fluoride and HFPO Production Costs Copolymers of Tetrafluoroethylene and Perfluoroalkyl Pervinyl Ether and Similar Products Patent Summary and Perfluoropropyl Perfluorovinyl Ether Design Bases and Assumptions and Perfluoropropyl Perfluorovinyl Ether Stream Flows and Perfluoropropyl Perfluorovinyl Ether Major Equipment and Perfluoropropyl Perfluorovinyl Ether Utilities Sunrmary and Perfluoropropyl Perfluorovbyl Ether Total Capital Investment and Perfluoropropyl Perfluorovinyl Ether Production Costs Copolymers of Tetrafluoroethylene and Ethylene Patent Summary Copolymers of Tetrafluoroethylene with Olefins Other than Ethylene Patent Summary xiv

15 TABLES 10.3 and Ethylene Design Bases and Assumptions and Ethylene Stream Flows and Ethylene Major Equipment and Ethylene Utilities Summary and Ethylene Total Capital Investment and Ethylene Production Costs Membrane Compositions Monomers for Ion-Exchange Membranes Patent Summary Polymerization of Tetrafluoroethylene and a Perfluoroalkylvinyl Ether with a Sulfonyl or Carboxyl Group Patent summary Treatment of Membrane Patent Summary Other Ion-Exchange Membranes Patent Summary Perfluoro-4-Oxa-5-Hexenesulfonyl Fluoride for Ion-Exchange Resin Design Bases and Assumptions Perfluoro-4-Oxa-5-Hexenesulfonyl Fluoride for Ion-Exchange Resin Stream Flows Perfluoro-4-Oxa-5-Hexenesulfonyl Fluoride for Ion-Exchange Resin Major Equipment Perfluoro-4-Oxa-5-Hexenesulfonyl Fluoride for Ion-Exchange Resin Utilities Summary.., xv

16 TABLES Perfluoro-4-Oxa-5-Bexenesulfonyl Fluoride for Ion-Exchange Resin Total Capital Investment Perfluoro-4-Oxa-5-Hexenesulfonyl Fluoride for Ion-Exchange Resin Production Costs Manufacture of Ion-Exchange Resin Design Bases and Assumptions Manufacture of Ion-Exchange Membrane Stream Flows Manufacture of Ion-Exchange Resin Major Equipment Manufacture of Ion-Exchange Resin Utilities Summary Manufacture of Ion-Exchange Resin Total Capital Investment Manufacture of Ion-Exchange Resin Production Costs Manufacture of Ion-Exchange Membrane Design Bases and Assumptions Manufacture of Ion-Exchange Membrane Major Equipment Manufacture of Ion-Exchange Membrane Utilities Summary , Manufacture of Ion-&change Membrane Total Capital Investment Manufacture of Ion-Exchange Membrane Production Costs