Fluorinated Polymers

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...... 34 4.7 Tetrafluoroethylene from Chlorodiflwromethane Utilities Summary ...... 36 4.8 Tetrafluoroethylene from Chlorodifluoromethane Total Capital Investment ...... 39 4.9 Tetraflwroethylene from Chlorodifluoromethane Production Costs ...... 41 5.1 Polytetrafluoroethyleneby Aqueous Suspension Polymerization Patent Summary ...... 228

IX TABLES

5.2 Polytetrafluoroethyleneby Aqueous Emulsion Polymerization Patent Summary ...... 231 5.3 Polytetrafluoroethylene by Solution Polymerization Patent Summary...... 235 5.4 Polytetrafluoroethylene by Polymerization Without a Diluent or Solvent Patent summary...... 236 5.5 Grades of PTFE...... 48 5.6 Coagulation of Polytetrafluoroethylene from a Dispersion Patent summary...... 238 5.7 Concentration of Polytetrafluoroethylene Dispersion Patent summary...... 239 5.8 Dispersion of Polytetrafluoroethylene in Medium Other than Water Patent summary...... 241 5.9 Polytetrafluoroethylene Powder-Processing Patent summary...... 242 5.10 Reclaiming of PolytetrafluoroethyleneWaste Patent summary...... 244 5.11 Polymerization of Tetrafluoroethylene by Suspension Process Design Bases and Assumptions ...... 51 5.12 Polymerization of Tetrafluoroethylene by Suspension Process Stream Flows ...... 54 5.13 Polymerization of Tetrafluoroethylene by Suspension Process Major Equipment ...... 57 5.14 Polymerization of Tetrafluoroethylene by Suspension Process Utilities Summary ...... 58 ,5.15 Polymerization of Tetrafluoroethylene by Suspension Process Total Capital Investment ...... 61

X TABLES

5.16 Polymerization of Tetrafluoroethylene by Suspension Process Production Costs ...... 63 5.17 Polymerization of Tetrafluoroethylene by Emulsion Polymerization Design Bases and Assumptions ...... 66 5.18 Polymerization of Tetrafluoroethylene by Emulsion Process Stream Flows ...... 68 5.19 Polymerization of Tetrafluoroethylene by Emulsion Process Major Equipment ...... 70 5.20 Polymerization of Tetrafluoroethylene by Emulsion Process Utilities Summary ...... , ...... 71 5.21 Polymerization of Tetrafluoroethylene by Emulsion Process Total Capital Investment ...... 73 5.22 Polymerization of Tetrafluoroethylene by Emulsion Process Production Costs ...... 75 5.23 Integrated TFE and PTFE Production Production Costs ...... 78 6.1 Hexafluoropropylene Preparation Patent Summary...... 245 6.2 Hexaflwropropylene from Tetrafluoroethylene Design Bases and Assumptions ...... 82 6.3 Hexaflwropropylene from Tetrafluoroethylene Stream Flows ...... 83 6.4 Hexaflwropropylene from Tetrafluoroethylene Major Equipment ...... 84 6.5 Hexafluoropropylene from Tetrafluoroethylene 0 Utilities Summary ...... 85 6.6 Hexafluoropropylene from Tetraflwroethylene Total Capital Investment ...... 87

Xi TABLES

6.7 Hexafluoropropylene from Tetrafluoroethylene Production Costs ...... 89 7.1 Polymers of Tetrafluoroethylene Containing Small Amounts of Hexafluoropropylene Patent summary...... 248 7.2 Copolymers of Tetrafluoroethylene and Hexaflwropropylene Patent summary...... 249 7.3 Fabrication and Application of Tetrafluoroethylene-Hexafluoropropylene Patent summary...... 252 7.4 Polymers Containing Hexaflwropropylene and Another Monomer Other than Tetrafluoroethylene Patent summary...... 254 7.5 Copolymerization of Tetrafluoroethylene and Hexaflwropropylene Design Bases and Assumptions ...... 94 7.6 Copolymerization of Tetrafluoroethylene and Hexafluoropropylene Stream Flows...... 96 7.7 Copolymerization of Tetrafluoroethylene and Hexafluoropropylene Major Equipment ...... , ...... 98 7.8 Copolymerization of Tetrafluoroethylene and Hexafluoropropylene Utilities Summary ...... 99 7.9 Copolymerization of Tetrafluoroethylene and Hexaflwropropylene Total Capital Investment ...... 101 0 7.10 Copolymerization of Tetrafluoroethylene and Hexafluoropropylene Production Costs ...... 103 8.1 Hexafluoropropylene Oxide from Hexafluoropropylene Patent summary...... 255 0- 8.2 Separation of Hexaflwropropylene and Hexaflwropropylene Oxide Patent Summary...... 257 0 Xii l

TABLES

8.3 Preparation of Perfluorinated Acyl Fluoride Patent summary...... 257 8.4 Perflwroalkyl Perfluorovinyl Ethers and Other Similar Ethers - Patent summary...... 258 8.5 Hexafluoropropylene Oxide from Hexafluoropropylene Design Bases and Assumptions ...... 108 8.6 Hexafluoropropylene Oxide from Hexafluoropropylene Stream Flows ...... 110 8.7 Hexafluoropropylene Oxide from Hexafluoropropylene Major Equipment ...... 111 8.8 Hexaflwropropylene Oxide from Hexafluoropropylene Utilities Summary ...... 112 8.9 Hexafluoropropylene Oxide from Hexafluoropropylene Total Capital Investment . . . , ...... 114 a- 8.10 Hexafluoropropylene Oxide from Hexafluoropropylene Production Costs ...... 116 8.11 Perfluoropropionyl Fluoride from Propionyl Chloride Design Bases and Assumptions ...... 119 8.12 Perfluoropropionyl Fluoride from Propionyl Chloride Stream Flows ...... 120 8.13 Perflwropropionyl Fluoride from Propionyl Chloride Major Equipment ...... 121 8.14 Perflwropropionyl Fluoride from Propionyl Chloride Utilities Summary ...... 121 8.15 Perfluoropropionyl Fluoride from Propionyl Chloride 0 Total Capital Investment ...... 123 8.16 Perfluoropropionyl Fluoride from Propionyl Chloride Production Costs ...... 124 8.17 Perflwropropyl Perfluorovinyl Ether from Perflwropropionyl Fluoride and HFPO Design Bases and Assumptions ...... 127 8.18 Perflwropropyl Perfluorovinyl Ether from Perfluoropropionyl Fluoride and HFPO Stream Flows ...... 129

Xiii TABLES

8.19 Perfluoropropyl Perfluorovinyl Ether from Perfluoropropionyl Fluoride and HFPO Major Equipment ...... 131 8.20 Perfluoropropyl Perfluorovinyl Ether from Perfluoropropionyl Fluoride and HFPO Utilities Summary ...... 132 8.21 Perfluoropropyl Perfluorovinyl Ether from Perfluoropropionyl Fluoride and HFPO Total Capital Investment ...... 134 8.22 Perfluoropropyl Perfluorovinyl Ether from Perfluoropropionyl Fluoride and HFPO Production Costs ...... 136 9.1 Copolymers of Tetrafluoroethylene and Perfluoroalkyl Pervinyl Ether and Similar Products Patent Summary ...... 261 9.2 Copolymerization of Tetrafluoroethylene and Perfluoropropyl Perfluorovinyl Ether Design Bases and Assumptions ...... 141 9.3 Copolymerization of Tetrafluoroethylene and Perfluoropropyl Perfluorovinyl Ether Stream Flows ...... 142 9.4 Copolymerization of Tetrafluoroethylene and Perfluoropropyl Perfluorovinyl Ether Major Equipment ...... 144 9.5 Copolymerization of Tetrafluoroethylene and Perfluoropropyl Perfluorovinyl Ether Utilities Sunrmary...... 145 9.6 Copolymerization of Tetrafluoroethylene and Perfluoropropyl Perfluorovbyl Ether Total Capital Investment ...... 147 9.7 Copolymerization of Tetrafluoroethylene and Perfluoropropyl Perfluorovinyl Ether Production Costs ...... 148 10.1 Copolymers of Tetrafluoroethylene and Ethylene Patent Summary ...... 265 10.2 Copolymers of Tetrafluoroethylene with Olefins Other than Ethylene Patent Summary ...... 267

xiv TABLES

10.3 Copolymerization of Tetrafluoroethylene and Ethylene Design Bases and Assumptions ...... 153 10.4 Copolymerization of Tetrafluoroethylene and Ethylene Stream Flows ...... 155 10.5 Copolymerization of Tetrafluoroethylene and Ethylene Major Equipment ...... 156 10.6 Copolymerization of Tetrafluoroethylene and Ethylene Utilities Summary ...... 157 10.7 Copolymerization of Tetrafluoroethylene and Ethylene Total Capital Investment ...... 159 10.8 Copolymerization of Tetrafluoroethylene and Ethylene Production Costs ...... 160 11.1 Membrane Compositions ...... 164 11.2 Monomers for Ion-Exchange Membranes Patent Summary...... 268 11.3 Polymerization of Tetrafluoroethylene and a Perfluoroalkylvinyl Ether with a Sulfonyl or Carboxyl Group Patent summary...... 270 11.4 Treatment of Membrane Patent Summary...... 273 11.5 Other Ion-Exchange Membranes Patent Summary ...... 283 11.6 Perfluoro-4-Oxa-5-HexenesulfonylFluoride for Ion-Exchange Resin Design Bases and Assumptions ...... 174 0- 11.7 Perfluoro-4-Oxa-5-HexenesulfonylFluoride for Ion-Exchange Resin Stream Flows ...... 178 11.8 Perfluoro-4-Oxa-5-HexenesulfonylFluoride for Ion-Exchange Resin 0 Major Equipment ...... 181 11.9 Perfluoro-4-Oxa-5-HexenesulfonylFluoride for Ion-Exchange Resin Utilities Summary . . , ...... 184

xv TABLES

11.10 Perfluoro-4-Oxa-5-BexenesulfonylFluoride for Ion-Exchange Resin Total Capital Investment ...... 186 11.11 Perfluoro-4-Oxa-5-HexenesulfonylFluoride for Ion-Exchange Resin Production Costs ...... 188 11.12 Manufacture of Ion-Exchange Resin Design Bases and Assumptions ...... 191 11.13 Manufacture of Ion-Exchange Membrane Stream Flows...... 192 11.14 Manufacture of Ion-Exchange Resin Major Equipment ...... 196 11.15 Manufacture of Ion-Exchange Resin Utilities Summary ...... 196 11.16 Manufacture of Ion-Exchange Resin Total Capital Investment ...... 198 11.17 Manufacture of Ion-Exchange Resin Production Costs ...... 200 11.18 Manufacture of Ion-Exchange Membrane Design Bases and Assumptions ...... 203 11.19 Manufacture of Ion-Exchange Membrane Major Equipment ...... 204 11.20 Manufacture of Ion-Exchange Membrane Utilities Summary ...... , ...... 205 11.21 Manufacture of Ion-&change Membrane Total Capital Investment ...... 208 11.22 Manufacture of Ion-Exchange Membrane a Production Costs ...... 210