Report No. 46

POLYOLS FROM ETHYLENE OXIDE AND PROPYLENE OXIDE

by YEN-CHEN YEN

December 1968

A private report by the

PROCESS ECONOMICS PROGRAM I STANFORD RESEARCH INSTITUTE MENLO PARK, CALIFORNIA I CONTENTS

1 INTRODUCTION, . , , ...... , . , , . , . , . , , . 1

2 SUMMARY ...... ,., ,, ,., , , , , , ,,,., , 3

3 INDUSTRY STATUS ...... , . . . , . . , ...... 15

4 CHEMISTRY ...... , . , . . . 25 Oxyalkylation Reactions ...... , . 25 Catalysts . . . , ...... , ...... 27 Hydroxy1 Groups and Unsaturation . , ...... , 29 Kinetics...,..,..,...... 31 Mechanism of Base-catalyzed Polyoxyalkylation . . . . . 33 Mechanism of Polyoxyalkylation with Boron-Trifluoride Catalyst ...... 37 Mechanism of Polyoxyalkylation Using Other Catalysts , , 38 Polymerization of Tetrahydrofuran . . , , ...... 38

5 POLYGLYCOLS FROM ETHYLENE OXIDE AND PROPYLENE OXIDE , . 43 Review of Processes . . . . . , . . , , . . . . , , . . 43 Reactors...... , ...... 47 Purification . . , ...... , . . . . , . , . 48 Manufacture of Polypropylene Glycol . , . . , . . . . . 52 Process Description . , . . . . , . . . . , . , . . , 52 Process Discussion , ...... , 57 Cost Estimate . . , ...... , . . . , . . 57 Manufacture of Polyethylene Glycol , . . . . , . . . . . 64 Process Description ...... 64 Process Discussion . , ...... , . . . . , . . , . . 68 Cost Estimate . . . . . , . . . . . , . , ...... 69 Other Polyglycols . . , ...... , , , . , . , . . . 69

6 POLYOLS FROM POLYHYDRIC ALCOHOLS ...... 75 Review of Processes ...... 75 Control of Diol Content ...... 81 Dealing with Polyhydric Alcohols Having High Melting Points ...... 81 Manufacture of Polyol from Glycerol and Propylene Oxide 82 Process Description ...... 82 Process Discussion ...... 89 Cost Estimate ...... 90

iii CONTENTS

6 (continued) Manufacture of Polyol from Pentaerythritol and Propylene Oxide..,.,..,, , .,. , ,,,., ., , , , , , . 97 Process Description . . . , ...... , . , . , . 97 Process Discussion ...... , ...... , . ; . . . 103 Cost Estimate , ...... , . . , . , , , . , . . , , . 103 Brief Evaluation of Processes for Producing Polyols from Propylene Oxide Containing Primary Hydroxy1 Groups . . . . 109

7 CARBOHYDRATE ADDUCTS . . , ...... , . . , , . , . . . 111 Review of Processes . . , . . , ...... , . . . . , . . 111 Manufacture of Sucrose-Propylene Adduct Based on a Lankro Patent ...... , . . . , , ...... 115 Process Description . . . , . . . . . , . . . . . , . . . 115 Process Discussion , , . , ...... , ...... 121 Cost Estimate . . , ...... , 121 Manufacture of Polyether Polyol from Starch . . . , . . . . 127 Process Description , . . . , . , . , . . , , . , . , . . 127 Process Discussion . . . , . . , ...... 132 Cost Estimate , . . . . , , ...... 133

8 NITROGEN-CONTAINING POLYOLS ...... 139 Review of Products ...... 139 Review of Processes ...... 147 Evaluation of Some Nitrogen-Containing Polyols ...... 148 Ethylene Diamine-Alkylene Oxide Adducts ...... 148 Propylene Oxide Adduct of Condensed Product of Ethylene Diamine and Acrylonitrile . , . . , . . . . , . . . , . . 151 Polyol Starting from Triethanolamine . . . . , ...... 152 Oxyalkylated Aromatic Amines . , ...... 154 Polyol Based on a Condensation Product of Phenol, Formaldehyde, and an Amine . , . . . . . , , , . . , . , 158 Fatty Amine-Ethylene Oxide Adducts and Similar Products . 159 Ethylene Oxide Adducts of Amides ...... , . . . , 161 N-methyl Glucamine-Alkylene Oxide Adducts , , . , . . . . 161 Polyol Made Through Oxazolidine ...... , . . . 162 Polyols from Melamine or Related Compounds . , . . , . , , 162 Polyol from Cyclopentadiene . , ...... , . 163 Polyol from N-aminoethylpiperazine . . . . , . , . . , . . 164 Polyol from N-alkyl Cyclohexyl and 1,3-Propane Diamine . . 164

iv CONTENTS

9 POLYOLS DERIVED FROM PHENOLS . , . . , . , . . . , . . . . 167 Review of Products and Processes . . , . , . . . , . . , . 167 Polyols from Phenol-Aldehyde Condensation Products . . , 167 Polyols from Polyhydric Phenols . . . . . , . . . . , . 171 Polyols from Naturally Occurring Substances , . , , . , 172 Others...... ,...... 172 Manufacture of Polyol from Phenol and Formaldehyde . . . 172 Process Description . . . , , ...... 172 Process Discussion . . . . , ...... , . 173 Cost Estimate . . , , . . . , . , . . . , ...... 173

10 PHOSPHORUS-CONTAININGPOLYOLS , . . , . . , . , . . . . . 177 Review of Products and Processes . . , . . . , ...... 177 Hydroxyalkyl Polyphosphate . . , . , . , . , . , . . . , 177 Phosphorus-ContainingPolyols Formed by Condensation Reaction Using Formaldehyde or Similar Compounds , . . 183 Phosphorus-ContainingPolyols Related to Starch or Sucrose.,,.,...,... , , , , , , ., . . . . 184 Polypropylene Glycol Phosphite . . . . . , , . . , . . 184 Phosphorus-ContainingPolyols Based on Four Patents . . . 185 Polyol from Phosphoric Acid and Propylene Oxide Based on a Wyandotte Patent . . . , . . . , ...... 185 Phosphorus-ContainingPolyol Based on a Kuhlmann Patent . . . , . , ...... 186 Polyol from Starch and Phosphoric Acid Based on an Olin Mathieson Patent . . , . . , . . . , , . , . , . 189 Polyol Containing Both Phosphorus and Nitrogen Based on a Kuhlmann Patent . . . . . , , . . . , . . , 189

11 MISCELLANEOUS RELATED PRODUCTS ...... 193 Polyols from 1,2 Epoxides Other Than Ethylene Oxide and Propylene Oxide . . . , . . . . . , . , . . . , . , . , . 193 Polyols from Epoxides Containing Rings of More Than Three Members ...... , . . . . . 197 Caprolactone Polyols . . . , ...... 198 Other Polyols . . , . . , . , ...... , ...... 201 High Molecular Weight Polymers . . , . . . . , . . . . . 201 Glycol Ethers ...... , . , . . . . 205

V CONTENTS

11 (continued) Manufacture of Polyol from Tetrahydrofuran and Ethylene Oxide ...... 205 Process Description ...... 205 Process Discussion ...... 211 Cost Estimate ...... 211

APPENDIX A DESIGN AND COST BASIS ...... 217

APPENDIX B PHYSICAL DATA ...... 223

APPENDIX C SPECIFICATIONS OF RAW MATERIALS AND FINISHED PRODUCTS ...... 225

APPENDIX D HANDLING AND SAFETY ...... 231

CITEDREFERENCES ...... 233

l

Vi ILLUSTRATIONS

5.1 Polypropylene Glycol . , . . , . . . , , . . . . . , . . . 53 5.2 Production Costs of Polypropylene Glycols at Different Production Scales , . . . . . , ...... , . . . . 63 5.3 Polyethylene Glycol . . . . , . . , . . . , . . . . . , . 65 6.1 Polyol from Glycerol and Propylene Oxide . . , ...... 85 6.2 Production Costs of Polyols from Glycerol and Propylene Oxide at Various Production Scales ...... 94 6.3 Relationship of Production Costs of Polyols to their Molecular Weight ...... , ...... 96 6.4 Polyol from Pentaerythritol and Propylene Oxide . . . . . 99 7.1 Sucrose-Propylene Oxide Adduct . , . . , ...... 117 7.2 Polyether Polyol from Starch , , , . , . . . , , . , . . 129 11.1 Polyol from Tetrahydrofuran and Ethylene Oxide , . . . . . 207

vii TABLES

2.1 Cost Features of Some Diols and Triols . , . . . , . . . . . 4 2.2 Cost Features of Some Polyols of High Functionality . . . . 5 2.3 Cost Features of Some Nitrogen-ContainingPolyols , . , . . 7 2.4 Cost Features of Some Phosphorus-ContainingPolyols . . . . 9 3.1 Commercial Polyether Polyols Produced in the United States . 17 3.2 Production of Polyether Polyols in the United States , . . . 21 3.3 Polyol Plant Capacities in the United States . . , . . . . 22 3.4 Polyol Plant Capacities Outside the United States , . . . . 24 5.1 Polyethylene or Polypropylene Glycols Summary of Processes ...... 45 5.2 Stabilizers Used in Polyether Polyols Summary of Patents . . , . , . , . , . , . , . . . , . . . . 51 5.3 Polypropylene Glycol Major Process Equipment and Utilities Summary . . . . . , . 53 5.4 Polypropylene Glycol Stream Flows . . . , ...... 55 5.5 Polypropylene Glycol Battery Limit and Utilities Investment . , ...... , . 59 5.6 Polypropylene Glycol Total Capital Investment . . . . , . . . , . . . , . . , . . 60 5.7 Polypropylene Glycol Production Costs . , . . . . . , ...... , ...... 61 5.8 Polyethylene Glycol Major Process Equipment and Utilities Summary . . . , . , . 65 5.9 Polyethylene Glycol Stream Flows , , . , . , . . , . . . , ...... 67 5.10 Polyethylene Glycol Battery Limit and Utilities Investment . . . . , ...... 70 5.11 Polyethylene Glycol Total Capital Investment . . . , ...... 71 5.12 Polyethylene Glycol Production Costs ...... 73

iX TABLES

6.1 Oxyalkylation of Polyhydric Alcohols

Summary of Processes , , , . , , . . , , . . . , , . . l , 77 6.2 Polyol from Glycerol and Propylene Oxide Major Process Equipment and Utilities Summary . , . , . . 85 6.3 Polyol from Glycerol .and Propylene Oxide Stream Flows., ., ., . , . . . . , , , , ...... 87 ii.4 Polyol from Glycerol and Propylene Oxide Battery Limit and Utilities Investment . . , . , . , . . . 91 6.5 Polyol from Glycerol and Propylene Oxide Total Capital Investment . . , , , ...... , . . . 92 6.6 Polyol from Glycerol and Propylene Oxide Production Costs ...... , . . . , . . , . , . . 93

6.7 Polyol from Pentaerythritol and Propylene Oxide Major Process Equipment and Utilities Summary . , . . . . 99 6.8 Polyol from Pentaerythritol and Propylene Oxide Stream Flows . . . . , ...... , . , ...... 101 6.9 Polyol from Pentaerythritol and Propylene Oxide Battery Limit and Utilities Investment ...... 104 6.10 Polyol from Pentaerythritol and Propylene Oxide Total Capital Investment . . . , _. . , . , ...... 105 6.11 Polyol from Pentaerythritol and Propylene Oxide Production Costs ...... , . , . , . . . . , . 107 7.1 Carbohydrate Adducts of Propylene Oxide and Ethylene Oxide Summary of Processes ...... , . , . , , , ...... 113 7.2 Sucrose-Propylene Oxide Adduct hjor Process Equipment and Utilities Summary ...... 117 7.3 Sucrose-PropyleneOxide Adduct Stream Flows ...... , ...... , . , . 119 7.4 Sucrose-Propylene Oxide Adduct Battery Limit and Utilities Investment , ...... 123. 7.5 Sucrose-Propylene Oxide Adduct Total Capital Investment . . . , , , . . . . . , . . . . . 124 7.6 Sucrose-Propylene Oxide Adduct Production Costs . . . . , , . , ...... 125

X TABLES

7.7 Polyol from Starch Major Process Equipment and Utilities Summary , . . , . . . 129 7.8 Polyol from Starch 0 Stream Flows . , , . . , , ...... , . . , , . . . . . 131 7.9 Polyether Polyol from Starch Battery Limit and Utilities Investment , . . , , . , . . . 134 7.10 Polyether Polyol from Starch Total Capital Investment , ...... , . . . 135 7.11 Polyether Polyol from Starch Production Costs ...... , . . . . . , . . . , . 137 8.1 Adducts of Propylene Oxide and Ethylene Oxide with Nitrogen Compounds Summary of Processes , . . . , ...... , . . . . . 141 8.2 Ethylene Diamine/Ethylene Oxide/Propylene Oxide Adduct 0 Production Costs , , . , ...... , . . . . 150 8.3 Polyol from Ethylene Diamine and Acrylonitrile Production Costs ...... , . . . . . 153 8.4 Polyol from Triethanolamine and Sucrose Production Costs ...... , . . . . , ...... 155 8.5 Polyol from Polymethylene Polyphenylamine Production Costs . . . , ...... 157 8.6 Phenol/Ammonia/Formaldehyde/PropyleneOxide Adduct Production Costs ...... , ...... 160 9.1 Polyols from Phenols or Phenolic-Containing Substances Summary of Processes ...... , . . . . . , , . . . . 169 9.2 Polyol from Phenol and Formaldehyde Battery Limit and Utilities Investment ...... 175 9.3 Polyol from Phenol and Formaldehyde Production Costs , ...... , . . . . . , . . , . . . . 176 10.1 Phosphorus-ContainingPolyols Summary of Processes ...... , . , . . . . , . . 179 10.2 Phosphorus-Containing Polyol from Propylene Oxide and Phosphoric.Acid Production Costs ...... 187

xi TABLES

10.3 Phosphorus-ContainingPolyol from Propylene Oxide, Phosphoric Acid, and Glycerol Production Costs , , , ...... , . . . 188 10.4 Phosphorus-ContainingPolyol from Starch, Phosphoric Acid, and Propylene Oxide Production Costs . . , . . . . . , . , , . , . . . , . , 190 10.5 Polyol Containing Both Phosphorus and Nitrogen production Costs ...... , . . . , . . . , . . . 192 11.1 polyols from Butylene Oxide, Styrene Oxide, or Other 1,2 Epoxides Summary of Processes, , . , . . . , . . , . . . . . , . . 195 11.2 Polyols from Tetrahydrofuran Summary of Processes . , ...... , . . . , . , , . . . 199 11.3 Other Polyols Summary of Patents...... 202 11.4 Polyols Made from Other Polyols Summary of Processes. . , ...... , . . . , . . . . . 203 ,11.5 Polyol from Tetrahydrofuran and Ethylene Oxide Major Process Equipment and Utilities Summary . . . . . , 207 11.6 Polyol from Tetrahydrofuran and Ethylene Oxide Stream Flows . . , . . , ...... , . , . . . , . . . . 209 11.7 Polyol from Tetrahydrofuran and Ethylene Oxide Battery Limit, Utilities Cost and Total Capital Investment . . . , . . . , . . . , , . . . . . , . , . . , 213 11.8 Polyol from Tetrahydrofuran and Ethylene Oxide Production Costs ...... , ...... , . , , 215

Xii