8

0 .

Report No. 105

VINYLIDENE CHLORIDE MONOMER AND POLYMERS

by LEONARD A. WASSELLE

A private report by the

l PROCESS ECONOMICS PROGRAM

I STANFORD RESEARCH INSTITUTE

I

MENLO PARK, CALIFORNIA

CONTENTS

LIST OF ILLUSTRATIONS . . . . . . . . . . . . . . . . . . . . . . . vii

LIST OF TABLES . . . . . . . . . . . . . . . . . . . . . . . . . . xi

1 INTRODUCTION . . . . . . . . . . . . . . . . . . . . . . . . . 1

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

General ........................... 3

Economic Aspects ....................... 4

Technical Aspects ...................... 7 Monomer ......................... 12

Ethane Chlorination ................ 12 Caustic Dehydrochlorination of 1,1,2-Trichloroethane .............. 13 Vinylidene Chloride from Vinyl Chloride ...... 14

Polymerization ..................... 16 Suspension Process ................. 18 Emulsion Process .................. 18

3 INDUSTRY STATUS . . . . . . . . . . . . . . . . . . . . . . . 19

Consumption and Market Pattern ................ 19 Vinylidene Chloride-Vinyl Chloride Copolymers ...... 19 Vinylidene Chloride-Alkyl Acrylate Latices ....... 20 Vinylidene Chloride-Acrylonitrile Resins ........ 20

Production and Growth .................... 21

Trends ............................ 22 Monomer Producers ...................... 23 Polymer Producers ...................... 24

4 VINYLIDENE CHLORIDE BY ETHANE CHLORINATION AND THERMAL DEHYDROCHLORINATION OF METHYL CHLOROFORM . . . . . 27

Introduction ............... .......... 27 Chemistry ................ .......... 29

Ethane Chlorination ......... .......... 29 Thermal Dehydrochlorination of Methyl Chloroform .... 35 Hydrochlorination of Vinyl Chloride . .......... 41

Review of Processes ........... .......... 43 Process Description ........... .......... 55 Process Discussion ............ .......... 68

Cost Estimates .............. .......... 71 Capital Costs ............ .......... 71 Production Costs .......... .......... 72

Vii

5 VINYLIDENE CHLORIDE BY CAUSTIC DEHYDROCHLORINATION OF 1,1,2-TRICHLOROETHANE ...................

Introduction ......................... Chemistry ..........................

Chlorination of Ethylene Dichloride ........... Ethylene Chlorination .................. Caustic Dehydrochlorination of 1,1,2-Trichloroethane . .

Review of Processes . . . . . Caustic Dehydrochlorination . . . . . Chlorination of Ethylene Dichloride .

Process Description . . . . . . . . . . . Process Discussion . . . . . . . . . . . . Cost Estimates . . . . . . . . . . . . . .

Capital Costs . . . . . . . . . . . . Production Costs . . . . . . . . . .

..........

..........

..........

..........

..........

..........

..........

..........

6 VINYLIDENE CHLORIDE FROM VINYL CHLORIDE BY DEHYDROCHLORINATION OF METHYL CHLOROFORM .

Introduction . . . . . . . . . . . . . . . Chemistry . . . . . . . . . . . . . . . .

Hydrochlorination of Vinyl Chloride . Chlorination of 1,1,-Dichloroethane .

THERMAL ..........

..........

..........

..........

..........

Dehydrochlorination of Methyl Chloroform ........ Chlorination of 1,2-Dichloroethylene ..........

Review of Processes ...................... Process Description ...................... Process Discussion ...................... Cost Estimates .........................

Capital Costs ...................... Production Costs .....................

7 MATERIALS OF CONSTRUCTION IN VINYLIDENE CHLORIDE MONOMER PLANT DESIGNS . . . . . . . . . . . . . . . . . . . .

8 STABILIZATION AND HANDLING OF VINYLIDENE CHLORIDE MONOMER . . 173

9 POLYMERIZATION OF VINYLIDENE CHLORIDE . . . . . . . . . . . .

Introduction ......................... Polymerization Chemistry ...................

Initiation ....................... Propagation ....................... Chain Transfer ..................... Termination .......................

Kinetics of Polymerization .................. Kinetics of Copolymerization .................

Copolymer Equation ................... Overall Rate of Copolymerization Equation ........ Q-e Scheme .......................

81 0

81 83 83 85 88 0 91 91 96 100 112 115 0 115 115

125

125 128 128 128 133 133 136 148

0

159 161 161 161

169

177

177 0

178 179 180 180 181 182 182 182 192 193

Viii

Homopolymerization ...................... 195 Copolymerization .................... 201

Initiators .......................... 205 Emulsifiers and Surfactants ................. 209

10 INDUSTRIAL PRODUCTION OF VINYLIDENE CHLORIDE COPOLYMERS . . . 211

Introduction ......................... Review of Processes .....................

General ......................... Suspension Polymerization ................ Emulsion Polymerization ................. Solution Polymerization .................

Suspension Copolymerization of Vinylidene/Vinyl Chlorides . . Bases of Design ..................... Process Description ................... Process Discussion ...................

Emulsion Copolymerization of Vinylidene Chloride, Ethyl Acrylate, and Methyl Methacrylate ...........

Bases of Design ..................... Process Description ...................

Process Discussion ...................... Cost Estimates ........................

Capital Costs ...................... Production Costs ....................

APPENDICES

A DESIGN AND COST BASIS . . . . . . . . . . . . . . . . . . . . 266

B PHYSICAL DATA . . . . . . . . . . . . . . . . . . . . . . . . 271

C PRODUCT SPECIFICATIONS AND PROPERTIES . . . . . . . . . . . . 275

D HANDLING AND HEAL THE HAZARDS . . . . . . . . . . . . . . . . . 285

'CITED REFERENCES. . . . . . . . . . . . . . . . . . . . . . . . . 291

PATENT REFERENCES BY COMPANY . . . . . . . . . . . . . . . . . . . 303

211 212 212 213 228 230 231 231 233 240

244 244 246 253 256 256 256

iX

ILLUSTRATIONS

4.1 Vinylidene Chloride by Ethane Chlorination and Thermal Dehydrochlorination of Methyl Chloroform Block Diagram . . . . . . . . . . . . . . . . . . . . . . . 28

4.2 Vinylidene Chloride by Ethane Chlorination and Thermal Dehydrochlorination of Methyl Chloroform Flow Sheet . . . . . . . . . . . . . . . . . . . . . . . . 307

4.3 Vinylidene Chloride by Ethane Chlorination and Thermal Dehydrochlorination of Methyl Chloroform Effect of Plant Capacity on Total Fixed Capital . . . . . . 77

4.4 Vinylidene Chloride by Ethane Chlorination and Thermal Dehydrochlorination of Methyl Chloroform Effect of Operating Level and Plant Capacity on Production Cost . 79

4.5 Vinylidene Chloride by Ethane Chlorination and Thermal Dehydrochlorination of Methyl Chloroform Effect of Raw Material Prices on Net Production Cost . . . 80

5.1 Vinylidene Chloride by Caustic Dehydrochlorination of 1,1,2-Trichloroethane from an Ethylene Dichloride Feed Block Diagram . . . . . . . . . . . . . . . . . . . . . . . 82

5.2 Vinylidene Chloride by Caustic Dehydrochlorination of 1,1,2-Trichloroethane Flow Sheet . . . . . . . . . . . . . . . . . . . . . . . . 309

5.3 Vinylidene Chloride by Caustic Dehydrochlorination of 1,1,2-Trichloroethane Effect of Plant Capacity on Total Fixed Capital . . . . . . . . . . . . . . . . . . 120

5.4 Vinylidene Chloride by Caustic Dehydrochlorination of 1,1,2-Trichloroethane Effect of Operating Level and Plant Capacity on Production Cost . . . . . . . . . . . 122

5.5 Vinylidene Chloride by Caustic Dehydrochlorination of 1,1,2-Trichloroethane Effect of Raw Material Prices on Net Production Cost . . . . . . . . . . . . . . . . . . 123

6.1 Vinylidene Chloride from Vinyl Chloride Chlorination and Thermal Dehydrochlorination of Methyl Chloroform Block Diagram . . . . . . . . . . . . . . . . . . . . . . . 126

6.2 Ethylidene Chloride Chlorination Reactions . . . . . . . . 138

Xi

6.3

6.4

6.5

6.6

9.1

9.2

.

9.3

9.4

9.5

9.6

9.7

9.8

10.1

10.2

10.3

10.4

Vinylidene Chloride from Vinyl Chloride by Thermal Dehydrochlorination of Methyl Chloroform Flow Sheet . . . . . . . . . . . . . . . . . . . . . . . . 311

Vinylidene Chloride from Vinyl Chloride by Thermal Dehydrochlorination of Methyl Chloroform Effect of Plant Capacity of Total Fixed Capital . . . . . . 165

Vinylidene Chloride from Vinyl Chloride by Thermal Dehydrochlorination of Methyl Chloroform Effect of Operating Level and Plant Capacity on Production Cost . . . . . . . . . . . . . . . . . . . . 167

Vinylidene Chloride from Vinyl Chloride by Thermal Dehydrochlorination of Methyl Chloroform Effect of Raw Material Prices on Net Production Cost . . . 168

Homopolymerization of Vinylidene Chloride . . . . . . . . . 196

Vinylidene Chloride by Emulsion Polymerization: Three-Stage Reaction . . . . . . . . . . . . . . . . . . . 198

Vinylidene Chloride by Emulsion Polymerization Effect of Surfactant Concentration . . . . . . . . . . . . 199

Vinylidene Chloride by Emulsion Polymerization Effect of Catalyst Concentration . . . . . . . . . . . . . 200

Copolymerization of Vinylidene Chloride and Vinyl Chloride. 203

Vinylidene Chloride-Vinyl Chloride Polymer Compositions . . 204

Polyvinylidene Chloride Polymerization Time Curves . . . . 207

Initiator Efficiency in Polyvinyl Chloride Polymerization . 208

Vinylidene Chloride-Vinyl Chloride Copolymer by Suspension Polymerization Block Diagram and Simplified Material Balance . . . . . . . 313

Vinylidene Chloride-Vinyl Chloride Copolymer by Suspension Polymerization Flow Sheet . . . . . . . . . . . . . . . . . . . . . . . . 315

Typical Batch Reactor for Suspension and Emulsion Polymerization . . . . . . . . . . . . . . . . . . . . . . 242

Vinylidene Chloride, Ethyl Acrylate, and Methyl Methacrylate Copolymer by Emulsion Polymerization Block Diagram and Simplified Material Balance . . . . . . . 317

0 -

0 -

0

Xii

10.5

10.6

10.7

10.8

10.9

10.10

B.l

C.1

c.2

D.l

D.2

Vinylidene Chloride, Ethyl Acrylate, and Methyl Methacrylate Copolymer by Emulsion Polymerization Flow Sheet . . . . . . . . . . . . . . . . . . . . . . . . 319

Comparison of Extensiblity of Films of Amophous and Crystalline 9O:lO Vinylidene Chloride: Ethyl Acrylate Copolymer . . . . . . . . . . . . . . . . . . . . 254

Vinylidene Chloride --Vinyl Chloride Copolymer by Suspension Process Effect of Plant Capacity on Total Fixed Capital . . . . . . . . . . . . . . . . . . 260

Vinylidene Chloride--Ethyl Acrylate, Methyl Methacrylate Copolymer by Emulsion Process Effect of Plant Capacity on Total Fixed Capital . . . . . . 261

Vinylidene Chloride--Vinyl Chloride Copolymer by Suspension Process Effect of Operating Level and Plant Capacity on Production Cost . . . . . . . . . . . 264

Vinylidene Chloride--Ethyl Acrylate, and Methyl Methacrylate Copolymer by Emulsion Process Effect of Operating Level and Plant Capacity on Production Cost . 265

Vapor Pressures of Chlorinated Hydrocarbons . . . . . . . . 274

Liquid Density--Vinylidene Chloride . . . . . . . . . . . . 279

Vapor Pressure--Vinylidene Chloride . . . . . . . . . . . . 279

Vinylidene Chloride Unloading and Storage Installation . . 288

Vinylidene Chloride Tank Farm . . . . . . . . . . . . . . . 289

Xiii

TABLES

2.1 Summary of Capital and Production Costs for Vinylidene Chloride Processes . . . . . . . . . . . . . 6

2.2 Summary of Capital and Production Costs for Polyvinylidene Chloride Copolymer Processes . . . . . . 8

2.3 Summary of Technical Aspects for Vinylidene Chloride Processes......................... 9

2.4 Summary of Technical Aspects for Polyvinylidene Copolymer Processes . . . . . . . . . . . . . . . . . . . . 17

3.1 Vinylidene Chloride Production . . . . . . . . . . . . . . 21

3.2 Copolymer Producers in the United States, Europe, and Japan......................... 25

3.3 Representative Patents on Polymerization Processes by Company and Process . . . . . . . . . . . . . . . . . . 26

4.1 Summary of Dehydrochlorination of Methyl Chloroform to Vinylidene Chloride . . . . . . . . . . . . . . . . . . 37

4.2 Ethane Chlorination Net Product Distribution . . . . . . . 44

4.3 Vinylidene Chloride by Ethane Chlorination and Thermal Dehydrochlorination of Methyl Chloroform Patent Summary . . . . . . . . . . . . . . . . . . . . . . 50

4.4 Vinylidene Chloride by Ethane Chlorination and Thermal Dehydrochlorination of Methyl Chloroform Bases and Assumptions . . . . . . . . . . . . . . . . . . . 62

4.5 Vinylidene Chloride by Ethane Chlorination and Thermal Dehydrochlorination of Methyl Chloroform Major Process Equipment and Utilities Summary . . . . . . . 64

4.6 Vinylidene Chloride by Ethane Chlorination and Thermal Dehydrochlorination of Methyl Chloroform Stream Flows . . . . . . . . . . . . . . . . . . . . . . . 66

4.7 Vinylidene Chloride by Ethane Chlorination and Thermal Dehydrochlorination of Methyl Chloroform Capital Investment . . . . . . . . . . . . . . . . . . . . 74

xv

4.8

4.9

4.10

5.1

5.2

5.3

5.4

5.5

5.6

5.7

5.8

5.9

5.10

6.1

6.2

Dehydrochlorination of Methyl Chloroform Capital Investment by Process Section . . . . . . . . . . . 75

Vinylidene Chloride by Ethane Chlorination and Thermal Dehydrochlorination of Methyl Chloroform Working Capital . . . . . . . . . . . . . . . . . . . . . . 76

Vinylidene Chloride by Ethane Chlorination and Thermal Dehydrochlorination of Methyl Chloroform Production Costs . . . . . . . . . . . . . . . . . . . . . 78

Summary of Chlorination of Ethylene Dichloride to 1,1,2-Trichloroethane . . . . . . . . . . . . . . . . . 84

Summary of Dehydrochlorination of Vinylidene Chloride from 1,1,2-Trichloroethane . . . . . . . . . . . . . . . . 89

Vinylidene Chloride by Caustic Dehydrochlorination of 1,1,2-Trichloroethane . . . . . . . . . . . . . . . . . 92

Chlorination of 1,1,2-Trichloroethane Patent Summary . . . 97

Vinylidene Chloride by Caustic Dehydrochlorination of 1,1,2-Trichloroethane Bases and Assumptions . . . . . . . . . . . . . . . . . . . 106

Vinylidene Chloride by Caustic Dehydrochlorination of 1,1,2-Trichloroethane Major Process Equipment and Utilities Summary . . . . . . . 108

Vinylidene Chloride by Caustic Dehydrochlorination of 1,1,2-Trichloroethane Stream Flows . . . . . . . . . . . . . . . . . . . . . . . 110

Vinylidene Chloride by Caustic Dehydrochlorination of 1,1,2-Trichloroethane Total Capital Investment . . . . . . . . . . . . . . . . . 118

Vinylidene Chloride by Caustic Dehydrochlorination of 1,1,2-Trichloroethane Working Capital . . . . . . . . . . . . . . . . . . . . . . 119

Vinylidene Chloride by Caustic Dehydrochlorination of 1,1,2-Trichloroethane Production Costs . . . . . . . . . . . . . . . . . . . . . 121

Summary of Chlorination of Ethylidene Chloride to Methyl Chloroform and Vinylidene Chloride . . . . . . . 129

Summary of Dehydrochlorination of Methyl Chloroform to Vinylidene Chloride . . . . . . . . . . . . . . . . . . 134

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l

xvi

6.3

6.4

6.5

6.6

6.7

6.8

6.9

6.10

6.11

6.12

9.1

9.2

9.3

9.4

9.5

Reaction Product Composition for Ethylidene Dichloride Chlorination . . . . . . . . . . . . . . . . . . . . . . . 139

Vinylidene Chloride from Vinyl Chloride Chlorination of Ethylidene Chloride Patent Summary: Fundamental . . . . . . . . . . . . . . . 141

Vinylidene Chloride from Vinyl Chloride Chlorination of Ethylidene Chloride Patent Summary: Photochemical . . . . . . . . . . . . . . 145

Vinylidene Chloride from Vinyl Chloride Chlorination of Ethylidene Chloride Patent Summary: Photochemical . . . . . . . . . . . . . . 147

Vinylidene Chloride from Vinyl Chloride by Thermal Dehydrochlorination of Methyl Chloroform Bases and Assumptions . . . . . . . . . . . . . . . . . . . 154

Vinylidene Chloride from Vinyl Chloride by Thermal Dehydrochlorination of Methyl Chloroform Major Process Equipment and Utilities Summary . . . . . . . 156

Vinylidene Chloride from Vinyl Chloride by Thermal Dehydrochlorination of Methyl Chloroform Stream Flows . . . . . . . . . . . . . . . . . . . . . . . 158

Vinylidene Chloride from Vinyl Chloride by Thermal Dehydrochlorination of Methyl Chloroform Total Capital Investment . . . . . . . . . . . . . . . . . 163

Vinylidene Chloride from Vinyl Chloride by Thermal Dehydrochlorination of Methyl Chloroform Working Capital . . . . . . . . . . . . . . . . . . . . . . 164

Vinylidene Chloride from Vinyl Chloride by Thermal Dehydrochlorination of Methyl Chloroform Production Costs . . . . . . . . . . . . . . . . . . . . . 166

Discussion of Suspension and Bulk Polymerization Kinetics . 184

Summary of Equations for Vinylidene Chloride Suspension Polymerization . . . . . . . . . . . . . . . . . 187

Kinetics of Emulsion Polymerization . . . . . . . . . . . . 189

Reactivity of Vinylidene Chloride with Important Monomers . 191

Typical Initiators for Vinylidene Chloride Polymerizations. 206

xvii

10.1

10.2

10.3

10.4

10.5

10.6

10.7

10.8

10.9

10.10

10.11

10.12

B.l

c.1

Vinylidene Chloride Polymers Patent Summary: 1970s . . . . . . . . . . . . . ...= l

Vinylidene Chloride Copolymer Patent Summary: 1960s . . . . . . . . . . . . . . . . . . .

Vinylidene-Vinyl Chloride Copolymer by Suspension Polymerization Bases and Assumptions . . . . . . . . . . . . . . . . . . .

Vinylidene-Vinyl Chloride Copolymer by Suspension Polymerization Major Process Equipment and Utilities Summary . . . . . . .

Vinylidene-Vinyl Chloride Copolymer by Suspension Polymerization Stream Flows . . . . . . . . . . . . . . . . . . . . . . .

Vinylidene Chloride, Ethyl Acrylate, and Methyl Methacrylate Copolymer by Emulsion Polymerization Bases and Assumptions . . . . . . . . . . . . . . . . . . .

Vinylidene Chloride, Ethyl Acrylate, and Methyl Methacrylate Copolymer by Emulsion Polymerization Major Process Equipment and Utilities Summary . . . . . . .

Vinylidene Chloride, Ethyl Acrylate, and Methyl Methacrylate Copolymer by Emulsion Polymerization Stream Flows . . . . . . . . . . . . . . . . . . . . . . .

Vinylidene Chloride-Vinyl Chloride Copolymer by Suspension Polymerization Total Capital Investment

Vinylidene Chloride, Ethy Methacrylate Copolymer by Total Capital Investment

Vinylidene Chloride-Vinyl by Suspension Polymer&at Production Costs . . . .

. . . . . . . . . . . . . . . . .

Acrylate, and Methyl Emulsion Polymerization . . . . . . . . . . . . . . . . .

Chloride Copolymer on

Vinylidene Chloride, Ethyl Acrylate, and Methyl Methacrylate Copolymer by Emulsion Polymerization . . . . .

Some Physical Properties of Chlorohydrocarbons . . . . . . 272 0

Sales Specification for Vinylidene Chloride Monomer Monomethyl Ether of Hydroquinone Inhibited . . . . . . . .

214

220

0 232

237 l

239

245

250

0 252

258

259

262 0

263

275

xviii

c.2 Specification and Typical Analysis . . . . . . . . . . . . 276

c.3 Physical Properties and Constants of Vinylidene Chloride Monomer . . . . . . . . . . . . . . 277

c.4 Properties of Saran latexes 112, 118, 137, and 143 . . . . . 280

c.5 Heat Seal and Water Vapor Transmission Properties of Saran Latex-Coated Glassine, Paper, and Paperboard . . . 280

C.6 Physical and Functional Properties of Saran Resin F300 and Saran Resin F310 . . . . . . . . . . . . . . . . . . . . 282

c.7 General Physical Properties of Saran Wrap-S . . . . . . . . 283

C.8 Properties of Molded Saran 281 . . . . . . . . . . . . . . . 284

xix