Report No. 69 ACETAL RESINS. June A private report by the PROCESS ECONOMICS PROGRAM STANFORD RESEARCH INSTITUTE I PARK, CALIFORNIA

Transcription

1 Report No. 69 ACETAL RESINS by GEORGE E. HADDELAND June 1971 A private report by the PROCESS ECONOMICS PROGRAM STANFORD RESEARCH INSTITUTE I MENLO PARK, CALIFORNIA

2 CONTENTS 1 INTRODUCTION 2 SUMMARY 3 INDUSTRY STATUS... History... Acetal Resin Production... Acetal Resin Applications... Competitive Materials and Prices... Raw Materials CHEMISTRY... Structure and Nomenclature... Polymerization of Formaldehyde... Mechanism... Kinetics... Polymerization of Trioxane... Mechanism... Kinetics... Polymerization States Copolymerization of Trioxk;... Comonomers... Mechanism and Kinetics... Polymerization of Higher Aldehydes... Halogenated Aldehyde Polymers STABILIZATION OF ACETAL RESINS... Kinds of Instability... Depolymerization from Chain Ends... Autooxidative Degradation... Degradation by Secondary Products of Oxidation... Thermal Degradation... Acidolysis and Hydrolysis... Stabilization Methods Esterification and Etherization of Chain Ends... Copolymerization... Additives

3 CONTENTS 6 ACETAL RESIN FROM FORMALDEHYDE... Review of Technology... Processing Routes... Polymerization Systems... Catalysts and Initiators... Molecular Weight Control... Polymer Stability and Toughness... Purification... Process Description... Process Discussion... Cost Estimates... Capital Costs... Production Costs... Discussion of Costs COPOLYMER ACETAL RESIN FROM TRIOXANE,. 159 Review of Technology Processing Routes Solution-Suspension Polymerizations Polymerization Catalysts Polymer Chain End Stabilization Process Description Process Discussion Cost Estimates Capital Investment Production Costs Discussion of Costs IRRADIATION POLYMERIZATION OF FORMALDEHYDE OR TRIOXANE. 209 Review of Technology Formaldehyde Trioxane Process Description Process Discussion Cost Estimates Capital Costs Production Costs Discussion of Costs Vi

4 CONTENTS 9 OTHER PROCESSES Tenneco Chemicals Diamond Shamrock W. R. Grace & Company Asahi Chemical Farbwerke Hoechst BASF, DEGUSSA Societ'a Italiana Resine APPENDIX A DESIGN AND COST BASIS. 245 APPENDIX B PHYSICAL DATA.,, 251 APPENDIX C POLYMER PROPERTIES., 257 APPENDIX D MATERIALS OF CONSTRUCTION, HANDLING, SAFETY, AND POLLUTION. 261 APPENDIX E TEST METHODS AND TERMINOLOGY. 267 REFERENCES PATENT REFERENCES BY COMPANY.,,. 329 vii

5 ILLUSTRATIONS Consumption of Acetal Resins in the United States, Western Europe, and Japan and Estimated Production Capacity in These Three Areas, 13 Acetylation Rate vs Sodium Acetate Catalyst Concentration.,.,. Polymer Weight Loss in Air at 230 C as a Function of Time... Polymer Weight Loss in Limited Air at 230 and 250 C,. Alternative Processing Routes for Acetal Resins from Formaldehyde. Polyoxymethylene Stability in Formaldehyde Solution Degradation Rate and Toughness of Formaldehyde Polymers FlowDiagram.,. 137 Influence of Plant Design Capacity, Stream Factor, and Methanol Cost on the Total Production Cost of Acetal Homopolymer Resin from Formaldehyde,, 157 Mono- and Copolymer Acetal Resins from Trioxane Alternative Processing Routes, 161 Trioxane-Ethylene Oxide Copolymers Influence of Solvent and Catalyst Concentration on the Molecular Weight.,,,.,, 171 Flow Diagram. 187 Copolymer Acetal Resin from Ethylene Oxide and Formaldehyde via Trioxane Production Costs for Various Plant Capacities and Stream Factors,,.,,. 207 Conversion as a Function of Polymerization Time, and Viscosity as a Function of Conversion for Irradiation Polymerization of Trioxane.,., Polymer Yield as a Function of Postpolymerization Time The Irradiation Polymerization of Trioxane Flow Diagram..,.,..., IX

6 ILLUSTRATIONS B.l Heat Capacity and Heat of Vaporization of Formaldehyde, Trioxane, and Acetal Resin,.,.,.,, 255 E.l Acetal Resin Molecular Weight from Inherent Viscosity, 267

7 TABLES Summary of Acetal Resin Capital and Manufacturing Costs by Catalytic Processes,. 5 Acetal Resin Producers 15 Acetal Resin Markets in the United States,, 18 Properties of Acetal Resins Compared with Those of.other Plastics and Metals. : 21 Effect of Initiators on Cationic Polymerization of Trioxane in a 50 wt% Solution of Cyclohexane at 60 C. 36 Polymerization of Trioxane in the Various States. 40 Copolymers of Trioxane with Cyclic Formals and Epoxy Compounds 42 End-Group Stabilization of Acetal Resins Patent Summary 57 End-Group Stabilization of Acetal Resins. 69 Formaldehyde or Trioxane Copolymers Patent Summary 71 Stabilizer Additives for Acetal Resins Patent Summary 89 Processes for the Polymerization of Formaldehyde Patent Summary 109 Catalysts and Initiators for the Polymerization of Formaldehyde Patent Summary,. 121 Major Process Equipment and Utilities Summary 136 StreamFlows Total Capital Investment.,. 151 Production Costs.,, 151 Processes for the Polymerization of Trioxane Polymers and Copolymers Patent Summary, 165 Xi

8 TABLES B.l B.2 c.1 c.2 Catalysts and Initiators for the Polymerization of Trioxane Polymers and Copolymers Patent Summary.,. 175 Thermal Stabilization of Trioxane Copolymer Chain Ends Patent Summary,. Major Process Equipment and Utilities Summary Stream Flows. c. Total Capital Investment,,. Production Costs. Irradiation Polymerization of Formaldehyde or Trioxane Patent Summary Properties of Preirradiated Postpolymerized Polyoxymethylene as Compared with Those of Commercial Polyformaldehyde Resin Irradiation Polymerization of Trioxane Major Process Equipment and Utilities Summary Irradiation Polymerization of Trioxane StreamFlows.,., Irradiation Polymerization of Trioxane Total Capital Investment,,. Irradiation Polymerization of Trioxane Production Costs,.,,. Properties of Trioxane and Ethylene Oxide., Properties of Solvents.,, Properties of Acetal Resins.,,.,,, Chemical Resistance of Copolymer Acetal Resin. m xii