Abstract Process Economics Program Report 153C SINGLE-SITE CATALYSTS FOR PROPYLENE-BASED POLYMERS (June 2002)

Transcription

1 Abstract Process Economics Program Report 153C SINGLE-SITE CATALYSTS FOR PROPYLENE-BASED POLYMERS (June 2002) Single-site catalysts (SSC) are considered one of the most significant innovations in the polymer industry in recent years. These catalysts allow a high degree of tailoring of molecular structure, which enables suppliers to optimize a resin s physical properties and processability. Metallocene-based polyethylenes and ethylene-based elastomers have already been successfully introduced in the market place. However, metallocene-based polypropylene resins are just beginning to be commercialized. This report reviews the patents issued to Exxon, Hoechst, BASF, Dow, Fina, Chisso, and Mitsui Toatsu to identify the likely commercial single-site catalyst systems for production of polypropylene. In addition, we will evaluate the economics for production of a typical organometallic complexes used in these single-site catalyst systems. The catalyst manufacturing economics representative of production of bridged zirconocene with cyclopentadienyl, indenyl, or fluorenyl ligands will have a significant impact on the success of metallocene based polymer commercialization. PEP 98 GMI

2 CONTENTS 1 INTRODUCTION REPORT OVERVIEW SUMMARY METALLOCENE STRUCTURES INDUSTRY ASPECTS TECHNICAL ASPECT PROCESS ECONOMICS INDUSTRY BACKGROUND PRODUCERS OF SINGLE-SITE CATALYST SYSTEMS PRODUCER PROFILES Akzo Nobel Albemarle Corporation Asahi Glass Company Boulder Scientific Company BP Amoco Chemicals (Formerly BP Chemicals) Engelhard Corporation Fine Organics Kanto Chemical Co Nippon Shokubai Co., Ltd Norquay Technology Inc Peroxid-Chemie Gmbh Phillips Petroleum Single-Site Catalysts L.L.C Targor GmbH Univation Technologies Witco Corporation iii

3 CONTENTS (Continued) W.R. Grace (Grace Davison) SINGLE-SITE CATALYSTS FOR POLYPROPYLENE PRODUCTION EXXON CHEMICAL Isotactic Polypropylene (ipp) One-Metallocene Systems Two-Metallocene Systems Other Isospecific Catalyst Systems rac-[dimethylsilylbis(1-indenyl)]hafnium dimethyl rac-[ch 2 CH 2 (4,5,6,7-tetrahydro-1-indenyl) 2 ]zirconium dichoride rac-[dimethylsilylbis(4,5,6,7-tetrahydro-1-indenyl)]zirconium dichoride rac-[dimethylsilylbis(4,5,6,7-tetrahydro-1-indenyl)]zirconium dimethyl Diamido-substituted, siladiyl-bridged zirconocenes Complexes of the Formula [(C 5 R X H 4-X )Si(R 1 )(R 2 )(NR')]MCl 2 (M = Ti, Zr, or Hf) [C 2 B 9 H 11 )W=N(2,6-Me 2 C 6 H 3 )(Me)Cl] Et 2 O Other Propylene Polymers Branched Copolymers Reactor Blends of Atactic and Isotactic Polypropylene Syndiotactic Polypropylene (spp) FINA Isotactic Polypropylene (ipp) rac-[dimethylsilylbis(2-methyl-1-indenyl)]zirconium Dichoride [Dimethylcarbon(3-t-butyl-1-cyclopentadienyl)(1-indenyl)]zirconium Dichoride and Related Complexes Mixed Metallocene / Ziegler-Natta Catalysts Hemiisotactic Polypropylene (hipp) Syndiotactic Polypropylene (spp) Stereoblock Polymers Reactor Blends iv

4 CONTENTS (Continued) 5 SYNTHESIS OF FINA/TARG OR/BASF HETEROATOM ZIRCONOCENE CATALYST HETEROATOM METALLOCENE SYSTEMS PROCESS CHEMISTRY Silane Addition Amine Addition Deprotanation to Form Amino Magnesium Salt Metallocene Formation Metallocene Oxidation Ligand Substitution REVIEW OF PROCESSES Alternative Metallocene Complex Synthesis Pathways Ligand Precursor Formation Metallocene Complex Formation PROCESS DESCRIPTION n-butyl Lithium Addition (Day 1) Silane Addition (Day 2) Amine Addition (Day 3) Filter, Concentrate, and i-prmgci Addition (Day 4) ZrCL4 Addition, MgC12 Removal, CH2C12 Addition, MeMgBr Addition, MgBrC1 Removal, Concentration, and Product Drying (Day 5) COST ESTIMATES Capital and Production Costs PRODUCTION OF METALLOCENE CATALYST SYSTEMS Solution Phase Systems Cost Contributions of Catalyst System Components Process Description Polymerization Process v

5 CONTENTS (Concluded) Polymerization Economics SYNTHESIS OF EXXON TYPE ZIRCONOCENE CATALYST PROCESS CHEMISTRY Thermal Depolymerization Alkylation Deprotonation Metallocene Formation PROCESS DESCRIPTION CAPITAL INVESTMENT AND PRODUCTION COSTS COST CONTRIBUTIONS OF CATALYST SYSTEM COMPONENTS Polymerization Process Polymerization Economics APPENDIX A: PATENT SUMMARY TABLES... A-1 APPENDIX B: DESIGN AND COST BASES... B-1 APPENDIX C: CITED REFERENCES... C-1 APPENDIX D: PROCESS FLOW DIAGRAM... D-1 vi

6 ILLUSTRATIONS 2.1 Exxon Metalocene Structure Other Substituted Cyclopentadienyl Metalocene Structures Fina / Targor / Basf Metalocene Structure Other Heteroatom Metalocene Structures Process Technologies for Polyproylene Production, Polypropylene Manufacturing Cost Comparison Core Skills of Participants in the Single-Site Catalyst Industry Melting Point vs. Ethylene Content in Propylene-Ethylene Random Copolymers Melting Point Depression vs. Comonomer Content in Propylene-Ethylene and Propylene-Hexene Random Copolymers Production of Fina Metallocene Catalyst... D Polypropylene ICP by a Fluidized Bed Process (Unipol Technology)... D Polypropylene Cost vs. Catalyst Activity Production of Exxon Zirconocene Type Catalyst... D Polypropylene ICP by the Spheripol Process with a Metallocene Catalyst... D Polypropylene Cost vs. Catalyst Activity vii

7 TABLES 2.1 Metallocene Catalyst Manufacture Process Economics Comparison Polypropylene Manufacture Process Economics Comparison U.S. Producers of Single-Site Polymerization Catalysts European Producers of Single-Site Polymerization Catalysts Japanese Producers of Single-Site Polymerization Catalysts Single-Site Catalysts for Polypropylene Production Patent Summary: BASF... A Single-Site Catalysts for Polypropylene Production Patent Summary: Hoechst... A Single-Site Catalysts for Polypropylene Production Patent Summary: Targor... A Single-Site Catalysts for Polypropylene Production Patent Summary: Exxon... A Single-Site Catalysts for Polypropylene Production Patent Summary: Exxon/Hoechst... A Single-Site Catalysts for Polypropylene Production Patent Summary: Fina... A Physical Properties of Ziegler-Natta IPP and MIPP Pysical Properties of BOPP Films Made from Ziegler-Natta IPP and MIPP Fina Metallocene Catalyst Design Bases and Assumptions Fina Metallocene Catalyst Stream Flows Fina Metallocene Catalyst Major Equipment Fina Metallocene Catalyst Total Capital Investment Fina Metallocene Catalyst Variable Production Costs Fina Metallocene Catalyst Variable Production Costs viii

8 TABLES (Concluded) 5.6 Projected Cocatalyst Prices for Commercial Scale Production Fina Metallocene / Unipol Process Design Bases and Assumptions Fina Metallocene / Unipol Process Stream Flows Fina Metallocene / Unipol Process Major Equipment Fina Metallocene / Unipol Process Total Capital Investment Fina Metallocene / Unipol Process Variable Production Cost Fina Metallocene / Unipol Process Production Costs Exxon Metallocene Catalyst Stream Flows Exxon Metallocene Catalyst Major Equipment Exxon Metallocene Catalyst Total Capital Investment Exxon Metallocene Catalyst Variable Production Cost Exxon Metallocene Catalyst Production Cost Exxon Metallocene / Spheripol Process Design Bases and Assumptions Exxon Metallocene / Spheripol Process Stream Flows Exxon Metallocene / Spheripol Process Major Equipment Exxon Metallocene / Spheripol Process Total Capital Investment Exxon Metallocene / Spheripol Process Variable Production Costs Exxon Metallocene / Spheripol Process Production Costs ix

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