KR970701211A - 올레핀 중합 촉매(olefin polymerization catalysts) - Google Patents

올레핀 중합 촉매(olefin polymerization catalysts)

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Publication number
KR970701211A
KR970701211A KR1019960704776A KR19960704776A KR970701211A KR 970701211 A KR970701211 A KR 970701211A KR 1019960704776 A KR1019960704776 A KR 1019960704776A KR 19960704776 A KR19960704776 A KR 19960704776A KR 970701211 A KR970701211 A KR 970701211A
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South Korea
Prior art keywords
catalyst composition
styrene
vinyl
divinylbenzene
additional
Prior art date
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KR1019960704776A
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English (en)
Inventor
브렌트 퍼텍 앨런
스티븐 시노모토 로널드
Original Assignee
더니스 피. 산티니
모빌 오일 코오포레이숀
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Priority claimed from US08/205,430 external-priority patent/US5461017A/en
Application filed by 더니스 피. 산티니, 모빌 오일 코오포레이숀 filed Critical 더니스 피. 산티니
Publication of KR970701211A publication Critical patent/KR970701211A/ko

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/165—Polymer immobilised coordination complexes, e.g. organometallic complexes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/6592—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring
    • C08F4/65922—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring containing at least two cyclopentadienyl rings, fused or not
    • C08F4/65925—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring containing at least two cyclopentadienyl rings, fused or not two cyclopentadienyl rings being mutually non-bridged
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/12—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides
    • B01J31/14—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides of aluminium or boron
    • B01J31/143—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides of aluminium or boron of aluminium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/22—Organic complexes
    • B01J31/2282—Unsaturated compounds used as ligands
    • B01J31/2295—Cyclic compounds, e.g. cyclopentadienyls
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/65912—Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with an organoaluminium compound
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/65916—Component covered by group C08F4/64 containing a transition metal-carbon bond supported on a carrier, e.g. silica, MgCl2, polymer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/40—Complexes comprising metals of Group IV (IVA or IVB) as the central metal
    • B01J2531/48—Zirconium
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/619—Component covered by group C08F4/60 containing a transition metal-carbon bond
    • C08F4/61912—Component covered by group C08F4/60 containing a transition metal-carbon bond in combination with an organoaluminium compound
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/619—Component covered by group C08F4/60 containing a transition metal-carbon bond
    • C08F4/61916—Component covered by group C08F4/60 containing a transition metal-carbon bond supported on a carrier, e.g. silica, MgCl2, polymer
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/619—Component covered by group C08F4/60 containing a transition metal-carbon bond
    • C08F4/6192—Component covered by group C08F4/60 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Inorganic Chemistry (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)

Abstract

본 발명은 다공성의 미립형 가교 수지상 스티렌 중합체 기질 및 그 표면상에 배치된 메탈로센 및 알루미녹산을 함유하는 올레핀 중합 촉매계에 관한 것이다.

Description

올레핀 중합 촉매 (OLEFIN POLYMERIZATION CATALYSTS)
본 내용은 요부공개 건이므로 전문내용을 수록하지 않았음

Claims (11)

  1. 스티렌의 가교 중합 생성물을 함유하는 미립의 다공성 유기 기질의 표면상에 분산되고 알루미녹산으로 활성화된 메탈로센 화합물을 함유하는 3 내지 10개의 탄소 원자를 지닌 알파 올레핀과 에틸렌을 공중합시키기 위한 촉매 조성물.
  2. 제1항에 있어서, 가교 스티렌 중합체의 입자가 평균 소공 직경이 110 내지 1050Å인 소공을 갖고 있음을 특징으로 하는 촉매 조성물.
  3. 제1항 또는 제2항에 있어서, 기질이 스티렌과 부가적인 비닐 단량체의 가교 공중합 생성물을 함유하는 촉매 조성물.
  4. 제3항에 있어서, 부가적인 비닐 단량체가 디비닐벤젠인 촉매 조성물.
  5. 제1항에 있어서, 기질이 공중합체내에 함유된 스티렌과 디비닐벤젠의 총 중량을 기준으로 할 때 디비닐벤젠을 6중량% 이상 함유하는 공중합체인 촉매 조성물.
  6. 제3항 내지 제5항 중 어느 한 항에 있어서, 공중합체가 기질 입자상에 표면 작용기를 제공하는 부가 단량체를 함유하는 촉매 조성물.
  7. 제6항에 있어서, 부가 단량체가 아크릴산, 메타크릴산, 비닐 아세테이트, 메틸비닐 에테르, 비닐 클로라이드, p-아세톡시 스티렌, 클로로 스티렌, 클로로 디비닐벤젠, 비닐 톨루엔, 에틸렌 글리콜 디아크릴레이트, 에틸렌 글리콜 디메타크릴레이트, 비닐 벤젠 클로라이드, 및 비닐 피리딘 중에서 선택되는 촉매 조성물.
  8. 제6항에 있어서, 부가 단량체가 p-아세톡시 스티렌이고, 공중합 생성물을 형성하는데 사용된 혼합물의 1 내지 30중량%를 차지하는 촉매 조성물.
  9. 제6항에 있어서, 알루미녹산이 메틸알루미녹산인 촉매 조성물.
  10. 제9항에 있어서, 메탈로센 화합물이 비스 시클로펜타디에닐 지르코늄 디클로라이드인 촉매 조성물.
  11. 제10항의 촉매 조성물을 사용하여 3 내지 10개의 탄소 원자를 지닌 알파 올레핀과 에틸렌을 공중합하는 방법.
    ※ 참고사항 : 최초출원 내용에 의하여 공개하는 것임.
KR1019960704776A 1994-03-01 1995-02-22 올레핀 중합 촉매(olefin polymerization catalysts) KR970701211A (ko)

Applications Claiming Priority (5)

Application Number Priority Date Filing Date Title
US20493194A 1994-03-01 1994-03-01
US08/204,931 1994-03-01
US08/205,430 US5461017A (en) 1991-12-13 1994-03-04 Olefin polymerization catalysts
US08/205,430 1994-03-04
PCT/US1995/002174 WO1995023816A1 (en) 1994-03-01 1995-02-22 Olefin polymerization catalysts

Publications (1)

Publication Number Publication Date
KR970701211A true KR970701211A (ko) 1997-03-17

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EP (1) EP0748340A4 (ko)
JP (1) JPH09509970A (ko)
KR (1) KR970701211A (ko)
CN (1) CN1142233A (ko)
AU (1) AU694765B2 (ko)
CA (1) CA2181259A1 (ko)
WO (1) WO1995023816A1 (ko)

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US6143686A (en) * 1994-08-03 2000-11-07 Exxon Chemical Patents, Inc. Supported ionic catalyst compositions
JP3582181B2 (ja) * 1995-10-04 2004-10-27 住友化学工業株式会社 オレフィン重合触媒用担体、オレフィン重合触媒及びオレフィン重合体の製造方法
US6063725A (en) * 1995-11-07 2000-05-16 Mitsui Chemicals, Inc. Olefin polymerization catalyst system
GB9613814D0 (en) * 1996-07-02 1996-09-04 Bp Chem Int Ltd Supported polymerisation catalysts
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US6100214A (en) * 1997-06-05 2000-08-08 Exxon Chemical Patents Inc. Polymeric supported catalysts for olefin polymerization
DE19941460A1 (de) * 1999-08-31 2001-03-01 Basf Ag Katalysatorsystem, dessen Herstellung und Verwendung zur Polymerisation von Olefinen
NO20013880L (no) 2000-08-22 2002-02-25 Rohm & Haas Matriks og fremgangsmåte for fremstilling av polyolefiner
GB0023662D0 (en) * 2000-09-27 2000-11-08 Borealis Tech Oy Supported catalyst
US7074736B2 (en) 2000-10-31 2006-07-11 Rohm And Haas Company Hydrozirconated matrix and process for polyolefin production
US20020107344A1 (en) * 2000-12-07 2002-08-08 Peterson Thomas Henry Supprt materials for use with polymerization catalysts
ATE353928T1 (de) * 2003-08-29 2007-03-15 Nitto Denko Corp Poröses harzkorn und verfahren für dessen herstellung
CN104558362B (zh) * 2013-10-29 2017-07-14 中国石油天然气股份有限公司 一种三元共聚物载体及其制备方法
CN104558265B (zh) * 2013-10-29 2017-05-10 中国石油天然气股份有限公司 一种茂金属催化剂体系及其制备方法
WO2017054398A1 (zh) 2015-09-28 2017-04-06 中国石油天然气股份有限公司 一种球形负载型过渡金属催化剂
CN106554433B (zh) * 2015-09-28 2019-06-11 中国石油天然气股份有限公司 一种球形负载型茂金属催化剂
CN107540775B (zh) * 2016-06-29 2019-10-11 中国石油天然气股份有限公司 一种有机/无机复合载体的制备方法
CN107540774B (zh) * 2016-06-29 2019-10-11 中国石油天然气股份有限公司 一种用于烯烃聚合催化剂有机载体的制备方法

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AU694765B2 (en) 1998-07-30
AU1880795A (en) 1995-09-18
EP0748340A1 (en) 1996-12-18
JPH09509970A (ja) 1997-10-07
EP0748340A4 (en) 1997-11-19
WO1995023816A1 (en) 1995-09-08
CA2181259A1 (en) 1995-09-08
CN1142233A (zh) 1997-02-05

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