KR880701741A - 신규한 지지 중합촉매 - Google Patents

신규한 지지 중합촉매

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KR880701741A
KR880701741A KR1019880700511A KR880700511A KR880701741A KR 880701741 A KR880701741 A KR 880701741A KR 1019880700511 A KR1019880700511 A KR 1019880700511A KR 880700511 A KR880700511 A KR 880700511A KR 880701741 A KR880701741 A KR 880701741A
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bis
metallocene
titanium
cyclopentadienyl
olefin polymerization
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KR950010227B1 (ko
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쥬니어 하워드 커티스 웰보른
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벤 씨. 카덴헤드
엑손 케미칼 패턴츠, 인코포레이티드
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    • 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
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    • 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
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    • 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
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    • 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
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    • 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
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    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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    • Y10S526/943—Polymerization with metallocene catalysts

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  • Macromonomer-Based Addition Polymer (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)

Abstract

내용 없음

Description

신규한 지지 중합촉매
본 내용은 요부공개 건이므로 전문내용을 수록하지 않았음

Claims (15)

  1. 주가율표의 IVB 및 VIB족 금속의 최소한 하나의 메탈로센, IVB, VB 및 VIB족 금속의 최소한 하나의 비-메탈로센 전이금속 화합물 및 알루옥산의, 지지체 존재하에 형성된, 지지된 반응생성물을 포함하는 올레핀 중합지지촉매.
  2. 제1항에 있어서, 지지체가 IIA, IIIA, IVB 또는 IVB족 원소의 다공성 무기산화물인 올레핀 중합지지촉매.
  3. 제1항 또는 제2항에 있어서, 지지체가실리카인 올레핀 중합지지촉매.
  4. 제1항 내지 제3항중 어느 한 항에 있어서, 메탈로센이 티타늄, 지르코늄, 하프늄 및 바나듐 메탈로센, 및 이들 둘이상의 혼합물로부터 선택된 올레핀 중합지지촉매.
  5. 제1항 내지 제4항중 어느 한 항에 있어서, 비-메탈로센 전이금속 화합물이 티타늄 테트라클로라이드, 바나듐 테트라클로라이드, 바나듐 옥시트리클로라이드 및 이들 둘이상의 혼합물로부터 선택된 올레핀 중합지지촉매.
  6. 제1항 내지 제5항중 어느 한 항에 있어서, 알룸옥산이 메틸 알룸옥산인 올레핀 중합지지촉매.
  7. 제1항 내지 제6항중 어느 한 항에 있어서, 지지된 생성물 내의알루미늄 대 전이금속 몰비가 1 : 1 내지 300 : 1의 범위내에 있는 올레핀 중합지지촉매.
  8. 제7항에 있어서, 몰비가 50 : 1 내지 5 : 1의 범위내에 있는 올레핀 중합지지촉매.
  9. 제1항 내지 제8항중 어느 한 항에 있어서, 메탈로센이 다음 일반식(Ⅰ)(Ⅱ) 및 (Ⅲ)으로 표시되고, 비-메탈로센 전이금속 화합물이 TrX'4-q(OR1)q, TrX'4-qR2 q, VOX'3및 VO(OR1)3으로 표시되는 올레핀 중합지지촉매.
    (C5R'k)gR"s(C5R'k)MQ3-g(Ⅱ)
    R"s(C5R'k)2MQ(Ⅲ)
    상기식에서, Cp는사이클로펜타디에닐 환이고 ; M은 4b, 5b 또는 6b족 전이금속이고 ; R은 탄소수 1 내지 20의 하이드로카빌그룹 또는 하이드로 카복시그룹이고 ; X는 할로겐이고 ; m은 1 내지 3, n은 0 내지 3, q는 0 내지 3이며 m+n+q의 합은 M의 산화상태와 같고 단, 일반식 TrX'4-q(OR1)q및 TrX'4-qR2 q에서 q는 0q4 이며 ; (C5R'5)m사이클로펜타디에닐 또는 치환된 사이클로펜타디에닐이며 ; R'는 각각 같거나 다르며, 수소, 또는 탄소수 1 내지 20의 알킬, 알케닐, 아릴, 알킬아릴 및 아릴알킬로부터 선택된 하이드로 카빌라디칼 이거나, 2개의탄소원작 함께 결합하여 C4내지 C6환을 형성하고 ; R"는 두(C5R'k)환을 연결하는 C1-C4알킬렌 라디칼, 디알킬 게르마늄 또는 실리콘, 또는 알킬 포스핀 또는 아민라디칼이고 ; Q는 탄소수 1 내지 20의 아릴, 알킬 알케닐, 알킬아릴 및 아릴 알킬 라디칼로부터 선택된 하이드로 카빌라디칼, 탄소수 1 내지 20의 하이드로카복시라디칼 또는 할로겐이며 이들은 각각 같거나 다를 수 있고 ; Q'는 탄소수 1 내지 20의 알킬리덴 라디칼이고 ; s는 0 또는 1 이고 ; g는 0.1 또는 2이고 ; s는 g가 0일 때 0이고 ; k는 s가 1일 때 4이며, s가 0일 때 5이고 ; Tr은 IVB, VB 또는 VIB족 금속이고 ; X'는 할로겐이고 ; R1은 탄소수 1 내지 20의 알킬, 아릴 또는 사이클로알킬그룹이고 ; R2는 탄소수 1 내지 20의 알킬, 아릴, 아르알킬 또는 치환된 아르알킬그룹이다.
  10. 제9항에 있어서, 메탈로센이 비스(사이클로펜타디에닐) 지르코늄 디클로라이드, 비스(사이클로펜타디에닐) 지르코늄 메틸 클로라이드, 비스(사이클로펜타디에닐) 지르코늄 디메틸, 비스(메틸사이클로펜타디에닐) 비르코늄 디클로라이드, 비스(메틸사이클로펜타디에닐) 지르코늄 메틸 클로라이드, 비스(메틸사이클로펜타디에닐) 지르코늄 메틸, 비스(펜타메틸사이클로펜타디에닐) 지르코늄 디클로라이드, 비스(펜타메틸사이클로펜타디에닐) 지르코늄 메틸 클로라이드, 비스(펜탈메틸사이클로펜타디에닐) 지르코늄 디메틸, 비스(n-부틸-사이클로펜타디에닐) 지르코늄 디클로라이드, 비스(n-부틸-사이클로펜타디에닐) 지르코늄 메틸 클로라이드, 비스(n-부틸-사이클로펜타디에닐) 지르코늄 디메틸, 비스(사이클로펜타디에닐) 티타늄 디페닐, 비스(사이클로펜타디에닐) 티타늄 디클로라이드, 비스(사이클로펜타디에닐) 티타늄 메틸 클로라이드, 비스(사이클로펜타디에닐) 티타늄 디메틸, 비스(메틸사이클로펜타디에닐) 티타늄 디페닐, 비스(메틸사이클로펜타디에닐) 티타늄 디클로라이드, 비스(메틸사이클로펜타디에닐) 티타늄 디페닐, 비스(메틸사이클로펜타디에닐) 티타늄 메틸 클로라이드, 비스(메틸사이클로펜타디에닐) 티타늄 디메틸, 비스(펜타메틸사이클로펜타디에닐) 티타늄 디클로라이드, 비스(펜타메틸사이클로펜타디에닐) 티타늄 디페닐, 비스(펜타메틸사이클로펜타디에닐) 티타늄 메틸클로라이드, 비스(펜타메틸사이클로펜타디에닐) 티타늄 디메틸, 비스(n-부틸-사이클로펜타디에닐) 티타늄 디페닐, 비스(n-부틸-사이클로펜타디에닐) 티타늄 디클로라이드 및 이들 혼합물로부터 선택되고, 비-메탈로센 화합물은 티타늄 테트라클로라이드, 바나듐 테트라클로라이드 ac 바나듐 옥시트리클로라이드로부터 선택된 올레핀 중합지지촉매.
  11. 최소한 하나의 메탈로센과 최소한 하나의 비-메탈로센 화합물을 불활성 탄화수소용매중의 지지체 슬러리와 불활성 탄화수소용매중의 알룸옥산에 첨가함을 특징으로 하는, 제1항에 정의돈 올레핀 중합지지촉매의 제조방법.
  12. 제11항에 있어서, 알루미늄과 금속을 기준으로 알룸옥산 대 메탈로센의 몰비가 300 : 1 내지 1 : 1의 범위내에 있고, 메탈로센화합물 대 1-메탈로센 전이금속화합물의 몰비가 비-메탈로센 전이금속화합물 몰당 메탈로센 100 내지 0.01몰의 범위내에 있음을 특징으로 하는 방법.
  13. 제1항 내지 제10항중 어느 한 항에 따른 지지촉매와 유기금속 보조촉매를 포함함을 특징으로 하는 올레핀 중합용 촉매계.
  14. 제13항에 있어서, 보조촉매가 알루미늄 알킬화합물을 포함함을 특징으로 하는 촉매계.
  15. 단량체를 제1항 내지 제10항중 어느 한 항에 따른 지지촉매, 제11항 또는 제12항에 따른 방법에 의해 제조된 지지촉매 또는 제13항 또는 제14항에 따른 촉매계의 존재하에 중합시킴을 특징으로 하는, 에틸렌 중합체, 또는 에틸렌과 알파-올레핀 또는 디올레핀의 공중합체를 제조하는 방법.
    ※ 참고사항 : 최초출원 내용에 의하여 공개하는 것임.
KR1019880700511A 1986-09-09 1987-09-09 올레핀 중합지지 촉매 KR950010227B1 (ko)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
US06/906,103 US5077255A (en) 1986-09-09 1986-09-09 New supported polymerization catalyst
US906.103 1986-09-09
US906103 1986-09-09
PCT/US1987/002308 WO1988002008A1 (en) 1986-09-09 1987-09-09 New supported polymerization catalyst

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