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KR900701859A - 올레핀의 고압 중합용의 지지된 메탈로센-알룸옥산 촉매. 그의 제조방법 및 그의 사용방법 - Google Patents

올레핀의 고압 중합용의 지지된 메탈로센-알룸옥산 촉매. 그의 제조방법 및 그의 사용방법

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Publication number
KR900701859A
KR900701859A KR1019900701098A KR900701098A KR900701859A KR 900701859 A KR900701859 A KR 900701859A KR 1019900701098 A KR1019900701098 A KR 1019900701098A KR 900701098 A KR900701098 A KR 900701098A KR 900701859 A KR900701859 A KR 900701859A
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Prior art keywords
cyclopentadienyl
aluminum
catalyst according
catalyst
metallocene
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KR1019900701098A
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Inventor
창 메인
Original Assignee
벤 씨. 카덴헤드
엑손 케미칼 패턴츠 인코포레이티드
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Publication of KR900701859A publication Critical patent/KR900701859A/ko
Withdrawn legal-status Critical Current

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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F10/00Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00Polymerisation catalysts
    • C08F4/42Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44Metals; 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
    • C08F4/60Metals; 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
    • C08F4/62Refractory metals or compounds thereof
    • C08F4/64Titanium, zirconium, hafnium or compounds thereof
    • C08F4/642Component covered by group C08F4/64 with an organo-aluminium compound
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00Polymerisation catalysts
    • C08F4/42Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44Metals; 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
    • C08F4/60Metals; 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
    • C08F4/62Refractory metals or compounds thereof
    • C08F4/639Component covered by group C08F4/62 containing a transition metal-carbon bond
    • C08F4/63912Component covered by group C08F4/62 containing a transition metal-carbon bond in combination with an organoaluminium compound
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00Polymerisation catalysts
    • C08F4/42Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44Metals; 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
    • C08F4/60Metals; 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
    • C08F4/62Refractory metals or compounds thereof
    • C08F4/639Component covered by group C08F4/62 containing a transition metal-carbon bond
    • C08F4/63916Component covered by group C08F4/62 containing a transition metal-carbon bond supported on a carrier, e.g. silica, MgCl2, polymer
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00Polymerisation catalysts
    • C08F4/42Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44Metals; 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
    • C08F4/60Metals; 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
    • C08F4/62Refractory metals or compounds thereof
    • C08F4/639Component covered by group C08F4/62 containing a transition metal-carbon bond
    • C08F4/6392Component covered by group C08F4/62 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10STECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S526/00Synthetic resins or natural rubbers -- part of the class 520 series
    • Y10S526/943Polymerization with metallocene catalysts

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)

Abstract

내용 없음

Description

올레핀의 고압 중합용의 지지된 메탈로센 -알룸옥산 촉매, 그의 제조방법 및 그의 사용방법
본 내용은 요부공개 건이므로 전문내용을 수록하지 않았음

Claims (10)

  1. (a) 0.5 내지 1.5의 트리알킬 알루미늄 대 물의 몰비를 제공하는데 충분한 양으로 10μ미만의 입경을 갖는 비탈수된 실리카겔을 트리알킬 알루미늄의 교반된 용액에 가한 다음, 그 혼합물을 반응시키고: (b) 상기 반응 혼합물에 에탈로센을 가하고: (c) 용매를 제거한 다음: (d) 고체를 건조시켜 자유 유동성 분말을 형성시킴으로써 제조된, 올레핀의 고압 중합용의 지지된 에탈로센-알롬옥산 촉매 착화합물.
  2. 제1항에 있어서, 상기 비탈수된 실리카켈의 함수율이 5 내지 2O중량%, 바람직하게는 8 내지 15중량%인 촉매.
  3. 제1 또는 2항에 있어서, 상기 메탈로센중의 알루미늄 대 전이금속의 몰비가 1000: 1내지 1 : 1인 촉매.
  4. 제1 내지 6항중어느 한 항에 있어서, 상기 비탈수된 실리카겔의 함수율이 5 내지 2O중량%이고, 트리알킬알루미늄 대 물의 몰비가 0:8 내지 1:2인 촉매.
  5. 제1 내지 4항중 어느 한 항에 있어서, 상기 메탈로센중의 알루미늄 대 전이금속의 몰비가 500: 1 내지 10: 1, 바람직하게는 100:1 내지 20: 1인 촉매.
  6. 제1 내지 5항중 어느 한 항에 있어서, 상기 트리알킬 알루미늄이 트리메틸 알루미늄 또는 트리에틸 알루미늄인 촉매.
  7. 제1 내지 6항중 어느 한 항에 있어서, 상기 비탈수된 실리카겔의 표면적이 200 내지 400㎡/g이고, 공극부피가 1 내지 2cc/g인 촉매.
  8. 제1 내지 7항중 어느 한 항에 있어서, 상기 메탈로센이 하기 일반식(I), (Ⅱ) 및 (Ⅲ)으로 이루어진 그룹으로부터 선택된 촉매.
    (Cp)mMRnXq(I)
    〔상기식(I)에서, CP는 사이클로펜타디에닐 환이고, M은 4b 또는 5b족 전이금속이려, R은 단소수 1 내시 2O의 하이드로카빌 라디칼 또는 하이그로카복시 라디칼이고, X는 할로겐이며, m은 1 내지 3의 정수이고, n은 O 내지 3의 정수이며, q는 O 내지 3의 정수이다〕;
    (C5R'k)gR″s(C5R′k)MQ3-g(Ⅱ)
    R″S(C5R′k)2MQ′ (Ⅲ)
    〔상기식 (Ⅱ) 및 (Ⅲ)에서, (C5R'k)는 사이클로펜타디에닐 또는 치환된 사이클로 펜타디에닐이고, R'는 각각 같거나 다르며, 수소이거나 또는 탄소수 1 내지 2O의 하이드로카빌 라디칼, 실리콘-함유 하이드로카빌라디칼 또는 2개의 탄소원자가 서로 결합하여 C4-C6환을 형성하는 하이드로카벨 라디칼이며, R는 C1-C4알킬렌 라디칼, 디 알킬 게르마늄 또는 실리콘, 또는 2개의 (C5R'k)환을 연결하는 알킬 포스핀 또는 아민 라디칼이고, q는 각각 같거나 다르며, 탄소수 1 내지 2O의 하이드로카빌 라디칼, 탄소수 1 내지 2O의 하이드로카복시 라디칼 또는 할로겐이며, Q'는 탄소수 1 내지 2O의 알킬리덴 라디칼이며, S는 O 또는 1이고, g는 O,1 또는 2이고, g가 O일때 S는 O이며, k는 s가 1일때 4이고, s가 O일때 5이며, M은 4b족 또는 5b족 전이금속이다〕
  9. 제8항에 있어서, 상기 메탈로센이 지르코노센, 하프노센 또는 티타노센인 촉매.
  10. 제8항 또는 9항에 있어서, 상기 지르코노센이 사이클로펜타디에닐 지르코늄 트리클로라이디: 펜타메틸사이클로펜타디에닐 지르코늄 트리클로라이드; 비스(사이클로 펜타디에닐)지르코늄 디페닐: 비스(사이클로펜타디에닐) 지르코늄 디클로라이드: 알킬 치환된 사이클로펜타디엔 및 그들의 디할라이드 착화합물: 디알킬, 트리알킬, 테트라알킬 및 펜타 알킬 사이클로펜타디엔, 및 그들의 디할라이드 착화합물: 및 실리콘, 인 및 탄소 가교결합된 사이클로펜타디엔 착화합물로 이루어진 그룹으로부터 선택된 촉매.
    ※ 참고사항 : 최초출원 내용에 의하여 공개하는 것임.
KR1019900701098A 1988-09-28 1989-09-26 올레핀의 고압 중합용의 지지된 메탈로센-알룸옥산 촉매. 그의 제조방법 및 그의 사용방법 Withdrawn KR900701859A (ko)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US250,293 1988-09-28
US07/250,293 US4935397A (en) 1988-09-28 1988-09-28 Supported metallocene-alumoxane catalyst for high pressure polymerization of olefins and a method of preparing and using the same
PCT/US1989/004183 WO1990003403A1 (en) 1988-09-28 1989-09-26 A supported metallocene-alumoxane catlyst for high pressure polymerisation of olefins and a method of preparing and using the same

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KR900701859A true KR900701859A (ko) 1990-12-04

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US (1) US4935397A (ko)
EP (1) EP0361866A1 (ko)
JP (1) JPH03501869A (ko)
KR (1) KR900701859A (ko)
AU (1) AU625601B2 (ko)
BR (1) BR8907098A (ko)
DK (1) DK129090A (ko)
FI (1) FI902637A7 (ko)
HU (1) HUT53916A (ko)
IL (1) IL91766A0 (ko)
PT (1) PT91829A (ko)
WO (1) WO1990003403A1 (ko)
YU (1) YU188189A (ko)

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