KR890009985A - 기체상 중합용 지지된 메탈로센-알룸옥산 촉매의 제조방법 - Google Patents

기체상 중합용 지지된 메탈로센-알룸옥산 촉매의 제조방법 Download PDF

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KR890009985A
KR890009985A KR1019880016810A KR880016810A KR890009985A KR 890009985 A KR890009985 A KR 890009985A KR 1019880016810 A KR1019880016810 A KR 1019880016810A KR 880016810 A KR880016810 A KR 880016810A KR 890009985 A KR890009985 A KR 890009985A
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gas phase
olefins
phase polymerization
metallocene
cyclopentadienyl
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챵 메인
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벤 씨.카덴헤드
엑손 케미칼 패턴츠, 인코포레이티드
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Abstract

내용 없음

Description

기체상 중합용 지지된 메탈로센-알룸옥산 촉매의 제조방법
본 내용은 요부공개 건이므로 전문내용을 수록하지 않았음

Claims (11)

  1. (a) 비탈수된 실리카겔을 알루미늄-트리알킬의 교반된 용액에, 알루미늄-트리알킬 대 물의 몰비가 3 : 1 내지 1: 2가 되도록 하기에 충분한 양으로 가하여 이 혼합물을 반응시키고; (b) 이 반응 혼합물에 메타로센을 가하며 ; (c) 용매를 제거하고 ; (d) 고형물을 건조시켜 자유 유동 분말을 수득하는 단계를 포함하는, 올레핀의 기체상 중합용 지지된 메탈로센-알룸옥산 촉매의 제조방법.
  2. 제1항에 있어서, 상기 비탈수된 실리카겔이 6 내지 10중량%의 수분함량을 갖는, 올레핀의 기체상 중합용 지지된 메탈로센-알룸옥산 촉매의 제조방법.
  3. 제1항 또는 2항에 있어서, 상기 메탈로센중의 알루미늄 대 전이금속 몰비가 1000 : 1 내지 1: 1, 바람직하게는 300 : 1 내지 10 : 1 인, 올레핀의 기체상 중합용 지지된 메탈로센-알룸옥산 촉매의 제조방법.
  4. 제1항 내지 3항중의 어느 한 항에 있어서, 상기 비탈수된 실리카겔이 7 내지 9중량%, 바람직하게는 7.5내지 8.5중량%의 수분 함량을 가지며; 알루미늄 트리알킬(이는 트리메틸 알루미늄 또는 트리에틸 알루미늄인 것이 바람직함)대 물의 몰비가 약 1.2 : 1 내지 약 0.9 : 1 인, 올레핀의 기체상 중합용 지지된 메탈로센-알룸옥산 촉매의 제조방법.
  5. 제1항 내지 4항중의 어느 한 항에 있어서, 상기 비탈수된 실리카겔이 표면적 200 내지 400㎡/g, 공극용적 1내지 2cc/g와 입자크기 30내지 60 를 가지고 ; 및/또는 상기 메탈로센중의 알루미늄 대 전이금속 몰비가 150 :1 내지 30 : 1이고 ; 및/또는 상기 고형물이 바람직하게 75℃ 내지 85℃의 온도에서 건조되는, 올레핀의 기체상 중합용 지지된 메탈로센-알룸옥산 촉매의 제조방법.
  6. 제1항 내지 5항중의 어느 한 항에 있어서, 상기 메탈로센이 하기 일반식(I), (Ⅱ) 또는 (Ⅲ)을 갖는, 올레핀의 기체상 중합용 지지된 메탈로센-알룸옥산 촉매의 제조방법 :
    (Cp)mMRnXq(Ⅰ)
    (C5Rk′)gRs″(C5R′)kMQ3-g(Ⅱ)
    Rs″(C5Rk′)2MQ′ (Ⅲ)
    상기식에서, Cp는 사이클로펜타디에닐 환이고 ; M은 IVB족 또는 VB족 전이금속이며 ; R은 탄소수 1 내지 20의 하이드로카빌그룹 또는 하이드로카복시그룹이고; X는 할로겐이며 ; m은 1 내지 3의 정수이고 ; n은 0 내지 3의 정수이며 ; q는 0 내지 3의 정수이고 ; (C5Rk′)는 사이클로펜타디에닐 또는 치환된 사이클로펜타디에닐이며 ; 각각의 R′는 같거나 다르며, 수소이거나, 탄소수 1 내지 20의 하이드로카빌라디칼, 실리콘-함유 하이드로카빌라디칼, 또는 2개의 탄소원자가 함께 결합하여 C4내지 C6환을 형성하는 하이드로카빌라디칼이고 ; R″는 2개의 (C5Rk′)환을 가교하는, C1-C4알킬렌 라디칼, 디알킬 게르마늄 또는 실리콘, 또는 알킬포스핀 또는 아민 라디칼이며 ; Q는 탄소수 1 내지 20의 하이드로카빌라디칼, 탄소수 1 내지 20의 하이드로카복시 라디칼 또는 할로겐이고, 같거나 다를 수 있으며 ; Q′는 탄소수 1내지 약 20의 알키리리덴 라디칼이고 ; s는 0 내지 1이며 ; g는 0,1 또는 2이고 ; s는 g가 0일때 0이며 ; k는 s가 1일때 4이고, s가 0일때 5이다.
  7. 제1항 내지 6항의 어느 한 항에 있어서, 상기 메탈로센이 지르코노센 또는 티타노센인, 올레핀의 기체상 중합용 지지된 메탈로센-알룸옥산 촉매의 제조방법.
  8. 제7항에 있어서, 상기 지르코노센이 사이클로펜타디에닐 지르코늄 트리클로라이드 ; 펜타메틸사이클로펜타디에닐 지르코늄 트리클로라이드 ; 비스(사이클로펜타디에닐)지르코늄 디-페닐 ; 비스(사이클로펜타디에닐)지르코늄 디클로라이드 ; 알킬 치환된 사이클로펜타디엔 및 이들의 디할라이드 착화합물 ; 디알킬, 트리알킬, 테트라알킬 및 펜타알킬 사이클로펜타디엔, 및 이들의 디할라이드 착화합물 ; 및 실리콘, 인 및 탄소 가교된 사이클로펜타티엔 착화합물로 이루어진 그룹중에서 선택되는, 올레핀의 기체상 중합용 지지된 메탈로센-알룸옥산 촉매의 제조방법.
  9. 제7항에 있어서, 상기 티타노센이 모노사이클로펜타디에닐 티타노센 ; 비스(사이클로펜타디에닐)티나늄 디페닐; 일반식 CP2Ti=CH2·Al(CH3)2Cl(여기에서, Cp는 사이클로펜타디에닐 또는 치환된 사이클로펜타디에닐 라디칼이다)의 카벤 및 이들의 유도체 ; 치환된 비스(Cp)Ti(Ⅳ)화합물 및 이들의 디할라이드 착화합물 ; 디알킬, 트리알킬, 테트라알킬 및 펜타알킬 사이클로펜타디에닐 티타늄 화합물 및 이들의 디할라이드 착화합물 ; 및 실리콘, 포스핀, 아민 또는 탄소-가교된 사이클로펜타디엔 착화합물 및 이들의 디할라이드 착화합물로 이루어진 그룹중에서 선택되는, 올레핀의 기체상 중합용 지지된 메탈로센-알룸옥산 촉매의 제조방법.
  10. 제1항 내지 9항중의 어느 한 항에 따른 지지된 메탈로센-알룸옥산 촉매를 사용한, 올레핀, 예를 들면 에틸렌 및 다른 α-올레핀의 중합방법.
  11. 알루미늄 트리알킬과 수분함유 무기 충진재를 합한 다음 메탈로센을 가하여 지지된 메탈로센-알룸옥산 촉매를 제조하는 방법에 있어서, 흡수되거나 흡착된 수분을 함유하는 실리카겔 형태의 상기 충진재를 알루미늄 트리알킬의 교반된 용액에 가하는 것을 특징으로 하는 방법.
    ※ 참고사항 : 최초출원 내용에 의하여 공개하는 것임.
KR1019880016810A 1987-12-17 1988-12-16 기체상 중합용 지지된 메탈로센-알룸옥산 촉매의 제조방법 KR960005917B1 (ko)

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US4925821A (en) * 1987-12-17 1990-05-15 Exxon Chemical Patents Inc. Method for utilizing triethyaluminum to prepare an alumoxane support for an active metallocene catalyst
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IL88494A (en) 1992-06-21
PL276458A1 (en) 1989-07-24
DK677488D0 (da) 1988-12-05
KR960005917B1 (ko) 1996-05-03
AU2596188A (en) 1989-06-29
US4912075A (en) 1990-03-27
ATE80167T1 (de) 1992-09-15
CA1327347C (en) 1994-03-01
YU228288A (en) 1990-10-31
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NO885363L (no) 1989-06-19
DE3874310T2 (de) 1993-02-25
AU621320B2 (en) 1992-03-12
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DE3874310D1 (de) 1992-10-08
EP0323716B1 (en) 1992-09-02
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FI885570A0 (fi) 1988-11-30
NO885363D0 (no) 1988-12-01
FI885570A (fi) 1989-06-18

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