KR960041190A - 메탈로센의 제조 방법 및 이의 용도 - Google Patents

메탈로센의 제조 방법 및 이의 용도 Download PDF

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KR960041190A
KR960041190A KR1019960018505A KR19960018505A KR960041190A KR 960041190 A KR960041190 A KR 960041190A KR 1019960018505 A KR1019960018505 A KR 1019960018505A KR 19960018505 A KR19960018505 A KR 19960018505A KR 960041190 A KR960041190 A KR 960041190A
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cyclopentadienyl
metallocene
dimethyl
zirconium
fluorenyl
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파페르 베른트
지이 알트 헬무트
브루스 웰치 엠
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비이 엠 달러
휘립프스 피트로오리암 캄파니
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Publication of KR960041190A publication Critical patent/KR960041190A/ko

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Abstract

동일한 시클로펜탈디에닐-함유 라디칼 치환제의 π 및 O 탄소 결합 모두에 의해 전이 금속에 결합된 시클로펜타디에닐-함유 라디칼을 포함하고 있는 메탈로센인 이중결합된 메탈로센은 적어도 하나의 불포화 치환체를 포함하는 시클로펜타디에닐-함유 라디칼을 포함하는 메탈로센을 환원시킴으로써 제조될 수 있다. 또한 적절한 중합반응 조건하에서 적어도 하나의 올레핀 단량체와 이러한 이중결합된 메탈로센을 접촉시키는 것으로 구성되는 중합체 생산방법.

Description

메탈로센의 제조 방법 및 이의 용도
본 내용은 요부공개 건이므로 전문내용을 수록하지 않았음

Claims (29)

  1. 불포화 단량체를 적절한 중합조건하에서 일반식(Ⅰ)의 메탈로센 또는 일반식(Ⅱ)의 적어도 하나의 단위를 갖는 메탈로센과 접촉시킴을 특징으로 하는, 중합체 형성 방법.
    상기 식에서, 각각의 Z는 동일하거나 상이한 시클로펜타디에닐-함유 라디칼이고, R은 두 개의 Z라디칼을 연결하는 2가 유기 라디칼이며, X는 1 또는 0이며, R′은 연결된 Z와 Me를 분리시키는 4개의 원소만이 존재하며 이 원자들이 탄소원자인 방식으로 Z와 Me를 연결하는 2가 유기 라디칼이며, Me는 전이 금속이며, Q는 히드로카빌, 히드로카빌옥시 또는 할라이드이며, R″은 각각 결합된 Z 및 Me을 분리시키는 원자의 수가 2,3 또는 4 이상이 되도록 하는 Z와 Me를 연결하는 2가 유기 라디칼이다.
  2. 제1항에 있어서, 중합이 메탈로센을 위한 조촉매의 존재하에 수행되는 방법.
  3. 제2항에 있어서, 조촉매가 하기 일반식의 반복 단위를 갖는 유기 알루미녹산 화합물을 포함하는 방법.
    상기 식에서, R은 1 내지 5개의 탄소원자를 갖는 히드로카빌 그룹이다.
  4. 제3항에 있어서, 조촉매가 메틸알루미녹산을 포함하는 방법.
  5. 제4항에 있어서, 메탈로센이 메탈로센과 메틸알루미녹산을 미립상의 건조 무기 지지물과 함께 배합한 후진공을 이용하여 생성 혼합물을 건조시킴으로써 제조된 고체 촉매 시스템으로서 이용되는 방법.
  6. 제4항에 있어서, 메탈로센이 메탈로센과 메틸알루미녹산을 배합한 후 생성된 혼합물을 올레핀과 접촉시켜 예비중합체를 형성한 다음, 진공을 이용하여 생성 고체를 건조시킴으로써 제조된 고체 촉매 시스템으로서 이용되는 방법.
  7. 제6항에 있어서, 메탈로센과 메틸알루미녹산을 예비중합반응이 수행되기 전에 미립상의 건조 무기 지지물과 배합되는 방법.
  8. 제1항에 있어서, 알파 올레핀이 중합되는 방법.
  9. 제1항 내지 제8항 중 어느 한 항에 있어서, 메탈로센이 일반식(Ⅰ)을 가지며 x가 1이고, R이 디알킬 메틸렌 또는 디알킬 실리렌인 방법.
  10. 제9항에 있어서, R′이 부타닐인 방법.
  11. 제9항에 있어서, 이중 결합된 메탈로센이 (시클로펜타디에닐) ((시클로펜타디에닐) (디메틸)메탄(1-인다닐)) 지르코늄(Ⅳ) 클로라이드, ((플루오레닐)(부타닐 시클로펜타디에닐)(디메틸)메탄) 지르코늄(Ⅳ) 클로라이드 또는 ((플루오레닐)(부타닐 인데닐)(디메틸)실란) 지르코늄(Ⅳ) 클로라이드인 방법.
  12. 제1항 내지 8항 중 어느 한 항에 있어서, 메탈로센이 일반식(Ⅰ)을 가지며, x가 0인 방법.
  13. 제12항에 있어서, R′Me에 결합된 말단 인다닐기를 가지며 인다닐기가 한 원자에 의해 이들이 부착된 Z기로부터분리되어 있는 방법.
  14. 제12항에 있어서, R′이 부타닐인 방법.
  15. 제14항에 있어서, 이중 결합된 메탈로센이 (시클로펜타디에닐)(부타닐-시클로펜타디에닐)지르코늄(Ⅳ) 클로라이드인 방법.
  16. 제1항 내지 8항 중 어느 한 항에 있어서, 메탈로센이 일반식(Ⅱ)를 가지는 방법.
  17. 제16항에 있어서, 메탈로센이 x가 1이고 R″이 2가의 포화 에틸렌 라디칼인 메탈로센인 방법.
  18. 제16항에 있어서, 메탈로센이 R″에 부착된 Z가 시클로펜타디에닐이고, 다른 하나의 Z가 프루오레닐이며 R이 2가의 포화 디메틸 메틸렌 라이칼인 메탈로센인 방법.
  19. 제16항에 있어서, 이중 결합된 메탈로센이 ((플루오레닐) 에텐시클로펜타디에닐)(디메틸)메탄)지르코늄 디클로라이드의 환원에 의해 생성되는 방법.
  20. 적어도 하나의 불포화 치환체를 갖는 시클로펜타디에닐-함유 라디칼을 갖는 출발물질 메탈로센을 불포화 치환체가 메탈로센의 금속에 결합된 포화 치환체로 전환되는 조건하에서, 환원제와 접촉시킴으로써 제조된 메탈로센을 포함하는 촉매 시스템과 적절한 중합 조건하에서 불포화 단량체를 접촉시킴을 특징으로 하는 중합체 생산 방법.
  21. 제20항에 있어서, 출발물질 메탈로센이 메탈로센의 금속에 결합된 적어도 2개의 시클로펜타디에닐-함유 리간드와 메탈로센의 금속에 결합된 적어도 하나의 할라이드를 함유하는 방법.
  22. 제20항에 있어서, 출발물질 메탈로센이 (시클로펜타디에닐(부트-3-에닐 시클로펜타디에닐)지르코늄 디클로라이드 또는 (시클로펜타디에닐)((시클로펜타디에닐)(인데닐)(디메틸메탄)지르코늄 디클로라이드인 가교되지 않은 메탈로센 또는 (부트-3-에닐 시클로펜타디에닐)(플루오레닐)(디메틸)메탄)지르코늄 디클로라이드, ((오메가부테닐인데닐)(플루오레닐)(디메틸)실란)지르코늄 디클로라이드 또는 ((플루오레닐)(에덴 시클로펜타디에닐)(디메틸)메탄)지르코늄 디클로라이드인 가교되고 샌드위치 결합된 메탈로센인 방법.
  23. 유기 리간드로서 (시클로펜타디에닐)((시클로펜타디에닐)(인데닐)(디메틸)메탄))을 갖는 메탈로센을 제외한 적어도 하나 이상의 불포화 치환체를 포함하는 시클로펜타디에닐-함유 라디칼을 포함하는 특정유형의 메탈로센을 환원제와 반응시킴을 특징으로 하는, 시클로펜타디에닐-함유 라디칼 치환체의 π결합 또는 탄소 σ결합 모두에 의해 전이 금속에 결합된 시클로펜타디에닐-함유 라디칼을 포함하는 메탈로센의 생산방법.
  24. 제23항에 있어서, 일반식(Ⅰ) 또는 (Ⅱ)의 이중 결합된 메탈로센의 생산 방법. (단, 일반식(Ⅰ)의 메탈로센은 유기 리간드로서 (시클로펜타디에닐) 및 ((시클로펜타디에닐)(인다닐)(디메틸)메탄)의 배합물을 갖는 샌드위치-결합된 메탈로센을 포함하지 않는다.)
    상기 식에서, 각각의 Z가 동일하거나 상이한 시클로펜타디에닐-함유 라디칼이고, R이 두 개의 Z라디칼을 연결하는 2가 유기 라디칼이며, x는 1 또는 0이며, R′은 연결된 Z와 Me를 분리시키는 4개의 원소만이 존재하며 이 원자들이 탄소원자인 방식으로 Z와 Me를 연결하는 2가 유기 라디칼이며, Me가 전이 금속이며, Q가 히드로카빌, 히드로카빌옥시 또는 할라이드이며, R″이 각각의 결합된 Z 및 Me을 분리하는 원자의 수가 2,3 또는 4개 이상이 되도록 하는, Z와 Me를 연결하는 2가 유기 라디칼이다.
  25. 제23항 또는 24항에 있어서, R″에 연결된 Z가 시클로펜타디에닐이고, 다른 하나의 Z는 플루오레닐이며, R은 디멜틸메틸렌이며, R″이 포화된 2가 에틸렌 라디칼이며, Me가 Zr이며, Q가 C1인 일반식(Ⅱ)의 메탈로센을 생산하는 방법.
  26. 제23항 또는 24항에 있어서, 메탈로센 (시클로펜타디에닐)(부타닐 시클로펜타디에닐)지르코늄(Ⅳ)클로라이드, ((플루오레닐)부타닐 시클로펜타디에닐)(디메틸)메탄)지르코늄(Ⅳ)클로라이드 또는 ((플루오레닐)(부타닐인데닐)디메틸 실란)지르코늄(Ⅳ)클로라이드를 생산하는 방법.
  27. 일반식(Ⅰ) 또는 (Ⅱ)의 이중 결합된 메탈로센(단, 일반식(Ⅰ)의 메탈 로센은 유기 리간드로서 (시클로펜타디에닐) 및 ((시클로펜타디에닐)(인다닐)(디메틸)메탄)의 배합물을 갖는 샌드위치-결합된 메탈로센을 포함하지 않는다.)
    상기 식에서, 각각의 Z는 동일하거나 상이한 시클로펜타디에닐-함유 라디칼이고, R은 두 개의 Z라디칼을 연결하는 2가 유기 라디칼이며, x는 1또는 0이며, R′은 연결된 Z와 Me를 분리시키는 4개의 원소만이 존재하고 이 원자들이 탄소원자인 방식으로 Z와 Me를 연결하는 2가 유기 라디칼이며, Me가 전이 금속이며, Q가 히드로카빌 또는 히드로카빌옥시이며, R″은 각각의 연결된 Z 및 Me을 분리하는 원자의 수가 2, 3 또는 4개 이상이 되도록 하는 Z와 Me를 연결하는 2가 유기 라디칼이다.
  28. 제27항에 있어서, (시클로펜타디에닐)(부타닐 시클로펜타디에닐)지르코늄(Ⅳ)클로라이드, ((플루오레닐)(부타닐 시클로펜타디에닐)(디메틸)메탄)지르코늄(Ⅳ) 클로라이드 또는 ((플루오레닐)(부타닐 인데닐)디메틸 실란)지르코늄(Ⅳ)클로라이드인 메탈로센.
  29. 제27항에 있어서, R″에 연결된 Z가 시클로펜타디에닐이고, 다른 하나의 Z는 플루오레닐이며, R은 디메틸메틸렌이며, R″이 포화된 2가 에틸렌 라디칼이며, Me가 Zr이며, Q가 C1인 일반식(Ⅱ)의 메탈로센.
    ※ 참고사항 : 최초출원 내용에 의하여 공개하는 것임.
KR1019960018505A 1995-05-30 1996-05-29 메탈로센의 제조 방법 및 이의 용도 KR960041190A (ko)

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