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KR950000722A - 메탈로센 및 그의 제조 방법 - Google Patents

메탈로센 및 그의 제조 방법 Download PDF

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Publication number
KR950000722A
KR950000722A KR1019940013126A KR19940013126A KR950000722A KR 950000722 A KR950000722 A KR 950000722A KR 1019940013126 A KR1019940013126 A KR 1019940013126A KR 19940013126 A KR19940013126 A KR 19940013126A KR 950000722 A KR950000722 A KR 950000722A
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South Korea
Prior art keywords
cyclopentadienyl
fluorenyl
compound
group
cyclopentadiene
Prior art date
Application number
KR1019940013126A
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English (en)
Other versions
KR100282461B1 (ko
Inventor
지이 알트 헬무트
파트시디스 콘스탄티노스
브루스 웰치 엠
엘 기어츠 롤프
파이퍼어 버언드
제이 파락칼 시리아크
아아르 화헤이 데릴
아아르 데크 해롤드
Original Assignee
제이 이이 휘립프스
휘립프스 피트로오리암 캄파니
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Priority claimed from US08/075,712 external-priority patent/US5399636A/en
Application filed by 제이 이이 휘립프스, 휘립프스 피트로오리암 캄파니 filed Critical 제이 이이 휘립프스
Publication of KR950000722A publication Critical patent/KR950000722A/ko
Application granted granted Critical
Publication of KR100282461B1 publication Critical patent/KR100282461B1/ko

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    • 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
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Abstract

활성 할로겐을 함유한 시클로펜타디엔-형 화합물을 표면 히드록실기를 갖는 무기 지지체와 접촉시키는 것으로 구성되는 지지된 시클로펜타디엔-형 화합물 형성 방법이 제공된다. 또한 지지된 시클로펜타디엔-형 화합물을 적합한 조건하에 전이 금속 화합물과 반응시키는 것으로 구성되는 지지된 메탈로센 제조 방법이 제공된다. 또한 말단 비닐기를 갖는 분지를 갖는 가교를 갖는 가교된 시클로펜타디엔-형 리간드 생성 방법이 제공된다. 또한 상기 리간드의 메탈로센이 제공된다. 또한 부가로 말단 활성 할로겐을 갖는 분지를 갖는 가교를 갖는 가교된 시클로펜타디엔-형 리간드 생성방법이 제공된다. 결과 얻어진 신규 리간드 및 그로부터 생성된 지지된 메탈로센이 또한 제공된다. 부가로 다른 효과를 갖는 적어도 두개의 메탈로센이 모두 표면 히드록시기를 갖는 무기 지지체에 결합된 지지된 메탈로센 촉매가 제공된다. 발병의 가교된 지지된 메탈로센을 사용하는 올레핀 중합이 결과 얻어진 중합 생성물과 더불어 또한 제공된다.

Description

메탈로센 및 그의 제조 방법
본 내용은 요부공개 건이므로 전문내용을 수록하지 않았음

Claims (27)

  1. 활성 할로겐을 갖는 시클로펜타디엔-형 화합물을 적합한 조건하에 표면히드록실기를 갖는 무기 지지체와 접촉시켜 활성 할로겐과 지지체상 히드록실기 간의 반응을 초래시킴으로써 시클로펜타디에닐-형기를 지지체에 화학적으로 결합시키는 것으로 구성되는 지지된 시클로펜타디엔-형 화합물 제조 방법.
  2. 제1항에 있어서,활성 할로겐을 갖는 적어도 두개의 다른 시클로펜타디에닐-형 화합물을 지지체와 반응시키는 방법.
  3. 제1항에 있어서, 상기 시클로펜타디엔-형 화합물이 비가교된 시클로펜타디엔-형 화합물인 방법.
  4. 제3항에 있어서, 상기 시클로펜타디엔-형 화합물의 일반식이 Z-Si(R)n-X3-n이고 식에서 n은 0-2 범위의 수이고, X는 할로겐이고, R은 알킬 또는 아릴기이고, Z는 치환 또는 비치환 시클로펜타디에닐, 인데닐, 또는 플루오레닐 라디칼인 시클로펜타디에닐-형인 방법.
  5. 제3항에 있어서, 상기 시클로펜타디에닐-형 화합물의 일반식이 Z-R'-Z이고, 식에서 각 Z는 같거나 다르고 치환 또는 비치환 시클로펜타디에닐, 인데닐, 또는 플루오레닐 라디칼이고, R'은 두개 Z 라디칼을 연결하고 활성 할로겐을 함유하는 가교인 방법.
  6. 제5항에 있어서, R'이 하기 일반식을 갖는 방법 :
    (식에서 R은 할라이드, 알킬라디칼 또는 아릴 라디칼이고, X는 할라이드이다.)
  7. 제5항에 있어서, R'이 하기 일반식의 분지를 갖는 방법.
    (식에서 X는 할라이드이고, 각각의 R은 같거나 다를 수 있고, 할라이드, 수소, 알킬 또는 아릴 라디칼이고, R″은 수소 또는 C1-10히드로카르빌기이고 R은 C1-10히드로카르빌기이다.)
  8. 제7항에 있어서, 각각의 R은 Cl인 방법.
  9. 제8항에 있어서, 두개의 Z가 분지된 메틸렌 라디칼에 결합된 방법.
  10. 제7항에 있어서, 각각의 R은 에틸 라디칼인 방법.
  11. 제7항에 있어서, 두개의 Z가 분지된 메틴 실릴 라디칼에 결합된 방법.
  12. 제7항에 있어서, 상기 시클로펜타디에닐-형 화합물은 2-(비스-9-플루오레닐메틸실릴)-1-트리클로로실릴에탄, 5-시클로펜타디에닐-5-(9-플루오레닐)-1-트리클로로실릴 헥산, 또는 1-클로로디메틸실릴-5-시클로펜타디에닐-5-(9-플루오레닐)헥산인 방법.
  13. 제1-12항중 임의의 한 항에 있어서, 염기성 유기 액체 존재하에 수행되는 방법.
  14. 제13항에 있어서, 상기 염기성 유기 액체가 피리딘으로 구성되는 방법.
  15. 제1항에 있어서, 상기 지지체가 본질적으로 실리카로 구성되는 방법.
  16. 디할로 올레핀 실란을 적합한 시클로펜타디엔-형 화합물의 알칼리 금속 염과 반응시켜 일반식 Z-R'-Z의 화합물(식에서 각각의 Z는 같음)을 생성하거나 또는 대안적으로 일반식 Z-R'-X의 화합물(식에서 X는 할로겐임)을 생성한 다음 다른 시클로펜타디엔-형 화합물의 알칼리 금속 염과 상기 화합물을 반응시켜 일반식 Z-R'-Z의 화합물(식에서 두개의 Z는 다르고 각각 시클로펜타디에닐-형 화합물로 구성되는 군으로부터 개별적으로 선택되고 R'은 디할로 올레핀 실란의 유기 잔기이다.)을 생성하는 것으로 구성되는 올레핀기를 함유한 분지를 갖는 가교된 시클로펜타디에닐-형 화합물 제조방법.
  17. 올레핀성 불포화 카르보닐 화합물을 피롤리딘 및 메탄올의 존재하에 시클로펜타디엔과 반응시켜 알케닐 풀벤을 얻고나서 상기를 시클로펜타디에닐-형 화합물의 알칼리 금속 염과 반응시켜 두개 시클로펜타디에닐-형기를 함유한 불포화-분지된 가교된 리간드를 얻는 것으로 구성되는 올레핀성 비닐기를 함유한 분지를 갖는 가교된 시클로펜타디에닐-형 화합물 제조방법.
  18. 제17항에 있어서, 5-헥센-2-온을 시클로펜타디에닐과 반응시켜 6-(3-부테닐)-6-메틸풀벤을 얻고나서 상기를 풀루오레닐리튬과 반응시킨 다음 가수분해시켜 5-시클로펜타디에닐-5-(9-플루오레닐)-1-헥센을 얻는 방법.
  19. 하기 일반식의 가교된 시클로펜타디에닐-형 화합물 :
    (식에서 n은 약 0-10 범위내 수이고, R은 Si, Ge, C 또는 Sn이고 ; R″은 수소, 또는 C1-10알킬기, 또는 C6-10아릴기로부터 선택된다.)
  20. 비스-9-플루오레닐메틸비닐실란.
  21. 5-시클로펜타디에닐-5-(9-플루오레닐)-1-헥센.
  22. 제19-21항중 임의의 한항에 따르거나 또는 제1-18항중 임의의 한항에 따른 방법에 의해 생성된 지지된 시클로펜타디에닐-형 생성물을 적합한 반응 조건하에 적합한 전이 금속 화합물과 반응시키는 것으로 구성된 메탈로센 생성 방법.
  23. (1) 적어도 두개의 산성이고, 치환가능한 수소를 갖는 일반식 ZH2의 탄화수소를 유기리튬 및 유기 할로실란과 접촉시켜 일반식 HZ-EXn+1의 리간드 선구체를 제조하고(식에서 적어도 하나의 X는 할로겐임) ; (2) 상기 리간드 선구체를 일반식 HZMa의 유기 알칼리 금속 화합물과 접촉시켜 일반식 ZH-EXn-ZH의 가교된 리간드를 형성하고(식에서 적어도 하나의 X는 할로겐임) ; (3) 상기 가교된 리간드를 무기물질 QH와 접촉시켜 무기 부분 Q에 화학적으로 결합된 가교된 리간드를 형성하고 ; 4) 무기 부분에 화학적으로 결합된 상기 가교된 리간드를 유기 리튬 및 일반식 MYm의 금속 할라이드와 접속시켜 상기 메탈로센을 제조하는 것으로 구성되고, 식에서, 각각의 Z는 시클로펜타디에닐, 인데닐, 테트라히드로 인데닐, 플루오네닐, 및 상기의 혼합물로 구성된 군으로부터 선택되는 같거나 다른 히드로카르빌 라디칼일 수 있고 ; 각각의 X는 같거나 다를 수 있고 수소, 불소, 염소, 브롬, 요오드, R, OR, NR2, PR2, 또는 OQ 및 상기 혼합물로 구성된 군으로부터 선택되고, 이때 R은 C1-20히드로카르빌 라디칼이고 Q는 실리카, 알루미나, 점토, 인산염화 알루미나, 및 상기의 혼합물로 구성된 군으로부터 선택되는 무기 부분이고 ; 각각의 Y는 같거나 다를 수 있고 알킬기, 수소, 불소, 염소, 브롬, 요오드, 및 상기의 혼합물로 구성된 군으로부터 선택되고 ; 각각의 E는 C, Sn, Si, Ge, B, Al, N, P, 및 상기의 혼합물로부터 선택되고 ; M은 Ti, Zr, Hf, Sc, Y, V, La 및 상기의 혼합물로 구성된 군으로부터 선택되는 금속이고 ; m은 금속 M의 나머지 원자가를 채우기에 충분한 수이고 ; Ma는 알칼리 금속이고 ; 및 n은 1 또는 2인 가교된 메탈로센 제조 방법.
  24. 제23항에 있어서, 실리카-0-1-시클로펜타디에닐-1-시클로펜타디에닐메틸실란 지르코늄 디클로라이드, 실리카-0-비스(9-플루오레닐)페닐실란 지르코늄 디클로라이드, 살리카-0-1-시클로펜타디에닐-9-플루오레닐메틸실란 하프늄 디클로라이드, 실리카-0-비스(9-플루오레닐)페닐실란 하프륨 디클로라이드, 실리카-0-1-시클로펜타디에닐-9-플루오레닐메틸실란 바나듐 디클로라이드, 실리카-0-1-시클로펜타디에닐-9-플루오레닐메틸실란 티타늄 디클로라이드, 실리카 0-비스(9-플루오레닐)페닐실란 티타늄 디클로라이드, 실리카-0-비스(2,8-디플루오로-9-플루오레닐)메틸실란 지르코늄 디클로라이드, 1-시클로펜타디에닐-9-플루오레닐에틸클로로실란 지르코늄 디클로라이드, 비스(9-플루오레닐)페닐클로로실란 지르코늄 디클로라이드, 1-시클로펜타디에닐-9-플루오레닐메틸클로로실란 하프늄 디클로라이드, 비스(9-플루오레닐)페닐클로로실란 하프늄 디클로라이드, 1-시클로펜타디에닐-9-플루오레닐메틸클로로실란 바나듐 디클로라이드, 비스(9-플루오레닐)페닐클로로실란 바나듐 디클로라이드, 2-시클로펜타디에닐-9-플루오레닐메틸클로로실란 티타늄 디클로라이드, 비스(9-플루오레닐)페닐클로로실란 티타늄 디클로라이드, 비스(2,8-디플루오로-9-플루오레닐)메틸클로로실란 지르코늄 디클로라이드 실리카-0-1-시클로펜타디에닐-9-플루오레닐메틸실란 지르코늄 디클로라이드, 알루미나-0-1-시클로펜타디에닐-9-플루오레닐메틸실란 지르코늄 디크로라이드, 벤토나이트-0-1-시클로펜타디에닐-9-플루오레닐메틸실란 지르코늄 디클로라이드, 및 상기의 혼합물로 구성된 군으로부터 선택되는 메탈로센을 생성하는 방법.
  25. 제23항에 있어서, 메탈로센 실리카-0-1-시클로펜타디에닐-9-플루오레닐메틸실란 지르코늄 디클로라이드를 생성하는 방법.
  26. 올레핀을 적합한 중합 조건하에 제22항에 따른 방법에 의해 생생된 지지된 메탈로센과 접촉시키는 것으로 구성된 올레핀 중합 방법.
  27. 제26항에 있어서, 상기 지지된 메탈로센이 올레핀 중합에 다른 효과를 주는 적어도 두개의 다른 메탈로센을 함유하는 방법.
    ※ 참고사항 : 최초출원 내용에 의하여 공개하는 것임.
KR1019940013126A 1993-06-11 1994-06-10 메탈로센 및 이의 제조 방법 KR100282461B1 (ko)

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