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KR890700612A - 촉매, 이의 제조방법 및 이의 사용방법 - Google Patents

촉매, 이의 제조방법 및 이의 사용방법

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KR890700612A
KR890700612A KR1019880701205A KR880701205A KR890700612A KR 890700612 A KR890700612 A KR 890700612A KR 1019880701205 A KR1019880701205 A KR 1019880701205A KR 880701205 A KR880701205 A KR 880701205A KR 890700612 A KR890700612 A KR 890700612A
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윌리암 터너 하워드
죠오지 흘랫키 그레고리
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존 제이. 마혼
엑손 케미칼 패턴츠, 인코포레이티드
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Abstract

내용 없음.

Description

촉매, 이의 제조방법 및 이의 사용방법
본 내용은 요부공개 건이므로 전문내용을 수록하지 않았음

Claims (18)

  1. (a) 적절한 용매 또는 희석제 중에서, 양성자와 반응할 수 있는 적어도 하나의 치환체를 함유한 비스(사이클로-펜타디에닐)금속 화합물[여기에서, 금속은 티탄, 지르코늄 및 하프늄으로 이루어진 군중에서 선택된다]로 구성된 제1화합물 하나 이상과, 양성자를 제공할 수 있는 양이온 및 전하를 띤 중심 금속 또는 준금속 원자를 보호하며 이 금속 원자에 공유적으로 배위결합된 다수의 친유성 라디칼을 포함하는 단일 배위 착화합물인 음이온[이는 부피가 크며 불안정하고 두화합물 간의 반응으로 형성된 금속 양이온을 안정화시킬 수 있다]을 포함하는 제 2화합물 하나 이상을 결합시키고: (b) 상기 단계 (a)의 접촉반응을 충분한 시간동안 유지시켜, 언급한 제2화합물의 양이온에 의해 제공된 양성자가 언급한 비스(사이클로펜타디에닐) 금속 화합물에 함유된 언급된 치환체와 반응되도록 하며: (c) 상기 단계 (b)로부터, 활성촉매를 직접적인 생성물로 또는 하나이상의 직접적인 생성물의 분해 산물로서 회수하는 단계를 포함하여, 촉매를 제조하는 방법.
  2. 제l항에 있어서, 언급한 비스(사이클로펜타디에닐)금속 화합물을 하기 일반식으로 나타낼 수 있는 방법.
    상기식에서, M은 티탄, 지르코늄 및 하프늄으로 구성된 군으로 부터 선택된 금속이고: (A-Cp)는 (Cp)(Cp*) 또는 Cp-A'-Cp*이고, Cp 빛 Cp*는 같거나 다르며, 치환되거나 비치환된 사이클로펜타디에닐 라디칼이고, A'는 공유 가교 그룹이며: L은 올FP핀, 디올레핀 또는 아린 리간드이며; X1과 X2는 독립적으로 하이드라이드 라디칼, 하이드로카빌 라디칼, 치환된-하이드로카빌 라디칼, 유기준금속 라디칼 등으로 이루어진 군중에서 선택되고: X'1와 X'2가 함께 금속원자에 결합되어 메탈라사이클을 형성하며. 여기에서 금속원자, X'1및 X'2는 탄소수 약3 내지 약20개의 하이드로카보사이클릭 환을 형성하고; R은 사이클로펜타디에닐 라칼 중 한 라디칼상에 존재하는 치환체이머, 금속원자에 또한 결합된다.
  3. 제1항 또는 2항에 있어서, 언급한 제2화합물을 하기 일반식으로 나타낼 수 있는 방법.
    상기식에서 L'는 중성 루이스 염기이고: H은 수소원자이며; [L'-H]는 브론스테드산이고; M'는 원소주 기율표상의 V-B즉 내지 V-A족, 즉V-B, VI-B, VII-B. VIII,I-B, II-B. III-A, IV-A 및 V-A 족으로 구성된 군중에서 선택된 금속 또는 준금속이며; Q1 내지 Qn은 독립적으로 하이드라이드 라디칼, 디알킬 아미도 라디칼, 알콕사이드 및 아릴옥사이드 라디칼, 하이드로카빌 및 치환된 하이드로카빌 라디칼, 및유기준금속 라디칼로 이루어진 군중에서 신택되고, Q1내지 Qn중의 어느하나는 하랄이드 라디칼일 수 있고,나머지 Q1내지 Qn은 독립적으로 상기 언급한 라디칼들 중에서 선택되며: m는 l 내지 7의 정수이고: n은2 내지 8의 정수이며: n-m은 d이다.
  4. 제1항 내지 3항중의 어느 한항에 있어서, 언급한 제2 화합물을 다음 일반식으로 나타낼 수 있는 방법.
    상기식에서, L'는 중성 루이스 염기이고 ∵ H는 수소원자이며: [L'-H]+는 부론스스테드산이고: B는 원자가 3의 붕소이며; Ar1및 Ar2는 같거나 다른 방향족 또는 치환된 방향족 탄화수소 라디칼이고, 이 라디칼들은 안정한 가교그룹에 의해 서로 연결될 수 있으며: X3및 X4는 독립적으로 하이드라이드 라디칼, 할라이드 라디칼, 하이드로카빌 및 치환된 하이드로카빌 라디칼, 및 유기준금속 라디칼 등으로 이루어진 군중에서 선택된다.
  5. 제1항 내지 4항중 어느 한항에 있어서, 제1화합물이 제 2항에서 도시한 일반식 1의 구조를 가지며, 언급한 제2화합물은 비치환 되거나 방향족 붕소화합물의 삼치환원 암모늄 염이고, 이때 언급한 제l화합물은 임의로, 치환되거나 비치환원 사이클로펜타디에닐 라디칼 2개 및 저급 알켈치환체 2개 또는 하이드라이드 2개를 함유한 비스(사이클로펜타디에닐)금속 화합물(여기에서, 금속은 바람직하게 지르코늄 또는 하프늄이다)인 방법.
  6. 제5항에 있어서, 언급한 제2화합물이 트리(n-부틸)암모늄 테트라(페닐)붕소이고, 이 경우에 바람직하게 언급한 제1화합물은 비스(펜타메틸사이클로펜타디에닐)지르코늄 디메틸이거나: 언급한 제2화합물이 N,N-디메틸아닐리늄 테트라(페닐)붕소이고, 이 경우에 언급한 제1화합물은 바람직하게 비스[1,3-비스(트리메틸실릴)사이클로펜타디에닐]지르코늄 디메틸인 방법.
  7. 제5항에 있어서, 언급한 제2 화합물이 트리(n-부틸)암노튬 테트라(p-톨릴)붕소, 트리(n-부틸)암모늄 테트라 (p-톨릴)붕소, 트리(n-부틸)암모늄 테트라(p-톨릴)붕소, 트리(n-부틸)암모늄 테트라(m-디메틸페닐)붕소 및 트리(n-부틸)암모늄 테트라(o,m-디메틸페닐)붕소로 이루어진 군중에서 선택되며, 이 경우에 언급한 제1화합물은 바람직하게 비스(펜타메틸사이클로펜타디에닐)지르코늄 디메틸이거나: 언급한 제2화합물이 트리(n-부틸)암모늄 데트라(p-톨릴)붕소 및 트리(n-부틸)암모늄 데트라(p-에틸페닐)붕소로 이루어진 군중에서 선택되며, 이 경우에 언급한 제1화합물은 바람직하게 비스(펜타메틸사이클로펜타디에닐)지르코늄 디메틸 및(펜타메틸사이클로펜타디에닐)(사이클로펜타디에닐)지르코늄늠 디메틸로 이루어진 군중에서 선택되거나: 또는 언급한 제2화합물이 트리(n-부틸)암모늄테트라(펜타플루오로페닐)붕소 및 N, N-디에틸아닐리늄 테트라(펜타플루오로페닐)붕소로 이루어진 군중에서 선택된 방법.
  8. 제1항 내지 4항중의 어느 한항에 있어서, 제1화합물이 제2항에 도시한 일반식 2의 구조를 가지며, 언급한 제2화합물은 테트라(치환된 방향족)붕소 화합물의 삼치환원 암모늄 염, 바랍직하게는 N,N-디메틸아닐리늄 테트라(펜타플루오로페닐)붕소이고, 이 경우에 언급한 제1화합물은 바람직하게는 1-비스(사이클로펜타디에닐)티타나-3-디메틸실라사이클로부탄, 1-비스(사이클로펜타디에닐)지르코나-3-디메틸실라사이클로부탄 및 1-비스(사이클로펜타디에틸)하프나-3-디메틸실라사이클로부탄으로 이루어진 군중에서 선택된 방법.
  9. 제1항 내지 4항중 어느 한항에 있어서, 제 1화합물이 제2항에 도시한 일반식 3의 구조를 가지며, 언급한 제2화합물이 테트라(치환된 방향족)붕소 화합물의 삼치환원 암모늄 염, 바람직하게는 트리(n-부틸)암모늄 테트라(펜타플루오로페닐)붕소이고, 이경우에 언급한 제1화합물을 바람직하게 비스(사이클로펜타디에닐)지르코늄(2,3-디메틸-1,3-부타디엔) 및 비스(사이클로펜타디에닐)하프늄(2,3-디메틸-1,3-부타디엔)으로 이루어진 군중에서 선택된 방법.
  10. 제l항 내지 4항중의 어느 한항에 있어서, 제1화합물이 제2항에 도시한 일반식 4의 구조를 가지며, 언급한 제2화합물이 테트라(치환원 방향족)붕소 화합물의 삼치환원 암모늄 염이고, 여기에서 언급한 제1화합물은(펜타메틸사아클로펜타디에닐)(테트라메틸사이클로펜타디에닐메틸렌)지르코늄 페닐 및 (펜타메틸사이클로펜타디에닐)(테트라메틸사이클로펜타디에닐에틸렌)하프늄 벤질로 이루어진 군중에서 선택되며, 이경우에 언급한 제2화합물은 바람직하게 트리(n-부틸)암모늄 테트라(펜타플루오로페닐)붕소 또는 N,N-디메틸아닐리늄 테트라(페닐)붕소 화합물인 방법.
  11. (a) 탄소원자 2 내지 약18개를 함유하는 ≠-올레핀, 디올레핀 및/또는 아세틸렌형 불포화 단량체를 단독으로 또는 이들을 함께 또는 다른 단량체와 함께 직절한 담체, 용매 또는 희석제 중에서 상기 제1항 내지 l0항 중의 어느 한항에 따른 방법에 의해 미리 제조하였거나 중합시에 동일장소에서 제조원 촉매와 접촉시키며: (b) 상기 단계(a)의 접촉반응을 충분한 시간동안 계속하여 상기 단량체 또는 단량체들의 적어도 일부를 중합시키고: (c) 중합체 생성물을 회수하는 단계를 포함하여, 탄소원자 2 내지 약18개를 갖는 ≠-올레핀. 디올레핀 및/또는 아세틸렌형 불포화 단량체를 단독으로 또는 이들을 함께 또는 다른 단량체와 함께 중합시키는 방법.
  12. 제1항 내지 10항 중의 어느 한항에 따른 방법으로 제조한 촉매.
  13. 제12항에 따른 촉매에 의해 제조되며, ≠-올레핀, 디올레핀, 아세틸렌형 불포화 단량체 및 이들의 혼합물로 이루어진 군중에서 선택된 단량체를 포함하는 중합체.
  14. 다음 일반식 유기금속 화합물을 함유한 조성물:
    상기식에서 Cp*는 퍼알킬-치환된 사이클로펜타디에닐 라디칼이며, 여기에서 언급한 알킬 치환체는 각각 같거나 다른 C1내지 C20알킬 라디칼일 수 있고: B는 붕소이며: Zr온 지르코늄이고: Ph'는 페닐 또는 알킬치환된 페닐 라디칼이며, 3개의 Ph'는 각각 같거나 또는 다를수 있고 알킬 치환체들은 탄소원자 1 내지 14개를 함유할 수 있고: R은 수소이거나 탄소수 1 내지 약14의 알킬 그룹이다.
  15. 제14항에 있어서. 일반식
    (여기에서, Cp*는(펜타메틸사이클로펜타디에닐)라디칼이다):
    (여기에서, Cp*는(펜타메틸사이클로펜타디에닐)라디칼이다):
    (여기에서, Cp*는 (펜타메틸사이클로펜타디에닐)라디칼이다): 또는
    (여기에서, Cp*는(에틸테트라메틸사이클로펜타디에닐)라디칼이다)의 유기금속물을 함유한 조성물.
  16. 조성물로서의 하기 일반식1 또는 2로 표시되는 유기금속 화합물.
    상기식에서, M은 티탄, 지르코늄 및 하프늄으도 이루이진 군중에서 선택된 금속이고: (A-Cp)는 (Cp)(Cp*) 또는 Cp-A'-Cp*이며, Cp 및 Cp*는 같거나 다른, 치환되거나 비치환된 사이클로펜타디에닐 라디칼이고, A'는 공유 가교 그룹이며: X1은 하이드라이드라디칼, 하이드로카빌라디칼, 치환된 하이드로카빌라디칼, 유기준금속 라디칼 등으로 이루어진 군중에서 선택되고: L'는 중성 루이스 염기이며 . M'는 윈소주기율표상의 V-B 내지 VI-A족, 즉 V-B, VI-B, VII-B, VIII, I-B. II-B, III-A, IV-A 및 V-A족으로 구성된 군으로 부터 선택된 금속 또는 준금속이고: Q1내지 Qn은 각각 독립적으로 하이브라이드 라디칼, 디알킬아미도 라디칼, 알콕사이드 및 아릴옥사이드 라디칼, 하이드로카빌 및 치환된 하이드로카빌 라디칼, 및 유기준금속 라디칼로 구성원 군중에서 선택되며, Q1내지 Qn중의 어느하나는 할라이드 라디칼일 수 있고 나머지 Q1내지 Qn은 독립적으로 언급한 라디칼들 중에서 선택되고; m은 1 내지 7의 정수이며: n은 2 내지 8 의 정수이고: n-m은 d이다.
  17. 제16항에 있어서, 언급한 음이온을 하기 일반식으로 나타낼 수 있는 조성물:
    상기식에서, B는 원작 3의 붕소이고: Ar1및 Ar2는 같거나 다른 방향족 또는 치환된-방향족 탄화수소 라디칼이며, 이들 라디칼들은 안정한 가교 그룹에 의해 서로서로 연결될 수 있고: X3와 X4는 독립적으로 하이드라이드 라디칼, 할라이드 라디칼, 하이드로카빌 및 치환된 하이드로카빌 라디칼, 유기준금속 라디칼 등으로 이루진 군중에서 선택된다.
  18. 제17항에 있어서, 언급한 음이온이 비치환된 테트라(방향족)붕소 음이온 및 치환된 방향족)붕소 음이온으로 이루어진 군증에서 선택원 조성물.
    ※ 참고사항 : 최초출원 내용에 의하여 공개하는 것임.
KR1019880701205A 1987-01-30 1988-01-27 촉매 및 이 촉매를 사용한 중합방법 KR960015192B1 (ko)

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