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KR960705626A - 에틸렌의 중합 및 공중합에 사용하기 위한 촉매 조성물(catalyst composition for use in the polymerization and copolymerization of ethylene) - Google Patents

에틸렌의 중합 및 공중합에 사용하기 위한 촉매 조성물(catalyst composition for use in the polymerization and copolymerization of ethylene) Download PDF

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KR960705626A
KR960705626A KR1019960702431A KR19960702431A KR960705626A KR 960705626 A KR960705626 A KR 960705626A KR 1019960702431 A KR1019960702431 A KR 1019960702431A KR 19960702431 A KR19960702431 A KR 19960702431A KR 960705626 A KR960705626 A KR 960705626A
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catalyst composition
ethylene
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transition metal
alkyl
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KR1019960702431A
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KR100355623B1 (ko
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입-콰이 로 프레데릭
에드워드 나우린 토마스
데니스 슈레겐버거 샌드라
팬듀랭 쉬로드카 프래딮
온키 치엔 그레이스
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데니스 피. 산티니
모빌 오일 코오포레이숀
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Abstract

본 발명은 지지체상에 2개의 전이 금속 성분을 갖는, 이중 하나의 성분은 메탈로센 형태인 에틸렌 중합 촉매에 관한 것으로서, 상기 지지체는 (i) 마그네슘 알킬이 혼입된 실라놀-함유 실리카와 (ii) 알코올을 반응시킴으로써 제로되는 무수성 물질이다. 상기 촉매는 또한 비-메탈로센 전이 금속 화합물도 포함하며, 단일 반응기내에서, 2가지 형태의 분자량 분포를 갖는 에틸렌 공중합체를 생성시킨다.

Description

에틸렌의 중합 및 공중합에 사용하기 위한 촉매 조성물 (CATALYST COMPOSITION FOR USE IN THE POLYMERIZATION AND COPOLYMERIZATION OF ETHYLENE)
본 내용은 요부공개 건이므로 전문내용을 수록하지 않았음
제4도는 기체상 중합 (및 공중합을 위한) 유체층 반응기의 개략도이다.

Claims (16)

  1. (a) 알루미늄 알킬 비-산소 함유 활성화제; 및 (b) 상기 알루미늄 알킬 활성화제에 의해 활성화되는 전이 금속 및 비-메탈로센전이 금속의 활성화된 메탈로센 화합물을 포함하는 조성물을 함유하는 고형의 무수성 지지체를 포함하고, 상기 지지체는, (1) RmMgR′n(식 중 Rm및 Rn은 C1-12의 알킬기이며, m 및 n은 각각 0.1 또는 2이되, 단, m＋n은 Mg의 원자가와 같고, RmMgR′n은 이것과 OH간의 물비가 0.5 : 1 내지 4 : 1이 되도록 하는 양으로 존재함)이 혼입된, OH 기를 갖는 실리카와; (2) 일반식 R″O-(식 중, R″는 C1-12의 알킬기임)를 가지며 상기 RmMgR′n중의 Rm및 R′n을 치환시키는데 효과적인 알콕시기를 제공하고, 알코올 대 Mg의 볼비가 0.5 내지 2.0이 되도록 하기에 효과적인 양으로 사용되는 유기 알코올 시약의 반응 생성물인, 고밀도 및 선형 저밀도의 2가지 형태의 분자량 분포를 갖는 에틸렌 중합체 및 공중합체를 제조하는데 사용하기 위한 촉매 조성물.
  2. 제1항에 있어서, 상기 각각의 Rm및 R′n이 C4-10알킬기인 촉매 조성물.
  3. 제2항에 있어서, 상기 각각의 Rm및 R′n이 부틸기인 촉매 조성물.
  4. 제2항에 있어서, 상기 각각의 Rm및 R′n이 n－부틸인 촉매 조성물.
  5. 제1항 내지 제4항 중 어느 한 항에 있어서, 상기 R″가 C1-8알킬기인 촉매 조성물.
  6. 제1항 내지 제5항중 어느 한 항에 있어서, 상기 R″O－가 알코올로서 제공되는 촉매 조성물.
  7. 제1항 내지 제6항중 어느 한 항에 있어서, 상기 반응 생성물이, (i) －OH기를 갖는 고형의 다공성 실리카와 비극성 용매로 이루어진 슬러리를 제공하는 단계; (ii) 상기 실리카에 상기 비극성 용매에 가용성인 상기 RmMgR′n을 혼입시켜 중간체(ii)를 형성시키는 단계(이때, 상기 Mg : －OH기는 2 이하임); 및 (iii) 상기 단계(ii)의 중간체를 R″OH : RmMgR′n의 몰비가 0.5 내지 2.0이 되도록 하기에 효과적인 양의 상기 R″OH로 처리하는 단계에 의해 형성되는 촉매 조성물.
  8. 제7항에 있어서, 상기 단계(iii) 후에, (iv) 상기 단계(iii)의 생성물을 TiCl4로 처리하여 티타늄－함유 중간체를 형성시키는 단계; 및 (v) 상기 티타늄－함유 중간체를 상기 활성화제와 결합시키는 단계를 추가로 포함하는 촉매 조성물.
  9. 제1항 내지 제8항 중 어느 한 항에 있어서, 상기 비-메탈로센 전이 금속이 티타늄인 촉매 조성물.
  10. 제9항에 있어서, 상기 비-메탈로센 전이 금속이 티타늄 테트라클로라이드인 촉매 조성물.
  11. 제1항 내지 제10항 중 어느 한 항에 있어서, 상기 활성화제가 트리메틸알루미늄인 촉매 조성물.
  12. 제1항 내지 제11항 중 어느 한 항에 있어서, 상기 메탈로센 전이 금속이 하기 일반식을 갖는 화합물로서 제공되는 촉매 조성물 :
    CpxMAyBz
    상기 식중에서, Cp는 비치환 또는 C1-6의 알킬 또는 알킬렌에 의해 치환되는 시클로펜타디에닐이고, x는 1 이상이며, 각각의 A 및 B는 할로겐 또는 C1-8의 알킬이고, y＋z는 3 이하이되, 단, x＋y＋z는 M의 원자가와 같아야 하며, M은 티타늄 지르코늄 또는 하프늄으로 구성되는 군에서 선택된다.
  13. 제12항에 있어서, 상기 메탈로센 화합물이 비스-(시클로펜타디에닐) 지르코늄 디클로라이드 및 비스-(n-부틸시클로펜타디에닐) 지르코늄 디클로라이드로 구성되는 군에서 선택되는 촉매 조성물.
  14. 제1항 내지 제13항 중 어느 한 항에 있어서, 상기 메틸로센 화합물이 메틸알루목산 용액에 의해 활성화되고, 상기 실리카는 기공용적이 1.0 내지 4.0㎤/g이며, 상기 용액은 부피가 상기 기공의 전체 용적과 동일한 촉매 조성물.
  15. 단일 반응기내에서, 제1항 내지 제14항 중 어느 한 항에 의해 촉매 존해하에 에틸렌을 중합시켜, 고밀도 및 선형 저밀도의 2가지 형태의 분자량 분포를 갖는 에킬렌 중합체를 형성시키는 것을 포함하는, 고밀도 및 선형 저밀도의 2가지 형태의 분자량 분포를 갖는 상기 에틸렌 중합체 및 공중합체를 제조 방법.
  16. 제15항에 있어서, 상기 에틸렌을 C3-8알파 올레핀과 공중합시켜, 고밀도 및 선형 저밀도의 2가지 형태의 분자량 분포를 갖는 상기 에틸렌 공중합체를 형성시키는 방법.
    ※ 참고사항 : 최초출원 내용에 의하여 공개하는 것임.
KR1019960702431A 1993-11-15 1994-11-15 촉매조성물을사용한에틸렌중합체및공중합체의제조방법 KR100355623B1 (ko)

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