KR940000484A - 촉매계의 제조방법, 올레핀의 (공)중합법과 최소한 하나의 올레핀의 (공)중합체 - Google Patents

촉매계의 제조방법, 올레핀의 (공)중합법과 최소한 하나의 올레핀의 (공)중합체 Download PDF

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KR940000484A
KR940000484A KR1019930010095A KR930010095A KR940000484A KR 940000484 A KR940000484 A KR 940000484A KR 1019930010095 A KR1019930010095 A KR 1019930010095A KR 930010095 A KR930010095 A KR 930010095A KR 940000484 A KR940000484 A KR 940000484A
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neutral metallocene
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transition metal
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잔도나 니콜라
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피. 안토니
솔베이(소시에떼 아노님)
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Abstract

주기율표 ⅢB, ⅣB, VB와 ⅥB족에서 선택한 전이금속에서 유도된 할로겐화 중성 메탈로센과 유기알루디늄 화합물의 혼합물을 제조하고 이에 이온화제를 첨가하여서 하는 촉매계왹 제조방법.
상술한 할로겐화 중성 메탈로센과 유기알루미늄 화합물의 혼합물을 제조하고, 올레핀을 이 혼합물과 접촉시키고 이에 이온화제를 첨가하여서 하는 (공)중합법.

Description

촉매계의 제초방법, 올레핀의 (공)중합법과 최소한 하나의 올레핀의 (공)충합체
본 내용은 요부공개 건이므로 전문내용을 수록하지 않았음

Claims (30)

  1. 일반식 AITT'T" (여기서 T', T'와 T"는 각각 임의로 산소를 함유할 수 있는 탄화수소를 나타낸다)의 최소한 하나의 유기알루미늄 화합물, 전이금속에서 유도된 최소한 하나의 중성메탈로센과 최소한 하나의 이온화제를 사용하여서 하는 촉매계의 제조방법에 있어서, 중성 메탈로선을 일반식 (CP)a(CP')bMXxZz의 화합물에서 선택하고, 이 식에서 -Cp는 중김원자터에 배위결합된 불포촤 탄화수소기를 나타내고, -Cp'는 중심원자M에 배위결합된 불포화 탄화수소기, 또는 주기율표 VA와 71A족에서 선택한 원소에서 유도된 기를 나타네고, CP와 Cp'기는 같거나다르며, 공유결할 7리를통하여 결합될 수 있고,-M는 주기율표 lIIB,7B, VB와7B족에서 선택한 전이금속을 나타내며, -a, b, x와 B는 (a+b+x+z)=m, x≥1, z≥0및 a와/또는 b≠0이 되는 정수를 나타내고, -m는 전이금속 M의 원자가를 나타내고, -x는 할로겐이고, -z는 임의로 산소를 함유할 수 있는 탄화수소기 또는 일반식 (-Rt-5-R'R"R'")의 실일기를 나타내며, -상기 식에서 R은 임의로 치환되는 알킬, 알켄일, 아릴. 알콕시 또는 시클로알킬기를 나타내고, -R'. R"와 R'"는 같거나 다르고 각 기는 할로겐 또는 임의로 치환되는 알킬, 알켄일, 아린, 알콕시 또는 시클로알킬기를 나타내며, -t는 0또는 1이다.
    첫단계에서 유기알루띠늄 화합물과 중성메탈로센의 혼합물을 최소한 하나의 탄화수소 희석제에서 제조하고, 둘째단계에서 이에 이온화제를 첨가함을 특징으로 하는 상기 제조방법.
  2. 제1항에 있어서, 불포화 탄화수소기를 임의로 치환되는 시클로펜타디엔일, 인덴일 또는 플루오렌일에서 선택함을 특징으로 하는 제조방법.
  3. 제1항 또는 제2항에 있어서, 전이금속이 지르코늄임을 특징으로 하는 제조방법.
  4. 제1항 또는 제3긍 중 어느 한 항에 있어서, 중성메탈로센을 방항족 탄화수소의 응액형태로 사용함을 특징으로 하는 제조방법.
  5. 제1항 내지 제4항 중 어느 한 항에 있어서, 이온화제를 방향족 탄화수소의 용액형태로 사용함을 특징으로 하는 제조방법.
  6. 제4항 또는 제5항에 있어서, 방향족 탄화수소가 톨루엔임을 특징으로 하는 제조방법.
  7. 제1항 군지 제6항 중 어느 한 항에 있어서, 유기알루미늄화합물, 중성메탈로센과 이온화제를, 이온화제와 중성메탈로센의 몰비가 0.1-10이고 유기알루미늄화합물과 중성메탈로센의 몰비가 10이상인 양으로 사용함을 특징으로 하는 제조방법.
  8. 제1항 내지 제7항 중 어느 한 항에 있어서, 이온화제를 르리페닐카르베늄테트라키스(펜타플루오로페닐)보레이트와 트리 (필타플루오로페닐)보란에서 선택함을 특징으로 하는 제조방법.
  9. 제 1항 내지 제8항 중 어느 한 항에 있어서, 유기 알루미늄 화합물을 트리에 틸알루미늄과 트리 이소부틸알루미늄에서 선택함을 특징으로 하는 제조방법.
  10. 제1항 내지 제9항 중 어느 한 항에 있어서, z가 0이외의 것이고 z가 일반식 (-Rt-SiR'R"R'")의 실일기인 경우에, 중성 메탈로센을 일반식 (Cp)a(Cp')bMXxHz의 화합물과 실란을 반응시켜서 제조함을 특징으로 하는 제조방법.
  11. 제10항에 있어서, 실란을 67개 이하의 탄소원자를 함유하는 비할로겐화 알켄일실란에서 선택함을 특징으로 하는 제조방법.
  12. 제11항에 있어서, 실린이 비닐(트리메톡시)실란임을 특징으로 하는 제조방법.
  13. 제1항 내지 제9항 중 어느 한 항에 있어서, z이 0이외의 것이고 B가 탄화수소기인 경우에, 중성 메탈로센을 일반식 (Cp)a(Cp')bMXxHz와 올레핀을 반응시켜서 제조함을 특징으로 하는 제조방법.
  14. 제13항에 있어서, 올레핀이 에딜렌임을 특징으로 하는 제조방법.
  15. 제1항 내지 제14항 중 어느 한 항에 있어서, 중성 메탈로센 과/또는 이온화제를 지지체상에 석출시킴을 특징으로 하는 제조방법.
  16. 제15항에 있어서, 지지체를 알룸옥산용액으로 처리함을 특징으로 하는 제조방법.
  17. 제15항 또는 제16항에 있어서, 지지체를 무기지지테에서 선택함을 특징으로 하는 제조방법.
  18. 제17항에 있어서, 지지테를 실리카, 알루미나와 염화마그네슘엑서 선택함을 특징으로 하는 제조방법.
  19. 일반식 AITT'T" (여기서 T, T'와 T"는 각각 임의로 산소를 함유할 수 있는 탄화수소를 나타낸다)의 최소한 하나의 유기알루미늄 화합물, 전이금속에서 유도된 최소한 하나의 기온화제를 함유하는 촉매계의 존재하의 최소한 하나의 올레핀의 (공)중합법에 있어서, 중성 메탈로센을 일반식 (Cp)a(Cp')bMXxHz의 화합물에서 선택하고, 이 식에서 -Cp는 중심원자M에 배위결합된 불포화 탄화수소기를 나타내고, -CP'는 중심원자M에 배위결합된 불포화 탄화수소기, 또는 주기율표 VA와 ⅥA족에서 선택한 원소에서 유도된 기를 나타내고, CP와 Cp'기는 같거나 다르며, 공유결합 다리를 통하여 결합될 수 있고, -M는 주기율표 ⅢB, ⅣB, ⅤB와 ⅥB족에서 선택한 전이금속을 나타내며, -a b, x와 z근 (a+b+x+z)=m, x≥1, z≥0및 a와,/또는 6≠0이 되는 정수를 나타내고,-m는 전이금속 M의 원자간를 나타내고, -x는 할로겐이고, -z는 임의로 산소를 함유할 수 있는 탄화수소기 또는 일반식 (-Rt-5-R'R"R'")의 실일기를 나타내며, -상기 식에서 R은 임의로 치환되는 알킬, 알컨일, 아린, 알콕시 또는 시클로알킬기를 나타내고, -t는 0 또는 1이다. 유기알루미늄 화합물과 중성메탈로센의 혼합물을 최소한 하나의 탄화수소 희석제에서 제조하고, 올레핀을 이 혼합물과 접촉시키고, 이에 이온화제를 첨가함을 특징으로 하는 상기 (공)중합법.
  20. 제19항에 있어서, 탄화수소 희석제를 지방족 탄화수소에서 선택함을 특징으로 하는 (공)중합법.
  21. 제19항 또는 제20항에 있어서, 유기알루미늄 화합물과 중성메탈로센을 유기알루디늄 화합물과 중성메탈로센의 몰비가 100이상이 되는 양으로 사용함을 특징으로 하는 (공)중합법.
  22. 제19항 내지 제21항 중 어느 한 항에 있어서, 중성 메달로센 과/또는 이온화재를 지지체상에 석출시킴을 특징으로 하는 (공)중합법.
  23. 제22항에 있어서, 지지체를 알룸옥산 용액으로 처리함을 특징으로 하는 (공)중합법.
  24. 제22항 또는 제23항에 있어서, 지지체를 무기지지체에서 선택함을 특징으로 하는 j공!중합법.
  25. 제24항에 딨어서, 지지체를 실리카 알루미나와 염화마그네슘에서 선택함을 특징으로 하는 (공)중합법.
  26. 제19항 내지 제25항 중 어느 한 항엑 있어서, z가 0이외의 것이고 z가 일반식 (-Rt-5-R'R"R"')의 실일기인 경우, 중성 메탈로센을 일반식 (Cp)a(Cp')bMXxHz의 화합뭍과 실란을 반응시켜서 제조함을 특징으로 하는 (공)중합법.
  27. 제26항에 있어서, 실란을 60개 이하의 탄소원자를 갖는 비할로겐화 알켄일실란에서 선택함을 특징으로 하는 (공)중합법.
  28. 제27항에 있어서, 실란이 비닐(트리메톡시)실란띰을 특징으로 하는 (공)중합법.
  29. 제19항 내지 제25항에 있어서, z가 0이외의 것이고 z가 탄화수소긴인 경우에, 중성 메탈로센을 일반식 (Cp)a(Cp')bMXXHZ의 화합물과 올레핀을 반응시켜서 제조함을 특징으로 하는(공)중합법.
  30. 0.5중량% 이하의 올리곰 함량, 2-10의 Mw/Mn 비을의 분자량 분포와 5중량 Prm이하의 전이금속 함량을 갖는 최소한 하나의 올레핀의 (공)중합체.
    ※ 참고사항 : 최초출원 내용에 의하여 공개하는 것임.
KR1019930010095A 1992-06-05 1993-06-04 촉매계의 제조방법, 올레핀의 (공)중합법과 최소한 하나의 올레핀의 (공)중합체 KR100282561B1 (ko)

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US5612271A (en) 1997-03-18
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RU2117677C1 (ru) 1998-08-20
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JPH0632830A (ja) 1994-02-08
TW286321B (ko) 1996-09-21
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