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KR940011493A - α-올레핀 중합체의 제조방법 - Google Patents

α-올레핀 중합체의 제조방법 Download PDF

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KR940011493A
KR940011493A KR1019930023802A KR930023802A KR940011493A KR 940011493 A KR940011493 A KR 940011493A KR 1019930023802 A KR1019930023802 A KR 1019930023802A KR 930023802 A KR930023802 A KR 930023802A KR 940011493 A KR940011493 A KR 940011493A
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도시히코 스가노
다카시 후지타
가즈요 기타가와
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요시다 마사키
미츠비시 유카 가부시키가이샤
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Abstract

성분(ⅱ) 및 (ⅲ)이 성분(ⅰ)에 지지되도록 함으로써 얻어진 고체촉매가 촉매인 것을 특징으로 하는 α-올레핀을 촉매의 존재하에 중합하는 α-올레핀 중합체의 제조방법.
성분(ⅰ)은 5 내지 1,O00㎛의 평균입경을 갖는 유기 다공성 중합체인데, 여기서 직경이 0.006 내지 10㎛인 모든 기공들의 총 기공부피는 0.3cc/g이상이며 직경이 0.05 내지 2㎛인 모든 기공들의 총 기공부피는 직경이 0.006 내지 10㎛인 모든 기공들의 총 기공부피의 50% 이상이며, 성분(ⅱ)는 구조

Description

α-올레핀 중합체의 제조방법
본 내용은 요부공개 건이므로 전문내용을 수록하지 않았음

Claims (21)

  1. α-올레핀을 중합시키기 위해 촉매와 접촉시키는 α-올레핀 중합체의 제조방법에 있어서, 성분(ⅰ)상에 지지된 성분(ⅱ) 및 (ⅲ)으로 이루어지는 고체촉매를 촉매로서 사용하는 것으로 이루어지며, 성분(ⅰ)은 5 내지 1,000㎛의 평균입경을 갖는 유기 다공성 중합체인데, 여기서 직경이 0.006 내지 10㎛인 모든 기공들의 총 기공부피는 0.3cc/g이상이며 직경이 0.05 내지 2㎛인 모든 기공들의 총 기공부피는 직경이 0.006 내지 10㎛인 모든 기공들의 총 기공부피의 50% 이상이며, 성분(ⅱ)는 구조(여기서 R은 1 내지 10 탄소원자를 갖는 탄화 수소기이다)를 갖는 화합물이며, 성분(ⅲ)은 적어도 하나의 콘주게이트된 5-원환 리간드를 갖는 주기율표에서 ⅣB 내지 ⅥB족의 천이금속의 화합물인 것을 특징으로 하는 제조방법.
  2. 제1항에 있어서, 유기 다공성 중합체, 성분(ⅰ)은 10 내지 700㎛의 평균입경을 갖는 것임을 특징으로 하는 제조방법.
  3. 제1항에 있어서, 유기 다공성 중합체, 성분(ⅰ)은 20 내지 500㎛의 평균입경을 갖는 것임을 특징으로 하는 제조방법.
  4. 제1항에 있어서, 유기 다공성 중합체, 성분(ⅰ)은 직경이 0.006 내지 10㎛인 모든 기공들의 총 기공부피가 0.8cc/g이상인 것임을 특징으로 하는 제조방법.
  5. 제1항에 있어서, 유기 다공성 중합체, 성분(ⅰ)은 직경이 0.006 내지 10㎛인모든 기공들의 총 기공부피가 1.0cc/g이상인 것임을 특징으로 하는 제조방법.
  6. 제1항에 있어서, 유기 다공성 중합체, 성분(ⅰ)은 직경이 0.005 내지 2㎛인 모든 기공들의 총 기공부피가 직경이 0.006 내지 10㎛인 모든 기공들의 총 기공부피의 60% 이상인 것임을 특징으로 하는 제조방법.
  7. 제1항에 있어서, 유기 다공성 중합체, 성분(ⅰ)은 2 내지 10 탄소원자를 갖는 α-올레핀의 중합체, 스티렌 또는 핵 및/또는 측쇄에서 탄화수소기를 갖는 그의 유도체의 중합체, 그리고 0, N 또는 할로겐 원자를 함유하는 극성 중합체로 구성되는 군으로부터 선택되는 것을 특징으로 하는 제조방법.
  8. 제1항에 있어서, 유기 다공성 중합체, 성분(ⅰ)은 2 내지 10 탄소원자를 갖는 α-올레핀의 중합체인 것을 특징으로 하는 제조방법.
  9. 제1항에 있어서, 유기 다공성 중합체, 성분(ⅰ)은 최종적으로 중합되는 것과 같은 것인 α-올레핀의 중합체인 것을 특징으로 하는 제조방법.
  10. 제1항에 있어서, 성분(ⅱ)는 알루목산인 것을 특징으로 하는 α-올레핀 중합체의 제조방법.
  11. 제1항에 있어서, 성분(ⅲ)은 다음식 (1) 또는 (2)로 표시되는 천이금속화합물인 것을 특징으로 하는 α-올레핀 중합체의 제조방법.
    Qa(C5H5-a-bR1 b)(C5H5-a-cR2 c)MeXY (1)
    Sa(C5H5-a-dR3 d)ZMeXY (2)
    상기식에서 Q는 2개의 콘주게이트된 5-원환 리간드를 가교결합하는 결합기를 나타내며, S는 콘주게이트된 5-원환 리간드와 Z기를 가교결합하는 결합기를 나타내며, a는 0 또는 1이며, b, c 및 d는 a가 0일 때 0≤b≤5, 0≤c≤5 및 0≤d≤5, a가 1일 때 0≤b≤4, 0≤c≤4 및 O≤d≤4인 조건을 충족하는 정수이며, R1, R2및 R3는 각각 할로겐 원자, 1 내지 12 탄소원자를 갖는 알콕시기, -Si(R)(R′)(R″)의 형 태로 규소원자를 함유하는 1 내지 24 탄소원자를 갖는 규소함유 탄화수소기, -P(R)(R′)의 형태로 인 원자를 함유하는 1 내지 18 탄소원자를 갖는 인함유 탄화 수소기, -N(R)(R′)의 형태로 질소원자를 함유하는 1 내지 18 탄소원자를 갖는 질소함유 탄화수소기, 또는 -B(R)(R′)의 형태로 붕소원자를 함유하는 1 내지 18 탄소원자를 갖는 붕소함유 탄화수소기이며, 단 b, c 또는 d가 2이상이고 복수의 R1, R2또는 R3가 존재할 때 그것들은 같거나 다를 수도 있으며, Me는 주기율표의 ⅣB족 내지 ⅥB족의 천이금속이며, Z는 산소(-O-), 황(-S-), 1 내지 20 탄소원자를 갖는 알콕시기, 1 내지 20 탄소원자를 갖는 알콕시기, 1 내지 20 탄소원자를 갖는 티오알콕시기, 1 내지 40 탄소원자를 갖는 규소함유 탄화수소기, 1 내지 40 탄소원자를 갖는 질소함유 탄화수소가 또는 1 내지 40 탄소원자를 갖는 인함유 탄화수소기이며, 단 Z기에 있어서 결합중 하나는 a가 1일 때 결합기인 S기에 결합되며, X 및 Y는 같거나 또는 다를 수도 있는데, 수소, 할로겐기, 1내지 20 탄소원자를 갖는 탄화수소기, 1 내지 20 탄소원자를 갖는 알콕시기, 아미노기, 1 내지 20 탄소원자를 갖는 인함유 틴화수소기, 또는 1 내지 20 탄소원자를 갖는 규소함유 탄화수소기이다.
  12. 제1항에 있어서, 성분(ⅲ)은 티타늄, 지르코늄 및 하프늄으로 구성되는 군으로 부터 선택된 금속, Me의 화합물인 것을 특징으로 하는 제조방법.
  13. 제11항에 있어서, 성분(ⅲ)은 a가 1(하나)이고 Q 또는 S는 알킬렌기와 알킬실릴렌기로 구성되는 군으로부터 선택되는 것을 특징으로 하는 제조방법.
  14. 제1항에 있어서, 촉매는 성분(ⅱ) 및 (ⅲ)이 성분(ⅰ)에 지지되게 한다음 결과물을 기상조건하에 올레핀과 접촉하도록 가져오는 예비중합을 시켜, 성분(ⅰ), (ⅱ) 및 (ⅲ)의 총량 1g당 올레핀의 중합체 0.01 내지 500g을 얻음으로써 제조된 고체인 것을 특징으로 하는 제조방법.
  15. 제14항에 있어서, 예비중합에 의해 얻은 α-올레핀 중합체의 양은 성분(ⅰ), (ⅱ) 및 (ⅲ)의 총량 1g당 0.1 내지 100g인 것을 특징으로 하는 제조방법.
  16. 제14항에 있어서, 예비중합에 의해 얻은 α-올레핀 중합체의 양은 성분(ⅰ), (ⅱ) 및 (ⅲ)의 총량 1g당 0.2 내지 30g인 것을 특징으로 하는 제조방법.
  17. 제14항에 있어서, 예비중합에 사용된 α-올레핀은 에틸렌, 프로필렌, 부텐-1, 3-메틸부텐-1, 및 그의 혼합물로 구성되는 군으로부터 선택되는 것을 특징으로 하는 제조방법.
  18. 제1항에 있어서, 촉매는 성분(ⅱ) 및 (ⅲ)을 성분(ⅰ)에 지지되게 함으로써 얻어지는 고체와 유기알루미늄 화합물의 조합인 것을 특징으로 하는 제조방법.
  19. 제14항에 있어서, 촉매는 성분(ⅱ) 및 (ⅲ)을 성분(ⅰ)에 지지되게 한다음 결과물을 지상조건하에 올레핀과 접촉하도록 가져오는 예비중합을 시킴으로써 얻어지는 고체와 유기알루미늄 화합물의 조합인 것을 특징으로 하는 제조방법.
  20. 제1항에 있어서, 중합은 제1단계중합이 기상조건하에 실질적으로 촉매의 존재하에 행해져 결정성 프로필렌 단일중합체, 또는 5중량% 미만의 에틸렌 함량을 갖는 프로필렌-에틸렌 공중합체를 얻으며, 제2단계중합이 촉매와 제1단계중합에서 얻은 중합제의 존재하에 행해져 에틸렌과 4 내지 20 탄소원자를 갖는 α-올레핀으로 구성되는 군으로부터 선택된 적어도 한 공단량체와 프로필렌의 중합비율 0/100 내지 80/20 몰비로 중합하도록 하고, 단, 제1단계중합에서 중합량의 제2단계중합에서 중합량에 대한 중량비가 95/5 내지 30/70인 것을 특징으로 하는 제조방법.
  21. 제1항에 있어서, 중합은 에틸렌, 프로필렌 및 4-20 탄소원자의 α-올레핀으로 구성되는 군으로부터 선택된 적어도 두 단량체를 10/90 내지 90/10의 몰비로 중합되도록 중합하는 것을 특징으로 하는 제조방법.
    ※ 참고사항 : 최초출원 내용에 의하여 공개하는 것임.
KR1019930023802A 1992-11-10 1993-11-10 α-올레핀 중합체의 제조방법 KR100244381B1 (ko)

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JP30013892A JP3202356B2 (ja) 1992-11-10 1992-11-10 α‐オレフィン重合用触媒および該触媒を用いたα‐オレフィン重合体の製造法
JP92-300138 1992-11-10
JP30114692A JP3202358B2 (ja) 1992-11-11 1992-11-11 α‐オレフィン重合用触媒および該触媒を用いたα‐オレフィン重合体の製造法
JP92-301146 1992-11-11
JP92-329509 1992-12-09
JP32950992A JP3202370B2 (ja) 1992-12-09 1992-12-09 プロピレンブロック共重合体の製造法

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