KR940021588A - 폴리 -1- 올레핀의 제조방법 - Google Patents

폴리 -1- 올레핀의 제조방법 Download PDF

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KR940021588A
KR940021588A KR1019940003947A KR19940003947A KR940021588A KR 940021588 A KR940021588 A KR 940021588A KR 1019940003947 A KR1019940003947 A KR 1019940003947A KR 19940003947 A KR19940003947 A KR 19940003947A KR 940021588 A KR940021588 A KR 940021588A
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브로이어스 베르너
렉트 라이너
뵘 루트비히
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아울미히, 루쯔
훽스트 아크티엔게젤샤프트
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Abstract

본 발명은 α-올레핀 중합시에 디알킬마그네슘계의 고활성 구형 지이글러 촉매를 사용하여 구형 중합체를 제조하는 방법에 관한 것이다. 본 발명의 추가의 잇점은 촉매의 활성이 높아서 중합에 필요한 촉매량이 극소량이라는 점이다. 본 발명에 따라 제조한 중합체내에 잔류하는 티타늄 및/또는 지르코늄의 함량은 10ppm 미만이다. 촉매는 수소에 대한 반응성이 양호하여 두 형태의 분자량 분포가 광범위한 중합체의 2단계 제조법에 특히 적합하다. 디에틸 설파이트와 같은 황함유 전자 공여체 대신에 에탄올과 같은 알콜을 사용하는 경우 냄새 문제가 적어지며 중합체의 사용 기회가 광범위해진다.
당해 중합체 및 공중합체는 입자 형태가 구형이고 유동행동이 매우 양호하여 조작, 건조 및 가공이 상당히 간단해지고 유리해진다.

Description

폴리-I-올레핀의 제조방법
본 내용은 요부공개 건이므로 전문내용을 수록하지 않았음
제 1 도는 1단계 중합공정에 사용되는 장치를 도시한 것이다
제 2 도는 2단계 중합공정에 사용되는 장치를 도시한 것이다

Claims (9)

  1. α-올레핀을 a) 하기 일반식(Ⅰ)의 오가노마그네슘 화합물을 오가노마그네슘 화합물 1mol당 염소화 탄화수소 0.5 내지 2.5mol의 양으로 지방족 1급 염소화 탄화수소와 반응시키고, b) 수득된 고체를 -20 내지 150℃의 온도에서 고체에 함유된 마그네슘 g원자당 0.001 내지 1mol의 양으로 알콜로 처리한 온도, c) 이렇게하여 수득한 지지체 물질은 20 내지 180℃의 온도에서 지지체 물질에 함유된 마그네슘 g원자당 0.1 내지 5mol의 양으로 하기 일반식(Ⅲ)의 화합물 하나 이상과 반응시킴으로써 제조된 전이금속 성분(성분 A)과 유기금속성 화합물(성분 B)을 포함하는 촉매의 존재하에 50 내지 150℃의 온도 및 1 내지 40bar의 압력에서 중합시켜 폴리올레핀을 제조하는 방법.
    상기식에서, R1및 R2는 탄소수 2 내지 12의 동일하거나 상이한 알킬 라디칼이며 ; X는 0 내지 2이고 ; M1은 티타늄 또는 지르코늄이며 ; R5는 탄소수 2 내지 10의 알킬 라디칼이고 ; X는 할로겐 원자이며 ; m은 0 내지 4의 정수이다.
  2. 제 1 항에 있어서, 오가노마그네슘 화합물과 지방족 1급 염소화 탄화수소와의 반응이 하기 일반식(Ⅱ)의 오가노알루미늄 화합물의 존재하에 또는 트리알킬알루미늄 또는 디알킬알루미늄 하이드라이드와 탄소수 4 내지 20의 디올레핀과의 반응 생성물의 존재하에 수행되는 방법.
    상기식에서, R3및 R4는 탄소수 1 내지 8의 동일하거나 상이한 알킬 라디칼이며 ; n은 0, 1, 2 또는 3이다.
  3. 제 1 항에 있어서, 일반식[(n-C4H9)1.2.1.7(n-C8H17)|0.3-0-8Mg]의 디알킬 마그네슘이 사용되는 방법.
  4. 제 1 항에 있어서, 사용된 알콜이 에탄올인 방법.
  5. 제 1 항에 있어서, 일반식 M1Xm(OR5)4-m(Ⅲ)의 화합물(여기서, M1, R5및 m은 제 1 항에서 정의한 바와 같다)이 TiCl4인 방법.
  6. 제 1 항에 있어서, 단계 b)가 생략되는 방법.
  7. 제 1 항에 있어서, 촉매 성분 A가 예비중합되는 방법.
  8. 제 1 항에 있어서, 중합반응이 기상 방법으로 하나 이상의 단계로 연속적으로 수행되는 방법.
  9. α-올레핀을 a) 하기 일반식(Ⅰ)의 오가노마그네슘 화합물을, 필요한 경우, 하기 일반식(Ⅱ)의 오가노알루미늄 화합물의 존재하에 또는 트리알킬알루미늄 또는 디알킬알루미늄 하이드라이드와 탄소수 4 내지 20의 디올레핀과의 반응 생성물의 존재하에 오가노마그네슘 화합물 1mol당 염소화 탄화수소 0.5 내지 2.5mol의 양으로 지방족 1급 염소화 탄화수소와 반응시키고, b) 수득된 고체를 -20 내지 150℃의 온도에서 고체에 함유된 마그네슘 g원자당 0.001 내지 1mol의 양으로 알콜로 처리한 다음, c) 이렇게하여 수득한 지지체 물질을 20 내지 180℃의 온도에서 지지체 물질에 함유된 마그네슘 g원자당 0.1 내지 5mol의 양으로 하기 일반식(Ⅲ)의 화합물 하나 이상과 반응시킴으로써 제조된 전이금속 성분(성분 A)과 유기금속성 화합물(성분 B)을 포함하는 촉매의 존재하에 50 내지 150℃의 온도 및 1 내지 40bar의 압력에서 기상 방법으로 하나 이상의 단계로 중합[여기서, 1단계 공정의 경우에는, 기체 분산기(11)를 갖는 반응기(1)와 순환 기체라인(13)을 포함하는 장치{여기서, 순환 기체 라인(13)에는 압축기(14)가 하부 스트림인 열교환기(15)와 함께 배열되어 있으며, 압축기(14)의 상부 스트림인 공급 라인(16)이 순환 기체 라인(13)쪽으로 통하고 있으며, 추가의 공급 라인(18)이 반응기(1)로 향하며, 반응기(1)의 최상부에는 순환 기체 라인(13)에서의 폐기체 라인(17)이 존재하며, 반응기(1)가 배출 라인(19)과 차단 장치(31)를 통하여 이송 라인(32)이 구비되어 있는 저장 호퍼(3)로 배출될 수 있다}에서 중합되며, 2단계 공정의 경우에는, 기체 분산기(21)를 갖고 배출라인(19)을 통하여 반응기(1)에 연결되어 있는 제 2 반응기(2)가 보충되어 있는 위에서 언급한 장치{여기서, 제 2 반응기에는 압축기(24)와 하부 스트림인 열교환기(25)가 삽입되어 있는 순화 기체 라인(23)이 구비되어 있고 공급 라인(26)은 압축기(24)의 상부 스트림인 순환 기체 라인(23)으로 향하고, 반응기(2)의 최상부에는 폐기체 라인(27)이 존재하며, 반응기(2)는 차단 장치(31)가 있는 배출 라인(29)을 통하여 저장 호퍼(3)로 배출된다}에서 중합된다]시켜 폴리올레핀을 제조하는 방법.
    상기식에서, R1및 R2는 탄소수 2 내지 12의 동일하거나 상이한 알킬 라디칼이며 ; X는 0 내지 1이고 ; R3및 R4는 탄소수 1 내지 8의 동일하거나 상이한 알킬 라디칼이며 ; n은 0, 1, 2 또는 3이고 ; M1은 티타늄 또는 지르코늄이며 ; R5는 탄소수 2 내지 10의 알킬 라디칼이고 ; X는 할로겐 원자이며 ; m은 0 내지 4의 정수이다.
    ※ 참고사항 : 최초출원 내용에 의하여 공개하는 것임.
KR1019940003947A 1993-03-02 1994-03-02 폴리-1-올레핀의 제조방법 KR100286409B1 (ko)

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WO2006079774A1 (en) * 2005-01-26 2006-08-03 Ineos Europe Limited Apparatus and process for the withdrawal of polymer from a gas-phase polymerization reactor
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JP3513205B2 (ja) 2004-03-31
EP0613909A1 (de) 1994-09-07
KR100286409B1 (ko) 2001-04-16
ATE159955T1 (de) 1997-11-15
EP0613909B1 (de) 1997-11-05
DE59404496D1 (de) 1997-12-11
SG52626A1 (en) 1998-09-28
CA2116752A1 (en) 1994-09-03
US5798309A (en) 1998-08-25
DE4306382A1 (de) 1994-09-08
JPH06322017A (ja) 1994-11-22
BR9400767A (pt) 1994-10-18

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