KR900006370A - 유기 염화 알루미늄 촉매작용된 개선된 폴리-n-부텐의 제조방법 - Google Patents

유기 염화 알루미늄 촉매작용된 개선된 폴리-n-부텐의 제조방법 Download PDF

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KR900006370A
KR900006370A KR1019890015345A KR890015345A KR900006370A KR 900006370 A KR900006370 A KR 900006370A KR 1019890015345 A KR1019890015345 A KR 1019890015345A KR 890015345 A KR890015345 A KR 890015345A KR 900006370 A KR900006370 A KR 900006370A
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butene
poly
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mixture
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쟈웅-예이 첸 프랑크
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해롤드 아인호른
엑손 케미칼 패턴츠 인코포레이티드
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F110/04—Monomers containing three or four carbon atoms
    • C08F110/08—Butenes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F240/00—Copolymers of hydrocarbons and mineral oils, e.g. petroleum resins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F10/04—Monomers containing three or four carbon atoms
    • C08F10/08—Butenes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/52—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides selected from boron, aluminium, gallium, indium, thallium or rare earths

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  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
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  • Detergent Compositions (AREA)
  • Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)

Abstract

내용 없음

Description

유기 염화 알루미늄 촉매작용된 개선된 폴리-n-부텐의 제조방법
본 내용은 요부공개 건이므로 전문내용을 수록하지 않았음
제1도는 폴리이소부틸렌 제조 공정과 통합됨으로써 폴리이소부틸렌 공정 단위로부터의 쓰고난 C4스트림을 본 발명의 개선된 폴리-n-부텐 중합체로 유리하게 전환시키는, 본 발명의 공정의 하나의 실시태양을 나타내는 다이아그램이다.

Claims (39)

  1. (a) 유기 알루미늄 촉매의 실질적인 부재하에, 주입되는 HCl과 n-부텐이 실질적으로 완전히 반응함으로써 1.0ppm 미만의 유리 HCl을 함유하는 처리된 공급스트림 혼합물을 생성하기에 충분한 조건하에, 공급스티림 혼합물 100중량부당 약 0.005 내지 0.6 중량부의 양으로 HCl을 공급스트림 혼합물내로 주입하는 단계; (b) 상기 처리된 공급스트림 혼합물 및 유기 염화 알루미늄 촉매를 별도의 스트림으로서 반응 영역내로 동시에 도입하는 단계; (c) 반응영역에 상기 도입된, 처리된 공급스트림 혼합물과 상기 도입된 촉매를, 폴리-n-부텐을 함유하는 중합반응 혼합물을 형성하기에 충분한 시간동안 및 그러한 조건하에 접촉시키는 단계; (d) 상기 반응 영역으로부터 상기 중합반응 혼합물을 회수하는 단계; 및 (e) 상기 회수된 중합반응 혼합물로부터 상기 폴리-n-부텐 생성물을 회수하는 단계를 포함하는, 약 90℃ 미만의 온도로 유지된 교반 반응 영역에서, 약 5중량% 미만의 이소부틸렌 및 약 12중량% 이상의 n-부텐을 함유하는 C4탄화수소의 공급스트림 혼합물로 부터, 약 300 내지 약 900범위의 Mn 및 약 1.4미만의 분자량 분포를 갖는 저분자량 폴리-n-부텐을 제조하는 방법.
  2. 제1항에 있어서, 상기 촉매가 하기 일반식(I)의 화합물로 이루어진 그룹으로부터 선택된 적어도 하나의 화합물을 포함하는 방법.
    (R)XAl(Cl)3-X(I)
    상기식에서, R은 C1내지 C20하이드로카빌이고, x는 1내지 2의 정수이다.
  3. 제2항에 있어서, 상기 R그룹이 탄소수 1내지 10의 측쇄 또는 직쇄 알킬을 포함하는 방법.
  4. 제3항에 있어서, 상기 R그룹이 C1내지 C4알킬을 포함하는 방법.
  5. 제4항에 있어서, 상기 알킬 그룹이 메틸, 에틸, 이소프로필, 프로필, n-부틸, 이소부틸 및 3급 부틸로 이루어진 그룹으로부터 선택된 적어도 하나의 일원을 포함하는 방법.
  6. 제1항에 있어서, 상기 촉매가 (CH3)AlCl2, (CH3)2AlCl2, C2H5AlCl2, (C2H5)AlCl, (CH3)2CHAlCl2, [(CH3)2CH]2AlCl, (C3H7)AlCl2, (C3H7)2AlCl, CH3CH(CH3)AlCl2, [CH3CH(CH3)]2AlCl, (CH3)3CAlCl, [(CH3)3C2]AlCl, C6H13AlCl2, C5H11AlCl2및 C10H21AlCl2로 이루어진 그룹으로부터 선택된 적어도 하나의 일원을 포함하는 방법.
  7. 제1항에 있어서, 상기 촉매가 C2C5AlCl2, (C2H5)2AlCl 및 그의 혼합물을 포함하는 방법.
  8. 제1항에 있어서, 유기 알루미늄 촉매를, 상기 도입된 처리된 공급스트림 혼합물의 중량을 기준으로 약 0.05 내지 1.5중량%의 양으로 상기 반응 영역내로 도입하는 방법.
  9. 제1항에 있어서, 폴리-n-부텐 생성물이 약 1.2 내지 1.4의 분자량 분포를 갖는 방법.
  10. 제1항에 있어서, 폴리-n-부텐 생성물이 100℃에서 3 내지 40센티스톡의 점도를 갖는 방법.
  11. 제1항에 있어서, 중합온도가 약 10℃ 내지 60℃인 방법.
  12. 제1항에 있어서, 폴리-n-부텐이 약 340 내지 약 800의 Mn을 갖는 방법.
  13. 제1항에 있어서, 유기 염화 알루미늄을 C4탄화수소와 혼합하여 가하는 방법.
  14. 제13항에 있어서, 상기 유기 염화 알루미늄 촉매가 (알킬)X알루미늄(클로라이드)3-X(여기서 알킬그룹은 1내지 4개의 탄소원자를 함유하며, x는 1내지 2의 정수이다)로 이루어진 그룹으로부터 선택된 하나의 일원을 포함하는 방법.
  15. 제1항에 있어서, 상기 유기 염화알루미늄 촉매가 이염화 에틸 알루미늄을 포함하는 방법.
  16. 제1항의 방법에 의해 제조된 폴리-n-부텐 생성물.
  17. (a) 유기 알루미늄 촉매의 실질적인 부재하에, 주입되는 HCl과 n-부텐이 실질적으로 완전히 반응함으로써 1.0ppm미만의 유리 HCl을 함유하는 처리된 공급스트림 혼합물을 생성하기에 충분한 조건하에, 공급스트림 혼합물 100중량부당 약 0.005 내지 0.6 중량부의 양으로 HCl을 공급스트림 혼합물내로 주입하는 단계; (b) 상기 처리된 공급스트림 혼합물 및 유기 염화 알루미늄 촉매를 별도의 스트림으로서 반응 영역내로 동시에 도입하는 단계; (c) 반응영역에 상기 도입된, 처리된 공급스트림 혼합물과 상기 도입된 촉매를, 폴리-n-부텐을 함유하는 중합반응 혼합물을 형성하기에 충분한 시간동안 및 그러한 조건하에 접촉시키는 단계; (d) 상기 반응 영역으로부터 상기 중합반응 혼합물을 회수하는 단계; 및 (e) 상기 회수된 중합반응 혼합물로부터 상기 폴리-n-부텐 생성물을 회수하는 단계를 포함하는, 약 5℃ 내지 80℃의 온도로 유지된 교반 반응 영역에서, 약 5중량% 미만의 이소부틸렌 및 약 12중량% 이상의 n-부텐을 함유하는 C4탄화수소의 공급스트림 혼합물로 부터, 약 300 내지 약 900범위의 Mn 및 약 1.4미만의 분자량 분포를 갖는 저분자량 폴리-n-부텐을 제조하는 연속적인 방법.
  18. 제17항에 있어서, 상기 회수된 중합반응 혼합물을 수성 알카리로 급냉시키고, 상기 급냉시킨 중합반응 혼합물로 부터 상기 폴리-n-부텐 생성물을 회수하는 방법.
  19. 제17항에 있어서, 상기 촉매가 하기 일반식(I)의 화합물로 이루어진 그룹으로부터 선택된 적어도 하나의 화합물을 포함하는 방법.
    (R)XAl(Cl)3-X(I)
    상기식에서, R은 C1내지 C20하이드로카빌이고, x는 1내지 2의 정수이다.
  20. 제19항에 있어서, 상기 R그룹이 탄소수 1내지 10의 측쇄 또는 직쇄 알킬을 포함하는 방법.
  21. 제20항에 있어서, 상기 R그룹이 C1내지 C4알킬을 포함하는 방법.
  22. 제21항에 있어서, 상기 알킬 그룹이 메틸, 에틸, 이소프로필, 프로필, n-부틸, 이소부틸 및 3급 부틸로 이루어진 그룹으로 부터 선택된 적어도 하나의 일원을 포함하는 방법.
  23. 제17항에 있어서, 상기 촉매가 (CH3)AlCl2, (CH3)2AlCl2, C2H5AlCl2, (C2H5)AlCl, (CH3)2CHAlCl2, [(CH3)2CH]2AlCl, (C3H7)AlCl2, (C3H7)2AlCl, CH3CH(CH3)AlCl2, [CH3CH(CH3)]2AlCl, (CH3)3CAlCl, [(CH3)3C2]AlCl, C6H13AlCl2, C5H11AlCl2및 C10H21AlCl2로 이루어진 그룹으로부터 선택된 적어도 하나의 일원을 포함하는 방법.
  24. 제17항에 있어서, 상기 촉매가 C2C5AlCl2, (C2H5)2AlCl 및 그의 혼합물을 포함하는 방법.
  25. 제17항에 있어서, 유기 알루미늄 촉매를, 상기 도입된 처리된 공급스트림 혼합물의 중량을 기준으로 약 0.05 내지 1.5중량%의 양으로 상기 반응 영역내로 도입하는 방법.
  26. 제17항에 있어서, 폴리-n-부텐 생성물이 약 1.2 내지 1.4의 분자량 분포를 갖는 방법.
  27. 제17항에 있어서, 폴리-n-부텐 생성물이 100℃에서 3 내지 40센티스톡의 점도를 갖는 방법.
  28. 제17항에 있어서, 중합온도가 약 10℃ 내지 60℃인 방법.
  29. 제17항에 있어서, 폴리-n-부텐이 약 340 내지 약 800의 Mn을 갖는 방법.
  30. 제17항에 있어서, 유기 염화 알루미늄을 C4탄화수소와 혼합하여 가하는 방법.
  31. 제20항에 있어서, 상기 유기 염화 알루미늄 촉매가 (알킬)X알루미늄(클로라이드)3-X(여기서 알킬그룹은 1내지 4개의 탄소원자를 함유하며, x는 1내지 2의 정수이다)로 이루어진 그룹으로부터 선택된 하나의 일원을 포함하는 방법.
  32. 제17항에 있어서, 상기 유기 염화알루미늄 촉매가 이염화 에틸 알루미늄을 포함하는 방법.
  33. 제32항에 있어서, 유기 염화 알루미늄을 C4탄화수소와 혼합하여 가하는 방법.
  34. 제33항에 있어서, 중합온도가 약 10℃ 내지 60℃인 방법.
  35. 제34항에 있어서, 폴리-n-부텐이 약 340 내지 약 800의 Mn을 갖는 방법.
  36. 제35항에 있어서, 유기 알루미늄 촉매를, 상기 도입된 처리된 공급스트림 혼합물의 중량을 기준으로 약 0.05 내지 1.5중량%의 양으로 도입하는 방법.
  37. 제36항에 있어서, 폴리-n-부텐 생성물이 약 1.2 내지 1.4의 분자량 분포를 갖는 방법.
  38. 제37항에 있어서, 폴리-n-부텐 생성물이 100℃에서 3 내지 40센티스톡의 점도를 갖는 방법.
  39. 제38항에 있어서, 상기 회수된 중합반응 혼합물을 수성 알칼리로 급냉시키고, 상기 급냉시킨 중합반응 혼합물로 부터 상기 폴리-n-부텐 생성물을 회수하는 방법.
    ※ 참고사항 : 최초출원 내용에 의하여 공개하는 것임.
KR1019890015345A 1988-10-26 1989-10-25 유기 염화 알루미늄 촉매작용된 개선된 폴리-n-부텐의 제조방법 KR0136589B1 (ko)

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Application Number Priority Date Filing Date Title
US262.918 1988-10-26
US07/262,918 US4952739A (en) 1988-10-26 1988-10-26 Organo-Al-chloride catalyzed poly-n-butenes process
US262,918 1988-10-26

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KR900006370A true KR900006370A (ko) 1990-05-08
KR0136589B1 KR0136589B1 (ko) 1998-04-25

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US4952739A (en) 1990-08-28
JPH02164832A (ja) 1990-06-25
KR0136589B1 (ko) 1998-04-25
DE68924831D1 (de) 1995-12-21
CA1323635C (en) 1993-10-26
EP0367385A2 (en) 1990-05-09
MX17985A (es) 1993-06-01
DE68924831T2 (de) 1996-05-02
MX172796B (es) 1994-01-13
BR8905448A (pt) 1990-05-29
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AR248285A1 (es) 1995-07-12
EP0367385B1 (en) 1995-11-15

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