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KR940003974A - 폴리올레핀의 제조방법 - Google Patents

폴리올레핀의 제조방법 Download PDF

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KR940003974A
KR940003974A KR1019930015663A KR930015663A KR940003974A KR 940003974 A KR940003974 A KR 940003974A KR 1019930015663 A KR1019930015663 A KR 1019930015663A KR 930015663 A KR930015663 A KR 930015663A KR 940003974 A KR940003974 A KR 940003974A
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빈터 안드레아스
안트베르크 마르틴
바흐만 베른트
돌레 폴커
퀴버 프랑크
로르만 위르겐
슈팔렉 밀터
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훽스트 아크티엔게젤샤프트
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Abstract

본 발명은 일반식 Ra-CH=Rb의 올레핀(여기서, Ra와Rb)는 동일하거나 상이하며, 수소원자 또는 탄소수 1내지 14의 탄화수소 라디칼이거나, Ra와Rb는 이들을 연결하는 원자와 함께 환을 형성할 수 있다)을, 온도 범위가 -60 내지 2000℃이고 압력 범위가 0.5 내지 :100bar인 조건하에서 전이금속 화합물인 다음 일반식 (I)의 메탈로센 (이는 메조 형태이거나 메조 : 라세미의 비율이 1 : 99를 초과하는 메조 : 라세미 혼합물이다) 및 공촉매로부터 형성된 촉매의 존재하에 용액, 현탁 또는 기상 중합 또는 공중합시켜 올레핀 중합체를 제조하는 방법에 관한 것이다.
상기식에서, M1은 Zr 또는 Hf이고, R1및 R2는 동일하거나 상이하며, 메틸 또는 염소이며, R3및 R6은 동일하거나 상이하고, 메틸, 이소프로필, 페닐, 에틸 또는 트리플루오로메틸이며, R4및 R5는 수소이거나 R3및 R6에 대해 정의한 바와 같거나, R4는 R6과 함께 지방족 또는 방향족 환을 형성하거나, 인접한 라디칼 R4는 이 러한 형태의 환을 형성하고,
R7이또는

Description

폴리올레핀의 제조방법
본 내용은 요부공개 건이므로 전문내용을 수록하지 않았음

Claims (15)

  1. 일반식 Ra-CH=Rb의 올레핀(여기서, Ra와Rb)는 동일하거나 상이하며, 수소원자 또는 탄소수 1 내지 14의 탄화수소 라디칼이거나, Ra와Rb는 이들을 연결하는 원자와 함께 환을 형성할 수 있다)을, 온도 범위가 -60 내지 200℃이고 압력 범위가 0.5 내지 100bar인 조건하에서 전이금속 화합물인 다음 일반식 (I)의 메탈로센(이는 메조 형태이거나 메조 : 라세미의 비율이 1 : 99를 초과하는 메조 : 라세미 혼합물이다) 및 공촉매로부터 형성된 촉매의 존재하에 용액, 현탁 또는 기상 중합 또는 공중합시켜 올레핀 중합체를 제조하는 방법.
    상기식에서, M1은 주기율표의 IVb족, Vb족 또는 Vlb족에 속하는 금속이고, R1및 R2는 동일하거나 상이하며, 수소원자, C1-Cl0-알킬 그룹, C1-C10-알콕시 그룹, C6-C10-아릴 그룹, C6-Cl0-아릴옥시 그룹, C2-Cl0-알케닐 그룹, C7-C40-아릴알킬그룹, C7-C40-알킬아릴 그룹, C8-C40-아릴알케닐 그룹 또는 할로겐 원자이고, 라디칼 R4및 R5는 동일하거나 상이하며, 수소원자, 할로겐 원자, 할고겐화될 수 있는 C1-C10-알킬 그룹, 할로겐화될 수 있는 C8-C10-아릴 그룹 및 -NR10 2, -SR10, -OSiR10 3, -SiR10 3또는 -PR10 2라디칼(여기서, R10은 한로겐 원자, C1-C10-알킬 그룹 또는 C6-C10-아릴 그룹이다)이고, R3및 R6은 동일하거나 상이하며, R6에 대해 정의한 바와 같거나 (단, R3및 R6은 수소가 아니다), 라디칼 R3내지 R6중의 둘 이상을 연결하는 원자와 함께 환 시스템을 형성하고,
    -Ge-, -Sn-, -0-. -S-, =S0, =S02, =NR11, =CO, PR11또는 =P(0)R11[여기서, R11, R12및 R13은 동일하거나 상이하며, 수소원자, 할로겐원자, C1-C10-알킬 그룹, C1-C10-플루오로알킬 그룹, C6-C10-아릴 그룹, C6-C10-플루오로아릴 그룹, C1-C10-알콕시 그룹, C2-C10-알케닐 그룹, C7-C40-아릴알킬 그룹, C8-C40-아릴알케닐 그룹 는 X7-C40-알킬아릴 그룹이거나, R11과 R12또는 R11과 R13은, 각각의 경우, 이들을 연결하는 원자와 함께 환을 형성하고, M2는 규소, 게르마늄 또는 주식이다]이며, R8및 R9는 동일하거나 상이하고, R11에 대해 정의한 바와 같으며, m 및 n은 동일하거나 상이하고, 0,1또는 2이고, m+n은 0,1또는 2이다.
  2. 제1항에 있어서, 일반식(I)에서 M1이 Zr 또는 Hf이고, R1및 R2가 동일하거나상이하며, 메틸 또는 염소이고, R3및 R6이 동일하거나 상이하며, 메틸, 이소프로필, 페닐, 에틸 또는 트리플루오로메틸이고, R4및 R5가 수소이거나 R3및 R6에 대해 정의한 바와 같거나, R4가 R6과 함께 지방족 또는 방향족 환을 형성하거나, 인접한 라디칼 R4가 이러한 형태의 환을 형성하고,
    R7이또는라디칼이며, m+n이 0 또는 1인 방법.
  3. 제1항 또는 제2항에 있어서, 일반식(I)의 메탈로센이 라세미 형태 : 메조 형태의 비율이 1 : 99를 초과하거나 순수한 메조 형태인 화합물 Me2Si(2,4-디메틸-1-인데닐)-1-인데닐)2ZrCl2, Me2Si(2-메틸-4-이소프로필-1-인데닐)2ZrCl2, Me2Si(2-에틸-4-메틸-1-인데닐)2ZrCl2, Ph(Me)Si(2-메틸-4-이소프로필-1-인데닐)2ZrCl2, Me2Si (2-메틸-4,5-벤조-인데닐)2ZrCl2, Me2Si(2,4,6-트리메틸-1-인데닐)2ZrCl2, Me2Si(2-메틸-4,6-디이소프로필-1-인데닐)2ZrCl2, Me2Si(2-메틸-α-아세나프트-인데 닐)2ZrCl2, Me2Si(2-메틸-4-페닐-1-인데닐)2ZrCl2, 에틸렌(2,4,6-트리메틸-1-인데닐)2ZrCl2, 에틸렌(2-메틸-4,5-벤조인데닐)2ZrCl2, 메틸에틸렌(2-메틸-α-아세나프트-인데닐)2ZrCl2또는 Ph(Me)Si(2-메틸-α-아세나프트인데닐)2ZrCl2인 방법.
  4. 제1항 내지 제3항중의 어느 한 항에 있어서, 사용되는 공촉매가 다음 일반식 (Ⅱ)의 선형 알루미녹산 및/또는 다음 일반식(Ⅲ)의 환형 알루미녹산인 방법.
    상기식에서, 라디칼 R14는 동일하거나 상이하며, C1-C6-알킬 그룹, C6-C1-아릴 그룹, 벤질 또는 수소이고, p는 2내지 50의 정수이다.
  5. 제1항 내지 제4항 중의 어느 한 항에 있어서, 사용되는 공촉매가 메틸알루미녹산인 방법.
  6. 제4항 또는 제5항에 있어서, 일반식(I)의 메탈로센이 중합반응에서 사용하기 전에 일반식(Ⅱ)및/또는 (Ⅲ)의 알루미녹산에 의해 예비활성화되는 방법.
  7. 제1항 내지 제6항중의 어느 한항에 있어서, 일반식(I)의 메조 형태의 메탈로센이, 점도지수 Ⅵ가 80㎤/g을 초과하고 분자량 Mw이 100,000g/mol을 초과하며 다분산성 Mw/Mn이 4.0이하이고 아이소택틱 지수가 60%이하인 폴리올레핀을 제조하는데 사용되는 방법.
  8. 제1항 내지 제6항중의 어느 한 항에 있어서, 일반식 (I)의 메탈로센의 메조 형태 : 라세미 형태의 비율이 1:99를 초과하는 혼합물이 두 가지 이상의 폴리올레핀 쇄, 즉 전체 폴리올레핀의 최대 99중량%를 차지하는, 아이소택틱 지수가 90%를 초과하고 다분산성이 4.0이하이며 아이소택틱 방식으로 결합된 α-올레핀 단위를 포함하는 중합체 쇄(a)와 전체 폴리올레핀의 1중량%이상을 차지하는, 아이소택틱 지수가 60%이하이고 점도지수 Ⅵ가 80㎤/g을 초과하고 분자량 Mw이 100,O0g/mol을 초과하며 다분산성 Mw/Mn이 4.0이하인 어택틱 폴리올레핀을 포함하는 중합체 쇄(b)를 포함하는 폴리올레핀을 제조하는데 사용되는 방법.
  9. 제1항 내지 제3항중의 어느 한 항에서 청구한 일반식(Ⅰ)의 메탈로센을 올레핀 중합시 촉매로서 사용되는 방법.
  10. 제1항 내지 제8항중의 어느 한 항에서 청구한 방법에 의해 제조가능한 올레핀 중합체.
  11. 제10항에 있어서, 점도지수 Ⅵ가 80㎤/g을 초과하고 분자량 Mw이 100,000g/mol을 초과하며 다분산성 Mw/Mn이 4.0이하이고 아이소택틱 지수가 60%이하인 올레핀 중합체.
  12. 제10항 는 제11항에 있어서, 두가지 이상의 폴리올레핀 쇄, 즉 전체 폴리올레핀의 최대 99중량%를 차지하는, 아이소택틱 지수가 90%를 초과하고 다분산성이 4.0이하이며 아이소택틱 방식으로 결합된 α-올레핀 단위를 포함하는 중합체쇄(a)와 전체 폴리올레핀의 1중량%이상을 차지하는, 아이소택틱 지수가 60%이하이고 점도지수 Ⅵ가 80㎤/g을 초과하고 분자량 Mw이 100,000g/mo1을 초과하며 다분산성 Mw/Mn이 4.0이하인 어택틱 폴리올레핀을 포함하는 중합체 쇄(b)를 포함하는 폴리올레핀 중합체.
  13. 순수한 메조 형태이거나 메조 형태 : 라세미 형태의 비율이 1 : 99를 초과하는 혼합물인 다음 일반식(I)의 화합물.
    상기식에서, M1은 주기율표의 IVb족, Vb족 또는 VIb족에 속하는 금속이고, R1및 R2는 동일하거나 상이하며, 수소원자, C1-C10-알킬그룹, C1-C10-알콕시 그룹, C6-C10-아릴 그룹, C6-C10-아릴옥시 그룹, C2-C10-알케닐 그룹, C7-C40-아릴알킬 그룹, C7-C40-알킬아릴 그룹, C8-C40-아릴알케닐 그룹 또는 할로겐 원자이고, 라디칼 R4및 R5는 동일하거나 상이하며, 수소원자, 할로겐화될 수 있는 C1-C10-알킬 그룹, 할로겐화될 수 있는 C6-C10-아릴 그룹 및 -NR10 2, -SR10, -ORiR10 3, -SiR10 3또는 -PR10 2라디칼 (여기서, R10은 할로겐 원자, C1-C10-알킬 그룹 는 C6-C10-아릴 그룹이다)이고, R3및 R6은 동일하거나 상이하며, R4에 대해 정의한 바와 같거나 (단, R3및 R6은 수소가 아니다), 라디칼 R3내지 R6중의 둘 이상은 이들을 연결하는 원자와 함께 환 시스템을 형성하고,
    -Ge-, -Sn-, -O-, -S-, =S0, =S02, =NR11, =CO, =PR11또는 =P(0)R11[여기서, R11,R12및 R13은 동일하거나 상이하며, 수소원자, 할로겐원자, C1-C10-알킬 그룹, C1-C1O-플로오로알킬 그룹, C6-C10-아릴 그룹, C6-C10-플루오로아릴 그룹, C1-C10-알콕시 그룹, C2-C10-알케닐 그룹, C7-C40-아릴알킬 그룹, C8-C40-아릴알케닐 그룹 는 C7-C40-알킬아릴 그룹이거나, R11과 R12또는 R11과 R13은, 각각의 경우, 이들을 연겨랗는 원자와 함게 환을 형성하고, M2는 규소, 게르마늄 또는 주석이다]이며, R8및 R9는 동일하거나 상이하고, R11에 대해 정의한 바와 같으며, m 및 n은 동일하거나 상이하고, 0,1 또는 2이고, m+n은 0,1또는 2이다.
  14. 제13항에 있어서, 일반식(I)에서 M1이 Zr 또는 Hf이고, R1및 R2가 동일하거나 상이하며, 메틸 또는 염소이고, R3및 R6이 동일하거나 상이하며, 메틸, 이소프로필, 페닐, 에틸 또는 트리플로우로메틸이고, R4및 R5가 수소이거나 R3및 R6에 대해 정의한 바와 같거나, R4가 R6과 함께 지방족 또는 방향족 환을 형성하거나, 인접한 라디칼 R4및 R5가 수소이거나 R3및 R6에 대해 정의한 바와 같거나, R4가 R6과 함께 지방족 는 방향족 환을 형성하거나, 인접한 라디칼 R4가 이러한 형태의 환을 형성하고,
    R7이또는m+n이 0 또는 1인 화합물.
  15. 제13항 또는 제14항에 있어서, 일반식(I)의 화합물이 Me2Si(2,4-디메틸-1-인데닐)2ZrCl2, Me2Si(2-메틸-4-이소프로필-1-인데닐)3ZrCl2, Me2Si(2-에틸-4-메틸-1-인데닐)2ZrCl2, Ph(Me)Si(2-메틸-4,5-벤조인데닐)2ZrCl2, Me2Si(2,4,6-트리메틸-1-인 데닐)2ArCl2, Me2Si(2-메틸 -4,6-디이소프로필-1-인데닐)2ZrCl2, Me2Si(2-메틸-α-아세나프트-인데닐)2ZrCl2, Me2Si(2-메틸-4-페닐-1-인데닐)2ZrCl2, 에틸렌(2,4,6-트리 메틸-1-인데닐)2ZrCl2, 에틸렌(2-메틸-4,5-벤조인데닐)2ZrCl2, 메틸에틸렌(2-메틸-α-아세나프트-인데닐)2ZrCl2또는 Ph(Me)Si(2-메틸-α-아세나프트인데닐)2ZrCl2인 화합물.
    ※ 참고사항 : 최초출원 내용에 의하여 공개하는 것임.
KR1019930015663A 1992-08-15 1993-08-13 폴리올레핀의 제조방법 및 이 방법으로 제조한 폴리올레핀 Expired - Lifetime KR100283825B1 (ko)

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Families Citing this family (102)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5504169A (en) * 1989-09-13 1996-04-02 Exxon Chemical Patents Inc. Process for producing amorphous poly-α-olefins with a monocyclopentadienyl transition metal catalyst system
TW309523B (ko) * 1991-11-30 1997-07-01 Hoechst Ag
US5830821A (en) * 1991-11-30 1998-11-03 Targor Gmbh Process for olefin preparation using metallocenes having benzo-fused indenyl derivatives as ligands
TW294669B (ko) * 1992-06-27 1997-01-01 Hoechst Ag
USRE39156E1 (en) 1992-08-15 2006-07-04 Basell Polyolefine Gmbh Process for the preparation of polyolefins
ES2128371T3 (es) 1992-08-15 1999-05-16 Targor Gmbh Procedimiento para la obtencion de poliolefinas.
IT1271406B (it) * 1993-09-13 1997-05-28 Spherilene Srl Procedimento per la preparazione di polimeri dell'etilene e prodotti ottenuti
US5817590A (en) * 1993-10-14 1998-10-06 Tosoh Corporation Catalyst for αE --olefin polymerization containing a Lewis base
IT1270253B (it) * 1994-06-20 1997-04-29 Spherilene Srl Copolimeri dell'etilene e procedimento per la preparazione di polimeri dell'etilene
WO1996000243A1 (en) * 1994-06-24 1996-01-04 Exxon Chemical Patents Inc. Polymerization catalyst systems, their production and use
CA2183419A1 (en) * 1994-12-20 1996-07-04 Luigi Resconi Reactor blend polypropylene, process for the preparation thereof and process for preparing metallocene ligands
DE69533310T2 (de) * 1994-12-20 2005-07-21 Mitsui Chemicals, Inc. Verfahren zur herstellung von ethylenpolymer und ethylenpolymer
IT1272922B (it) * 1995-01-23 1997-07-01 Spherilene Srl Procedimento per la preparazione di composti metallocenici
IT1272923B (it) * 1995-01-23 1997-07-01 Spherilene Srl Composti metallocenici,procedimento per la loro preparazione,e loro utilizzo in catalizzatori per la polimerizzazione delle olefine
US5516848A (en) * 1995-01-31 1996-05-14 Exxon Chemical Patents Inc. Process to produce thermoplastic elastomers
US5539056A (en) * 1995-01-31 1996-07-23 Exxon Chemical Patents Inc. Thermoplastic elastomers
TR28706A (tr) * 1995-02-14 1997-01-13 Royal Mobilya Dekorasyon Ve Ak Yatak haline dönüsebilen koltuk ya da kanepeler icin hareket mekanizmalari.
UA47394C2 (uk) * 1995-05-16 2002-07-15 Юнівейшн Текнолоджіз, Ллс Етиленовий полімер, який має підвищену придатність до обробки та вирiб, що містить етиленовий полімер
DE69623528T2 (de) * 1995-05-16 2003-03-20 Univation Technologies,Llc Herstellung von Polyethylen unter Verwendung eines stereoisomeren Metallocens
US6787618B1 (en) 1995-12-01 2004-09-07 Basell Polypropylen Gmbh Metallocene compound and high molecular weight copolymers of propylene and olefins having two or four to thirty-two carbon atoms
DE19544828A1 (de) * 1995-12-01 1997-06-05 Hoechst Ag Hochmolekulare Copolymere
FI104826B (fi) 1996-01-30 2000-04-14 Borealis As Heteroatomilla substituoituja metalloseeniyhdisteitä olefiinipolymerointikatalyytti-systeemejä varten ja menetelmä niiden valmistamiseksi
US6211310B1 (en) 1997-06-05 2001-04-03 Union Carbide Chemicals & Plastics Technology Corporation Manufacture of stereoregular polymers
US5693727A (en) * 1996-06-06 1997-12-02 Union Carbide Chemicals & Plastics Technology Corporation Method for feeding a liquid catalyst to a fluidized bed polymerization reactor
DE69720609T2 (de) * 1996-07-16 2003-11-13 Basell Polyolefine Gmbh Verfahren zur Modifikation von die Rac/Meso-Verhältnis einer Metallocenverbindung
DE19637669A1 (de) 1996-09-16 1998-03-19 Hoechst Ag Verfahren zur Herstellung einer methylenverbrückten Biscyclopentadienylverbindung
WO1998022477A1 (en) * 1996-11-22 1998-05-28 Boulder Scientific Company Preparation of chiral titanocenes
US5847176A (en) * 1997-06-30 1998-12-08 Boulder Scientific Company Preparation of chiral titanocenes
FI971565A7 (fi) * 1997-04-14 1998-10-15 Borealis As Olefiinien polymerointiin tarkoitettujen katalysaattorisysteemien substituoituja metalloseeniyhdisteitä, niiden välituotteet ja valmistusmenetelmä
US6160072A (en) * 1997-05-02 2000-12-12 Ewen; John A. Process for polymerizing tactioselective polyolefins in condensed phase using titanocenes
EP0930320A1 (en) * 1997-07-22 1999-07-21 Mitsui Chemicals, Inc. Ethylene/alpha-olefin copolymers, compositions, and processes for the preparation of the copolymers and the compositions
US6265512B1 (en) 1997-10-23 2001-07-24 3M Innovative Company Elastic polypropylenes and catalysts for their manufacture
KR100274973B1 (ko) * 1997-11-24 2000-12-15 성재갑 올레핀계 단량체의 중합 촉매
DE19806918A1 (de) * 1998-02-19 1999-08-26 Aventis Res & Tech Gmbh & Co Katalysatorsystem, Verfahren zu seiner Herstellung und seine Verwendung zur Polymerisation von Olefinen
EP0953582A1 (en) * 1998-04-27 1999-11-03 Fina Research S.A. Polyolefin production
US6306960B1 (en) 1998-05-13 2001-10-23 Exxonmobil Chemical Patents Inc. Articles formed from foamable polypropylene polymer
US6784269B2 (en) 1998-05-13 2004-08-31 Exxonmobil Chemical Patents Inc. Polypropylene compositions methods of making the same
WO1999058587A1 (en) 1998-05-13 1999-11-18 Exxon Chemical Patents Inc. Propylene homopolymers and methods of making the same
MXPA00002181A (es) 1998-07-02 2003-04-22 Montell Technology Company Bv Procedimiento para la preparacion de polimeros de alfa-olefinas sustancialmente amorfos composiciones que los contienen, y procedimiento para la preparacion de ligandos puenteados.
US6177527B1 (en) * 1998-09-08 2001-01-23 Union Carbide Chemical & Plastics Technology Corporation Process for the preparation of polyethylene or polypropylene
US6174930B1 (en) 1999-04-16 2001-01-16 Exxon Chemical Patents, Inc. Foamable polypropylene polymer
US6500563B1 (en) 1999-05-13 2002-12-31 Exxonmobil Chemical Patents Inc. Elastic films including crystalline polymer and crystallizable polymers of propylene
CA2373271C (en) 1999-05-13 2009-04-07 Exxonmobil Chemical Patents Inc. Elastic fibers and articles made therefrom, including crystalline and crystallizable polymers of propylene
US6750284B1 (en) * 1999-05-13 2004-06-15 Exxonmobil Chemical Patents Inc. Thermoplastic filled membranes of propylene copolymers
US6863989B1 (en) 1999-10-08 2005-03-08 The Procter & Gamble Company Adhesives comprising linear isotactic polymers
US6746780B1 (en) 1999-10-08 2004-06-08 The Procter & Gamble Company Bodies of polymeric material comprising linear, isotactic polymers
EP1237955A1 (en) * 1999-10-08 2002-09-11 The Procter & Gamble Company Bodies of polymeric material comprising linear, isotactic polymers
ES2210015T3 (es) 1999-11-04 2004-07-01 Exxonmobil Chemical Patents Inc. Espumas de copolimero de propileno y su uso.
US6809168B2 (en) * 1999-12-10 2004-10-26 Exxonmobil Chemical Patents Inc. Articles formed from propylene diene copolymers
US6977287B2 (en) * 1999-12-10 2005-12-20 Exxonmobil Chemical Patents Inc. Propylene diene copolymers
JP2003516440A (ja) * 1999-12-10 2003-05-13 エクソンモービル・ケミカル・パテンツ・インク プロピレンジエン共重合ポリマー
EP1263815B1 (en) 1999-12-22 2007-03-28 ExxonMobil Chemical Patents Inc. Adhesive alpha-olefin inter-polymers
US6960676B2 (en) * 2000-02-08 2005-11-01 Exxonmobil Chemical Patents Inc. Method of preparing group 14 bridged biscyclopentadienyl ligands
US6384142B1 (en) 2000-02-08 2002-05-07 Exxonmobil Chemical Patents Inc. Propylene impact copolymers
KR100626258B1 (ko) * 2001-06-22 2006-09-21 보레알리스 테크놀로지 오와이 4-, 5-, 6- 또는 7-위치에서 실록시 또는 게르밀옥시 기로치환된 인데닐 잔기를 함유하는 메탈로센 촉매
US6916892B2 (en) * 2001-12-03 2005-07-12 Fina Technology, Inc. Method for transitioning between Ziegler-Natta and metallocene catalysts in a bulk loop reactor for the production of polypropylene
KR100458600B1 (ko) * 2002-02-07 2004-12-03 주식회사 엘지화학 메틸렌 브릿지된 메탈로센 촉매를 이용한 올레핀-시클릭올레핀 공중합체의 제조 방법
US6706828B2 (en) * 2002-06-04 2004-03-16 Crompton Corporation Process for the oligomerization of α-olefins having low unsaturation
US20030236365A1 (en) * 2002-06-24 2003-12-25 Fina Technology, Inc. Polyolefin production with a high performance support for a metallocene catalyst system
US8008412B2 (en) 2002-09-20 2011-08-30 Exxonmobil Chemical Patents Inc. Polymer production at supersolution conditions
US20080153997A1 (en) * 2006-12-20 2008-06-26 Exxonmobil Research And Engineering Polymer production at supercritical conditions
US7223822B2 (en) 2002-10-15 2007-05-29 Exxonmobil Chemical Patents Inc. Multiple catalyst and reactor system for olefin polymerization and polymers produced therefrom
CA2499951C (en) 2002-10-15 2013-05-28 Peijun Jiang Multiple catalyst system for olefin polymerization and polymers produced therefrom
US7550528B2 (en) 2002-10-15 2009-06-23 Exxonmobil Chemical Patents Inc. Functionalized olefin polymers
US7541402B2 (en) 2002-10-15 2009-06-02 Exxonmobil Chemical Patents Inc. Blend functionalized polyolefin adhesive
US7700707B2 (en) 2002-10-15 2010-04-20 Exxonmobil Chemical Patents Inc. Polyolefin adhesive compositions and articles made therefrom
US7195806B2 (en) * 2003-01-17 2007-03-27 Fina Technology, Inc. High gloss polyethylene articles
DE10303225A1 (de) * 2003-01-28 2004-08-05 Inventis Technologies Gmbh Katalysatorkombination, isotaktische Polymere sowie ein Verfahren zur Herstellung von linearen isotaktischen Polymeren und dessen Verwendung
JP2005099712A (ja) * 2003-08-28 2005-04-14 Sharp Corp 表示装置の駆動回路および表示装置
US20050234198A1 (en) * 2004-04-20 2005-10-20 Fina Technology, Inc. Heterophasic copolymer and metallocene catalyst system and method of producing the heterophasic copolymer using the metallocene catalyst system
US8178636B2 (en) * 2004-05-04 2012-05-15 Basell Polyolefine Gmbh Process for the preparation of atactic 1-butene polymers
JP2008506825A (ja) * 2004-07-22 2008-03-06 バーゼル・ポリオレフィン・ゲーエムベーハー フラクション化可能な１−ブテンポリマー類の製造法
RU2371459C2 (ru) * 2004-07-22 2009-10-27 Базель Полиолефине Гмбх Композиция полимеров 1-бутена
US7169864B2 (en) * 2004-12-01 2007-01-30 Novolen Technology Holdings, C.V. Metallocene catalysts, their synthesis and their use for the polymerization of olefins
US7232869B2 (en) * 2005-05-17 2007-06-19 Novolen Technology Holdings, C.V. Catalyst composition for olefin polymerization
US7868197B2 (en) 2005-12-14 2011-01-11 Exxonmobil Chemical Patents Inc. Halogen substituted heteroatom-containing metallocene compounds for olefin polymerization
US8242237B2 (en) 2006-12-20 2012-08-14 Exxonmobil Chemical Patents Inc. Phase separator and monomer recycle for supercritical polymerization process
ATE547469T1 (de) 2007-04-09 2012-03-15 Exxonmobil Chem Patents Inc Weiche heterogene isotaktische polypropylenzusammensetzungen
ES2446294T3 (es) 2007-06-04 2014-03-07 Exxonmobil Chemical Patents Inc. Polimerización de propileno en un sistema homogéneo en condiciones de superdisolución
US20090053959A1 (en) * 2007-08-21 2009-02-26 Sudhin Datta Soft and Elastic Nonwoven Polypropylene Compositions
US7906588B2 (en) * 2007-10-26 2011-03-15 Exxonmobil Chemical Patents Inc. Soft heterogeneous isotactic polypropylene compositions
US8318875B2 (en) 2008-01-18 2012-11-27 Exxonmobil Chemical Patents Inc. Super-solution homogeneous propylene polymerization and polypropylenes made therefrom
US7812104B2 (en) 2008-01-18 2010-10-12 Exxonmobil Chemical Patents Inc. Production of propylene-based polymers
DE102008005949A1 (de) 2008-01-24 2009-07-30 Evonik Degussa Gmbh Polyolefine mit Isotaktischen Strukturelementen, Verfahren zu deren Herstellung und deren Verwendung
US8227392B2 (en) * 2008-01-25 2012-07-24 Exxonmobil Research And Engineering Company Base stocks and lubricant blends containing poly-alpha olefins
DE102009027445A1 (de) 2009-07-03 2011-01-05 Evonik Degussa Gmbh Modifizierte Polyolefine mit besonderem Eigenschaftsprofil, Verfahren zu deren Herstellung und deren Verwendung
DE102009027447A1 (de) 2009-07-03 2011-01-05 Evonik Degussa Gmbh Modifizierte Polyolefine mit besonderem Eigenschaftsprofil, Verfahren zu deren Herstellung und deren Verwendung
DE102009027446A1 (de) 2009-07-03 2011-01-05 Evonik Degussa Gmbh Modifizierte Polyolefine mit besonderem Eigenschaftsprofil, Verfahren zu deren Herstellung und deren Verwendung
GB0918736D0 (en) 2009-10-26 2009-12-09 Isis Innovation Catalysts
US9469791B2 (en) 2011-04-28 2016-10-18 Adherent Laboratories, Inc. Polyolefin based hot melt adhesive composition
EP2573091A1 (en) 2011-09-23 2013-03-27 Lummus Novolen Technology Gmbh Process for recycling of free ligand from their corresponding metallocene complexes
KR101499819B1 (ko) * 2011-11-03 2015-03-10 주식회사 엘지화학 비담지 비균일계 폴리올레핀 중합용 촉매 조성물 및 그의 제조 방법
US10308742B2 (en) * 2014-02-11 2019-06-04 Univation Technologies, Llc Producing polyolefin products with improved stiffness, toughness, and processability
GB201407000D0 (en) * 2014-04-17 2014-06-04 Isis Innovation Catalysts
US20150299525A1 (en) 2014-04-18 2015-10-22 IFS Industries Inc. Low density and high performance packaging hot melt
JP6695341B2 (ja) 2015-01-06 2020-05-20 エスシージー ケミカルズ カンパニー，リミテッド ＳｉＯ２層状複水酸化物微小球、およびエチレン重合用の触媒担体としてのその使用
SG11201705078TA (en) 2015-01-06 2017-07-28 Scg Chemicals Co Ltd SIO<sb>2</sb>-LAYERED DOUBLE HYDROXIDE MICROSPHERES AND METHODS OF MAKING THEM
GB201608384D0 (en) 2016-05-12 2016-06-29 Scg Chemicals Co Ltd Unsymmetrical metallocene catalysts and uses thereof
US11993699B2 (en) 2018-09-14 2024-05-28 Fina Technology, Inc. Polyethylene and controlled rheology polypropylene polymer blends and methods of use
CN113474404A (zh) 2019-02-20 2021-10-01 弗纳技术股份有限公司 具有低翘曲的聚合物组合物
US20220389133A1 (en) 2019-10-30 2022-12-08 China Petroleum & Chemical Corporation Metallocene compound, and preparation method therefor and application thereof
BR112023019645A2 (pt) 2021-04-26 2023-11-07 Fina Technology Folhas de polímero catalisadas de sítio único finas

Family Cites Families (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3826075A1 (de) * 1988-07-30 1990-02-01 Hoechst Ag 1-olefin-isoblockpolymer und verfahren zu seiner herstellung
US5243001A (en) * 1990-11-12 1993-09-07 Hoechst Aktiengesellschaft Process for the preparation of a high molecular weight olefin polymer
DE59104869D1 (de) * 1990-11-12 1995-04-13 Hoechst Ag 2-Substituierte Bisindenylmetallocene, Verfahren zu ihrer Herstellung und ihre Verwendung als Katalysatoren bei der Olefinpolymerisation.
DE59209354D1 (de) 1991-03-09 1998-07-09 Targor Gmbh Verfahren zur Herstellung chemisch einheitlicher Cycloolefincopolymere
TW300901B (ko) * 1991-08-26 1997-03-21 Hoechst Ag
JP3394997B2 (ja) * 1991-10-15 2003-04-07 バーゼル・ポリオレフィン・ゲゼルシャフト・ミト・ベシュレンクテル・ハフツング 特異的に置換されたインデニル配位子を持つメタロセンを用いてオレフィンポリマーを製造する方法
TW309523B (ko) * 1991-11-30 1997-07-01 Hoechst Ag
TW318184B (ko) * 1991-11-30 1997-10-21 Hoechst Ag
AU651915B2 (en) * 1991-11-30 1994-08-04 Basell Polyolefine Gmbh Metallocenes having benzo-fused indenyl derivatives as ligands, processes for their preparation and their use as catalysts
ES2113900T3 (es) * 1992-06-13 1998-05-16 Targor Gmbh Proceso para la preparacion de catalizadores de metalocenos quirales, puenteados del tipo bisindenilo.
TW294669B (ko) * 1992-06-27 1997-01-01 Hoechst Ag
ES2128371T3 (es) 1992-08-15 1999-05-16 Targor Gmbh Procedimiento para la obtencion de poliolefinas.

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ATE177436T1 (de) 1999-03-15
ZA935924B (en) 1994-02-11
EP0584609A2 (de) 1994-03-02
CA2104036A1 (en) 1994-02-16
FI933573A7 (fi) 1994-02-16
JP3548755B2 (ja) 2004-07-28
EP0584609B1 (de) 1999-03-10
FI110103B (fi) 2002-11-29
US6028152A (en) 2000-02-22
TW309524B (ko) 1997-07-01
FI933573A0 (fi) 1993-08-12
US5672668A (en) 1997-09-30
ES2128371T3 (es) 1999-05-16
AU666565B2 (en) 1996-02-15
US5693836A (en) 1997-12-02
EP0584609A3 (en) 1994-08-24
KR100283825B1 (ko) 2001-03-02
JPH06157662A (ja) 1994-06-07
DE59309424D1 (de) 1999-04-15
AU4459193A (en) 1994-02-17
KR100301337B1 (ko) 2001-09-22
EP0882731A3 (de) 2000-05-31
EP0882731A2 (de) 1998-12-09

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