KR960010689A - 촉매 시스템 및 폴리올레핀 생성 방법 - Google Patents

촉매 시스템 및 폴리올레핀 생성 방법 Download PDF

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KR960010689A
KR960010689A KR1019950030166A KR19950030166A KR960010689A KR 960010689 A KR960010689 A KR 960010689A KR 1019950030166 A KR1019950030166 A KR 1019950030166A KR 19950030166 A KR19950030166 A KR 19950030166A KR 960010689 A KR960010689 A KR 960010689A
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metallocene
fluorenyl
radical
zirconium dichloride
group
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KR100377078B1 (ko
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엠 웰치 브루스
엘 기어츠 룰프
제이 팔락칼 시리악
엠 펫티존 테드
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제이 이이 휘립프스
휘립프스 피트로오리암 캄파니
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Abstract

브릿징된 플루오레닐-함유 메탈로센, 브릿징되지 않은 메탈로센, 및 적합한 보조 촉매로 구성되는 촉매 시스템 및 올레핀 중합체를 생산하기 위한 상기 촉매 시스템의 사용, 또한 상기 방법에 의해 생성된 신규한 올레핀 중합체.

Description

촉매 시스템 및 폴리올레핀 생성 방법
본 내용은 요부공개 건이므로 전문내용을 수록하지 않았음

Claims (34)

  1. 3이상의 분자량 분포, 즉 Mw/Ma 를 갖는 폴리올레핀을 생산하는 방법으로서, 적어도 제1 및 제2에탈로센을 결합시켜 제조한 촉매 시스템의 존재하에 적합한 중합 조건 하에서 올레핀을 중합하거나 또는 두개 이상의 올레핀을 공중합하는것으로 구성되고 상기에서 상기 제1메탈로센이 플루오레닐 기를 함유한 브릿징된 메탈로센이고 상기 제2메탈로센이 브릿징되지 않은 메탈로센이고 상기 제1메탈로센이 상기 같은 중합 조건하에서 유일한 메탈로센으로 사용된다면 제2메탈로센이 같은 중합 조건하에서 유일한 메탈로센으로 사용되는 경우 생산되는 것보다 고분자량 폴리올레핀을 생산하는 방법.
  2. 제1항에 있어서, 상기 제1메탈로센이 일반식(Z)-R'-(Z')MeQk의 플루오레닐-함유 브릿징된 메탈로센이고 식에서 R'은 Z및 Z'을 연결하는 유기 기이고; Z은 치환 또는 비치환 플루오레닐 라디칼이고; Z'은 치환 또는 비치환 플루오레닐 라디칼, 치환 또는 비치환 인데닐 라디칼, 치환 또는 비치환 시클로펜타디에닐 라디칼, 옥타히드로플루오레닐 라디칼, 또는 테트라히드로인데닐 라디칼이고, 상기 Z 및 Z'상 각각의 치환체는 C1-10히드로카르빌 또는 히드로카르빌옥시 라디칼이고; Me는 전이 금속으로 Ti, Zr, 또는 Hf이고; 각각의 Q는 수고, C1-10알킬 기, C1-10알콕시 기, C6-10아릴옥시 기, C2-10알케닐 기, C7-40아릴알킬기, C8-40알칼아릴 기, 또는 할로이고; 및 k는 전자가를 채우기에 충분한 수인 방법.
  3. 제2항에 있어서, R′이 C1-10히드로카르빌 알킬렌 라디칼인 방법.
  4. 제2항에 있어서, R′이 각각의 히드로카르빌 치환체가 1-10개 탄소 원자를 함유하는 디히드로카르빌 실릴렌 라디칼인 방법.
  5. 제1항에 있어서, 상기 제1 및 제2 메탈로센이 지르코늄-하유 메탈로센인 방법.
  6. 제5항에 있어서, 상기 제1 메탈로센이 브릿징된 메탈로센의 브릿징된 리칸드의 다른 시클로펜타디에닐-알킬 플루오레닐 기를 분리하는 원자 하나 만을 갖는 메탈로센인 방법.
  7. 제5항에 있어서, 상기 제2메탈로센이 플루오레닐 라디칼을 함유하지 않는 방법.
  8. 제5항에 있어서, 상기 제2메탈로센이 플로오레닐-함유 메탈로센인 방법.
  9. 제8항에 있어서, 상기 플오레날-함유 메탈로선에 알킬 기가 1-6개의 탄소 원자를 갖는 9-아시클릭 알킬 플루오레닐 메탈로선으로 구성되는 방법.
  10. 제5항에 있어서, 상기 제12메탈로센이 1,2-비스(플루오레닐)에탄 지르코늄 디클로라이드, 비스(플루오레닐) 디메틸 실릴 지르코늄 디클로라이드, 비스(플루오레닐) 디페닐 실릴 지르코늄 디클로라이드, 플루오레닐-메틸렌-시클로펜타디에닐 지르코늄 디클로라이드, 또는 (인데닐)-에틸렌-(플루오레닐) 지르코늄 디클로라이드인 방법.
  11. 제10항에 있어서, 상기 제2메탈로센이 시클로펜타디에닐-플루오레닐 지르코늄 디클로라이드, 비스(n-부틸 시클로펜타디에닐) 지르코늄 디클로라이드, 인데닐 펜타메틸시클로펜타디에닐 지르코늄 디클로라이드, 9-메틸플루오레닐 시클로펜타디에닐 지르코늄 디클로라이드, 또는 비스(9-메틸플루오레닐) 지르코늄 디클로라이드인 방법.
  12. 제1-11항 중 임의의 한 항에 있엇, 상기 촉매 시스템의 메탈로센이 상기 제1 및 제2메탈로센만으로 구성되는 방법.
  13. 제1-11항 중 임의의 한 한에 있어서, 각각의 R은 같거나 다르고 수소 또는 C1-14알킬 라디칼이거나 또는 두개의 R′이 그들을 연결하는 원자와 함께 고리르 형성하는 일반식 RCH=CJR의 하나 이상의 올레핀을 중합시키는 것을 구성되는 방법.
  14. 제13항에 있어서, 에틸렌이 단일 중합되는 방법.
  15. 제13항에 있어서, 에틸렌이 하나 이상의 C4-20알파 올레핀과 공중합되는 방법.
  16. 제15에 있어서, 에틸렌이 하나 이상의 C4-20알파 올레핀과 공중합되는 방법.
  17. 제16항에 있어서, 에틸렌이 헥센과 공중합되는 방법.
  18. 제1-11항 중 임의의 한 항에 있어서, 상기 제1메탈로센이 상기 제2메탈로센보다 공단량체를 병합하는데 보다 효과적이어서 중공합체의 분자량 분포 중 평균값 이하 보다는 평균값 이상에서 보다 많은 공단량체 병합이 발생한 상기 에틸렌 및 상기 고분자 알파 올레핀의 공중합체를 생산하는 방법.
  19. 제18항에 있어서, 같은 중합 조건 하의 상기 제2메탈로센의 경우 보다 상기 제1메탈로센의 경우에 수소가 중합체 분자량을 적게 변화시키는 방법.
  20. 제1-11항 중 임의의 한 항에 있어서, 중합을 수소 존재하에 수행하는 방법.
  21. 제1-11항 중 임의의 한 항에 있어서, 중합을 연속 루우프 반응기내에서 수행하는 방법.
  22. 제1-11항 중 임의의 한 항에 있어서, 입자 형태 중합 조건하에서 수행하는 방법.
  23. 제1-11항 중 임의의 한 항에 있어서, 하나 이상의 상기 메탈로센이 고체상에 퇴적되는 방법.
  24. 제23항에 있어서, 하나 이상의 상기 메탈로센이 실질적으로 중합조건 하에서 중합 매질내 불요성인 고체 형태의 알킬 알루미녹산 상에 퇴적되는 방법.
  25. 제24항에 있어서, 제1메틸로센이 알킬 알루미녹산 상에 지지되고나서 지지된 메탈로센이 제2메탈로센과 합쳐지는 방법.
  26. 제25항에 있어서, 상기 고체 형태의 알킬 알루미녹산을 유기알루미녹산의 용액과 유기 보록신을 메탈로센을 위한 보조 촉매로서 사용하기에 적합한 고체를 생산하는데 충분한 조건하에서 접촉시켜 제조하는 방법.
  27. 하기로 구성된 올레핀 또는 올레핀의 혼합물로부터 분자량 분포, 즉 Mw/Ma 이 3 이상인 폴리올레핀을 제조하는데 적합한 촉매 시스템; (1) 적어도 다른 제1 및 제2메탈로센으로서, 상기 제1메탈로센이 플루오레닐기를 함유한 브릿징된 메탈로센이고 상기 제2메탈로센이 브릿징되지 않은 메탈로센이고 상기 제1메탈로센이 유일한 메탈로센으로 사용된다면 같은 중합 조건하에서 제2메탈로센이 유일한 메탈로센으로 사용되는 경우 생산되는 것보다 고분자량의 폴리올레핀을 생산하는 메찰로센, 및 (2) 메탈로센에 적합한 보조 촉매.
  28. 제27항에 있어서, 상기 제1메탈로센이 같은 중합 조건 하에서 상기 제2메탈로센보다 공단량체를 병합하는데 효과적인 촉매 시스템.
  29. 제28항에 있어서, 수소가 같은 중합 조건 하의 상기 제2메탈로센의 경우 보다 상기 제1메탈로센의 경우에 중합체 분자량을 적게 변화시키는 촉매 시스템.
  30. 제27항에 있어서, 상기 촉매 시스템을 상기 제1메탈로센을 실질적으로 중합 조건 하에서 중합 매질내불용성인 고체 형태의 알킬 알루미녹산 상에 지지시키고 나서 지지된 메탈로센을 상기 제2메탈로센과 혼합시켜제조하는 촉매 시스템.
  31. 제30항에 있어서, 상기 고체 형태의 알킬 알루미녹산을 유기알루미녹산의 용애과 유기 보록신을 메탈로센을 위한 보조 촉매로서 사용하기에 적합한 고체를 생산하는데 충분한 조건하에서 접촉시켜 제조하는 촉매 시스템.
  32. 제27-31항 중 임의의 한 항에 있어서, 상기 제1메탈로센이 일반식(Z)-R′-(Z′)MeQK의 플루오레닐-함유 브릿징된 메탈로센이고 식에서 R′은 Z 및 Z′을 연결하는 유기 기이고; Z은 치환 또는 비치환 플루오레닐 라디칼이고; Z′은 치환 또는 비치환 플루오레닐 라디칼, 치환 또는 비치환 인데닐 라디칼, 치환 또는 비치환 시클로펜타디에닐 라디칼, 옥타히드로플루오레닐 라디칼, 또는 테트라히드로인데닐 라디칼이고, 상기 Z 및 Z′상 각각의 치환체는 C1-10히드로카르빌 또는 히드로바르빌옥시 라디칼이고;Me는 전이 금속으로 Ti, Zr, 또는 Hf이고; 각각의 Q는 수소, C1-10알킬 기, C1-10알콕시 기, C6-10아릴 기, C6-10아릴옥시 기, C2-10알케닐 기, C7-40아릴알킬 기, C8-40알길아릴 기, 또는 할로이고; 및 k는 전저가를 채우기에 충분한 수인 방법.
  33. 제27-31항 중 임의의 한 항에 있어서, 상기 촉매 시스템의 메탈로센이 상기 제1 및 제2메탈로센 만으로 구성되고 상기 메탈로센이 지르코늄-함유 메탈로센인 촉매 시스템.
  34. 제27-31항 중 임의의 한 항에 있어서, 상기 제1메탈로센이 1,2-비스(플루오레닐) 에탄 지르코늄 디클로라이드, 비스(플루오레닐)(디메틸) 실릴 지르코늄 디클로라이드, 비스(플루오레닐)(디페닐) 실릴 지르코늄디클로라이드, (플루오레닐)-메틸렌-(시클로펜타디에닐) 지르코늄 디클로라이드, 또는 (인데닐)-에틸렌-(플루오레닐) 지르코늄 디클로라이드이고 상기 제2메탈로센이 (시클로펜타디에닐)(플루오레닐) 지르코늄 디지르코늄 디클로라이드, (9-메틸플루오레닐)(시클로펜타디에닐)지르코늄 디클로라이드, 또는 비스 (9-메틸플루오레닐) 지르코늄 디클로라이드인 촉매 시스템.
    ※ 참고사항 : 최초출원 내용에 의하여 공개하는 것임.
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Publication number Priority date Publication date Assignee Title
CA2067525C (en) * 1991-05-09 1998-09-15 Helmut G. Alt Organometallic fluorenyl compounds, preparation and use
US6143854A (en) * 1993-08-06 2000-11-07 Exxon Chemical Patents, Inc. Polymerization catalysts, their production and use
US5770755A (en) * 1994-11-15 1998-06-23 Phillips Petroleum Company Process to prepare polymeric metallocenes
BE1009186A3 (fr) * 1995-03-13 1996-12-03 Solvay Solide catalytique pour la (co)polymerisation d'ethylene, procede pour sa preparation, systeme catalytique pour la (co)polymerisation d'ethylene et procede de (co)polymerisation d'ethylene.
FI952098A7 (fi) * 1995-05-02 1996-11-03 Borealis As LLDPE-polymeerien valmistusmenetelmä
EP0786466B1 (en) * 1996-01-25 2003-04-16 Tosoh Corporation Olefin polymerisation process which comprises a transition metal catalyst.
US5726264A (en) * 1996-06-14 1998-03-10 Phillips Petroleum Company Processes to produce metallocene compounds and polymerization processes therewith
DE19637669A1 (de) 1996-09-16 1998-03-19 Hoechst Ag Verfahren zur Herstellung einer methylenverbrückten Biscyclopentadienylverbindung
US6180736B1 (en) * 1996-12-20 2001-01-30 Exxon Chemical Patents Inc High activity metallocene polymerization process
US5886202A (en) * 1997-01-08 1999-03-23 Jung; Michael Bridged fluorenyl/indenyl metallocenes and the use thereof
DE19709866A1 (de) 1997-03-11 1998-09-17 Basf Ag Geträgertes Katalysatorsystem zur Polymerisation von Alk-1-enen
JP2001514287A (ja) 1997-08-27 2001-09-11 ザ ダウ ケミカル カンパニー アルファ−オレフィン類とビニル芳香族モノマーとのインターポリマー類のレオロジー変性
US6069213A (en) * 1997-12-16 2000-05-30 Union Carbide Chemicals & Plastics Technology Corporation Mixed catalyst system
DE69907785T2 (de) 1998-03-09 2004-02-12 Basell Poliolefine Italia S.P.A. Mehrstufiges Verfahren zur Olefinpolymerisation
US6207606B1 (en) * 1998-05-15 2001-03-27 Univation Technologies, Llc Mixed catalysts and their use in a polymerization process
BR9910611B1 (pt) 1998-05-18 2009-05-05 processo para produção de uma composição de catalisador.
US6245868B1 (en) 1998-05-29 2001-06-12 Univation Technologies Catalyst delivery method, a catalyst feeder and their use in a polymerization process
CA2245375C (en) 1998-08-19 2006-08-15 Nova Chemicals Ltd. Dual reactor polyethylene process using a phosphinimine catalyst
US6258903B1 (en) * 1998-12-18 2001-07-10 Univation Technologies Mixed catalyst system
US6818585B2 (en) 1998-12-30 2004-11-16 Univation Technologies, Llc Catalyst compounds, catalyst systems thereof and their use in a polymerization process
US6239060B1 (en) 1998-12-31 2001-05-29 Phillips Petroleum Company Supported metallocene catalyst system and method for polymerizing olefins
US6339134B1 (en) 1999-05-06 2002-01-15 Univation Technologies, Llc Polymerization process for producing easier processing polymers
DE19940151A1 (de) * 1999-08-24 2001-03-01 Targor Gmbh Geträgerte Katalysatorsysteme, Verfahren zu ihrer Herstellung und Verfahren zur Herstellung von Poly-1-alkenen mit bimodaler oder multimodaler Molekularmassenverteilung
CN1217733C (zh) 1999-12-16 2005-09-07 菲利浦石油公司 有机金属化合物催化剂
US20080281063A9 (en) * 1999-12-30 2008-11-13 Sukhadia Ashish M Ethylene polymers and copolymers with high optical opacity and methods of making the same
US7041617B2 (en) 2004-01-09 2006-05-09 Chevron Phillips Chemical Company, L.P. Catalyst compositions and polyolefins for extrusion coating applications
JP2001316415A (ja) * 2000-05-10 2001-11-13 Tosoh Corp オレフィン重合用触媒およびオレフィン重合体の製造方法
JP2001316414A (ja) * 2000-05-10 2001-11-13 Tosoh Corp オレフィン重合用触媒およびオレフィン重合体の製造方法
EP1201683A1 (fr) * 2000-10-30 2002-05-02 SOLVAY POLYOLEFINS EUROPE - BELGIUM (Société Anonyme) Procédé pour la polymérisation des alpha-oléfines
US6534609B2 (en) * 2001-03-13 2003-03-18 Chevron Phillips Chemical Company Lp Method for making and using a metallocene catalyst system
CA2347410C (en) 2001-05-11 2009-09-08 Nova Chemicals Corporation Solution polymerization process catalyzed by a phosphinimine catalyst
SG96700A1 (en) * 2001-09-27 2003-06-16 Sumitomo Chemical Co Catalyst component for addition polymerization, process for producing catalyst for addition polymerization and process for producing addition polymer
JP2003096125A (ja) * 2001-09-27 2003-04-03 Sumitomo Chem Co Ltd 付加重合用触媒成分、付加重合用触媒および付加重合体の製造方法、並びにメタロセン系遷移金属化合物の用途
CA2480006A1 (en) * 2002-04-12 2003-10-23 Hong Yang Azaborolyl group 4 metal complexes, catalysts and olefin polymerization process
US7550528B2 (en) 2002-10-15 2009-06-23 Exxonmobil Chemical Patents Inc. Functionalized olefin polymers
ES2394304T3 (es) * 2002-10-15 2013-01-30 Exxonmobil Chemical Patents, Inc. Sistema de múltiples catalizadores para la polimerización de olefinas y polímeros producidos a partir de éstos
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
US7223822B2 (en) 2002-10-15 2007-05-29 Exxonmobil Chemical Patents Inc. Multiple catalyst and reactor system for olefin polymerization and polymers produced therefrom
WO2004094487A1 (en) 2003-03-21 2004-11-04 Dow Global Technologies, Inc. Morphology controlled olefin polymerization process
DE102004008313B4 (de) * 2004-02-20 2014-01-16 Wankel Super Tec Gmbh Kreiskolbenbrennkraftmaschine mit einer verbesserten Innendichtung
ATE361323T1 (de) * 2004-03-12 2007-05-15 Saudi Basic Ind Corp Katalysatorzusammensetzung für die polymerisation von olefinen und polymerisationsverfahren unter dessen verwendung
JP4752187B2 (ja) * 2004-03-24 2011-08-17 東ソー株式会社 エチレン系樹脂組成物
US7696280B2 (en) 2004-04-30 2010-04-13 Chevron Phillips Chemical Company, Lp HDPE resins for use in pressure pipe and related applications
US7294599B2 (en) 2004-06-25 2007-11-13 Chevron Phillips Chemical Co. Acidic activator-supports and catalysts for olefin polymerization
US7163906B2 (en) * 2004-11-04 2007-01-16 Chevron Phillips Chemical Company, Llp Organochromium/metallocene combination catalysts for producing bimodal resins
WO2006065651A2 (en) 2004-12-17 2006-06-22 Dow Global Technologies Inc. Rheology modified polyethylene compositions
KR100753478B1 (ko) * 2005-02-15 2007-08-31 주식회사 엘지화학 혼성 담지 메탈로센 촉매 및 이를 이용한 폴리에틸렌 공중합체의 제조방법
US20060205898A1 (en) * 2005-03-08 2006-09-14 Goyal Shivendra K Dual reactor polyethylene resins with balanced physical properties
US20060235147A1 (en) * 2005-04-14 2006-10-19 Nova Chemicals (International) S.A. Dual reactor polyethylene resins for food packaging - films, bags and pouches
US20060247373A1 (en) * 2005-04-28 2006-11-02 Nova Chemicals (International) S.A. Dual reactor polyethylene resins for electronic packaging-films, tapes, bags and pouches
EP1734058A1 (en) * 2005-06-13 2006-12-20 Total Petrochemicals Research Feluy Ethylene and alpha-olefins polymerisation catalyst system based on fluorenyl ligand
US7312283B2 (en) † 2005-08-22 2007-12-25 Chevron Phillips Chemical Company Lp Polymerization catalysts and process for producing bimodal polymers in a single reactor
US7226886B2 (en) * 2005-09-15 2007-06-05 Chevron Phillips Chemical Company, L.P. Polymerization catalysts and process for producing bimodal polymers in a single reactor
EP1803747A1 (en) 2005-12-30 2007-07-04 Borealis Technology Oy Surface-modified polymerization catalysts for the preparation of low-gel polyolefin films
US7517939B2 (en) 2006-02-02 2009-04-14 Chevron Phillips Chemical Company, Lp Polymerization catalysts for producing high molecular weight polymers with low levels of long chain branching
US7619047B2 (en) * 2006-02-22 2009-11-17 Chevron Phillips Chemical Company, Lp Dual metallocene catalysts for polymerization of bimodal polymers
KR100886681B1 (ko) * 2006-03-31 2009-03-04 주식회사 엘지화학 선형 저밀도 폴리에틸렌의 제조방법
JP5306183B2 (ja) * 2006-05-02 2013-10-02 ダウ グローバル テクノロジーズ エルエルシー 高密度ポリエチレン組成物、それを作製する方法、それから作製された製品、およびそのような製品を作製する方法
US7456244B2 (en) * 2006-05-23 2008-11-25 Dow Global Technologies High-density polyethylene compositions and method of making the same
CN101490163A (zh) * 2007-05-02 2009-07-22 陶氏环球技术公司 高密度聚乙烯组合物、其制备方法、由其制得的注塑制品以及该制品的制备方法
US7572948B2 (en) * 2007-05-16 2009-08-11 Chevron Phillips Chemical Company, Lp Fulvene purification
US7897539B2 (en) * 2007-05-16 2011-03-01 Chevron Phillips Chemical Company Lp Methods of preparing a polymerization catalyst
US8058200B2 (en) * 2007-05-17 2011-11-15 Chevron Phillips Chemical Company, L.P. Catalysts for olefin polymerization
US7981517B2 (en) * 2007-08-28 2011-07-19 Dow Global Technologies Inc. Bituminous compositions and methods of making and using same
US7799721B2 (en) * 2007-09-28 2010-09-21 Chevron Phillips Chemical Company Lp Polymerization catalysts for producing polymers with high comonomer incorporation
US8119553B2 (en) * 2007-09-28 2012-02-21 Chevron Phillips Chemical Company Lp Polymerization catalysts for producing polymers with low melt elasticity
ES2408589T3 (es) 2008-12-18 2013-06-21 Univation Technologies, Llc Método para tratamiento de un lecho de siembra para una reacción de polimerización
US8604142B2 (en) 2009-01-23 2013-12-10 Evonik Oxeno Gmbh Polyolefin gas phase polymerization with 3-substituted C4-10-alkene
US9056970B2 (en) 2009-01-30 2015-06-16 Dow Global Technologies Llc High-density polyethylene compositions, method of producing the same, closure devices made therefrom, and method of making such closure devices
KR101673043B1 (ko) 2009-06-16 2016-11-04 셰브론 필립스 케미컬 컴퍼니 엘피 메탈로센-ｓｓａ 촉매시스템을 이용한 알파 올레핀 올리고머화 및 윤활제 블렌드 제조를 위한 생성된 폴리알파올레핀의 용도
MX2012000254A (es) 2009-06-29 2012-01-25 Chevron Philips Chemical Company Lp El uso de catalizadores de depuracion de hidrogeno para controlar niveles de hidrogeno y peso molecular de polimero en un reactor de polimerizacion.
SG176975A1 (en) 2009-06-29 2012-02-28 Chevron Phillips Chemical Co Dual metallocene catalyst systems for decreasing melt index and increasing polymer production rates
US8716414B2 (en) 2009-11-06 2014-05-06 Lg Chem, Ltd. Mixed metallocene catalyst composition and method for preparing polyolefin using the same
EP2402376A1 (en) * 2010-06-29 2012-01-04 Borealis AG Process for producing a prepolymerised catalyst, such prepolymerised catalyst and its use for producing a polymer
US8476394B2 (en) 2010-09-03 2013-07-02 Chevron Philips Chemical Company Lp Polymer resins having improved barrier properties and methods of making same
US8440772B2 (en) 2011-04-28 2013-05-14 Chevron Phillips Chemical Company Lp Methods for terminating olefin polymerizations
US8487053B2 (en) 2011-11-30 2013-07-16 Chevron Phillips Chemical Company Lp Methods for removing polymer skins from reactor walls
US8501882B2 (en) 2011-12-19 2013-08-06 Chevron Phillips Chemical Company Lp Use of hydrogen and an organozinc compound for polymerization and polymer property control
US8703883B2 (en) 2012-02-20 2014-04-22 Chevron Phillips Chemical Company Lp Systems and methods for real-time catalyst particle size control in a polymerization reactor
US10273315B2 (en) 2012-06-20 2019-04-30 Chevron Phillips Chemical Company Lp Methods for terminating olefin polymerizations
US8916494B2 (en) 2012-08-27 2014-12-23 Chevron Phillips Chemical Company Lp Vapor phase preparation of fluorided solid oxides
US8940842B2 (en) 2012-09-24 2015-01-27 Chevron Phillips Chemical Company Lp Methods for controlling dual catalyst olefin polymerizations
US8937139B2 (en) 2012-10-25 2015-01-20 Chevron Phillips Chemical Company Lp Catalyst compositions and methods of making and using same
US8895679B2 (en) 2012-10-25 2014-11-25 Chevron Phillips Chemical Company Lp Catalyst compositions and methods of making and using same
KR101437509B1 (ko) 2012-12-03 2014-09-03 대림산업 주식회사 성형성 및 기계적 물성이 우수한 멀티모달 폴리올레핀 수지 제조를 위한 촉매 조성물 및 이를 이용한 중합 방법
IN2015DN03815A (ko) 2012-12-28 2015-10-02 Univation Tech Llc
RU2647855C2 (ru) 2013-01-14 2018-03-21 ЮНИВЕЙШН ТЕКНОЛОДЖИЗ, ЭлЭлСи Способы получения каталитических систем с повышенной производительностью
US9034991B2 (en) 2013-01-29 2015-05-19 Chevron Phillips Chemical Company Lp Polymer compositions and methods of making and using same
US8877672B2 (en) 2013-01-29 2014-11-04 Chevron Phillips Chemical Company Lp Catalyst compositions and methods of making and using same
US8815357B1 (en) 2013-02-27 2014-08-26 Chevron Phillips Chemical Company Lp Polymer resins with improved processability and melt fracture characteristics
US9181369B2 (en) 2013-03-11 2015-11-10 Chevron Phillips Chemical Company Lp Polymer films having improved heat sealing properties
US10577440B2 (en) 2013-03-13 2020-03-03 Chevron Phillips Chemical Company Lp Radically coupled resins and methods of making and using same
US10654948B2 (en) 2013-03-13 2020-05-19 Chevron Phillips Chemical Company Lp Radically coupled resins and methods of making and using same
US9828451B2 (en) 2014-10-24 2017-11-28 Chevron Phillips Chemical Company Lp Polymers with improved processability for pipe applications
EP3294781B1 (en) 2015-05-08 2021-08-04 ExxonMobil Chemical Patents Inc. Polymerization process
KR102578006B1 (ko) 2015-05-11 2023-09-12 더블유.알. 그레이스 앤드 캄파니-콘. 개질된 점토, 지지된 메탈로센 중합 촉매의 제조 방법, 제조된 촉매, 및 이의 용도
US10940460B2 (en) 2015-05-11 2021-03-09 W. R. Grace & Co.-Conn. Process to produce modified clay, modified clay produced and use thereof
US9708426B2 (en) 2015-06-01 2017-07-18 Chevron Phillips Chemical Company Lp Liquid-solid sampling system for a loop slurry reactor
WO2017078974A1 (en) 2015-11-05 2017-05-11 Chevron Phillips Chemical Company Lp Radically coupled resins and methods of making and using same
US9645131B1 (en) 2015-12-04 2017-05-09 Chevron Phillips Chemical Company Lp Polymer compositions having improved processability and methods of making and using same
US9645066B1 (en) 2015-12-04 2017-05-09 Chevron Phillips Chemical Company Lp Polymer compositions having improved processability and methods of making and using same
US10005861B2 (en) 2016-06-09 2018-06-26 Chevron Phillips Chemical Company Lp Methods for increasing polymer production rates with halogenated hydrocarbon compounds
WO2018063765A1 (en) 2016-09-27 2018-04-05 Exxonmobil Chemical Patents Inc. Polymerization process
WO2018063767A1 (en) 2016-09-27 2018-04-05 Exxonmobil Chemical Patents Inc. Polymerization process
WO2018063764A1 (en) 2016-09-27 2018-04-05 Exxonmobil Chemical Patents Inc. Polymerization process
WO2018118155A1 (en) 2016-12-20 2018-06-28 Exxonmobil Chemical Patents Inc. Polymerization process
EP3583140B1 (en) 2017-02-20 2023-03-08 ExxonMobil Chemical Patents Inc. Supported catalyst systems and processes for use thereof
US10723819B2 (en) 2017-02-20 2020-07-28 Exxonmobil Chemical Patents, Inc. Supported catalyst systems and processes for use thereof
US10550252B2 (en) 2017-04-20 2020-02-04 Chevron Phillips Chemical Company Lp Bimodal PE resins with improved melt strength
WO2019027585A1 (en) 2017-08-04 2019-02-07 Exxonmobil Chemical Patents Inc. MIXED CATALYSTS COMPRISING UNDRAWNED HAFNOCENES WITH -CH2-SIME3 FRACTIONS
US10844150B2 (en) 2017-08-04 2020-11-24 Exxonmobil Chemical Patents Inc. Mixed catalysts with 2,6-bis(imino)pyridyl iron complexes and bridged hafnocenes
US10703838B2 (en) 2017-10-31 2020-07-07 Exxonmobil Chemical Patents Inc. Mixed catalyst systems with four metallocenes on a single support
CN115850552B (zh) 2017-12-01 2024-08-06 埃克森美孚化学专利公司 催化剂体系和使用其的聚合方法
US10926250B2 (en) 2017-12-01 2021-02-23 Exxonmobil Chemical Patents Inc. Catalyst systems and polymerization processes for using the same
WO2019118073A1 (en) 2017-12-13 2019-06-20 Exxonmobil Chemical Patents Inc. Deactivation methods for active components from gas phase polyolefin polymerization process
US10865258B2 (en) 2018-01-31 2020-12-15 Exxonmobil Chemical Patents Inc. Mixed catalyst systems containing bridged metallocenes with a pendant group 13 element, processes for making a polymer product using same, and products made from same
US10851187B2 (en) 2018-01-31 2020-12-01 Exxonmobil Chemical Patents Inc. Bridged metallocene catalysts with a pendant group 13 element, catalyst systems containing same, processes for making a polymer product using same, and products made from same
WO2019173030A1 (en) 2018-03-08 2019-09-12 Exxonmobil Chemical Patents Inc. Methods of preparing and monitoring a seed bed for polymerization reactor startup
US11447587B2 (en) 2018-05-02 2022-09-20 Exxonmobil Chemical Patents Inc. Methods for scale-up from a pilot plant to a larger production facility
US11459408B2 (en) 2018-05-02 2022-10-04 Exxonmobil Chemical Patents Inc. Methods for scale-up from a pilot plant to a larger production facility
WO2020014138A1 (en) 2018-07-09 2020-01-16 Exxonmobil Chemical Patents Inc. Polyethylene cast films and methods for making the same
WO2020023207A1 (en) 2018-07-26 2020-01-30 Exxonmobil Chemical Patents Inc. Multilayer foam films and methods for making the same
EP3880739B1 (en) 2018-11-13 2025-03-19 ExxonMobil Chemical Patents Inc. Polyethylene films
EP3880738B1 (en) 2018-11-13 2025-03-19 ExxonMobil Chemical Patents Inc. Polyethylene blends and films
US10774161B2 (en) 2019-01-31 2020-09-15 Chevron Phillips Chemical Company Lp Systems and methods for polyethylene recovery with low volatile content
WO2020163079A1 (en) 2019-02-06 2020-08-13 Exxonmobil Chemical Patents Inc. Films and backsheets for hygiene articles
WO2021126458A1 (en) 2019-12-17 2021-06-24 Exxonmobil Chemical Patents Inc. Films made of polyethylene blends for improved sealing performance and mechanical properties
EP4097153A1 (en) 2020-01-27 2022-12-07 Formosa Plastics Corporation, U.S.A. Process for preparing catalysts and catalyst compositions
US11339229B2 (en) 2020-01-27 2022-05-24 Formosa Plastics Corporation, U.S.A. Process for preparing catalysts and catalyst compositions
WO2021183337A1 (en) 2020-03-12 2021-09-16 Exxonmobil Chemical Patents Inc. Films made of polyethylene blends for improved bending stiffness and high md tear resistance
WO2022232760A1 (en) 2021-04-30 2022-11-03 Exxonmobil Chemical Patents Inc. Processes for transitioning between different polymerization catalysts in a polymerization reactor
US12077616B2 (en) 2021-12-15 2024-09-03 Chevron Phillips Chemical Company Lp Production of polyethylene and ethylene oligomers from ethanol and the use of biomass and waste streams as feedstocks to produce the ethanol
US11845814B2 (en) 2022-02-01 2023-12-19 Chevron Phillips Chemical Company Lp Ethylene polymerization processes and reactor systems for the production of multimodal polymers using combinations of a loop reactor and a fluidized bed reactor
US12466900B2 (en) 2022-04-19 2025-11-11 Chevron Phillips Chemical Company Lp Loop slurry periodogram control to prevent reactor fouling and reactor shutdowns
WO2023239560A1 (en) 2022-06-09 2023-12-14 Formosa Plastics Corporaton, U.S.A. Clay composite support-activators and catalyst compositions
US12606648B2 (en) 2023-07-13 2026-04-21 Chevron Phillips Chemical Company Lp Centralized hydrocarbon treatment in a polymer production process
US20250066274A1 (en) 2023-08-22 2025-02-27 Chevron Phillips Chemical Company Lp Integrated processes utilizing water electrolysis and oxidative dehydrogenation of ethane

Family Cites Families (46)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1720793A (en) 1928-03-05 1929-07-16 Francis A Kunkle Heat-operated alarm
US3280220A (en) * 1963-04-29 1966-10-18 Phillips Petroleum Co Blend of high density polyethylene-1-butene copolymer
US3242099A (en) 1964-03-27 1966-03-22 Union Carbide Corp Olefin polymerization catalysts
JPS5610506A (en) * 1979-07-09 1981-02-03 Mitsui Petrochem Ind Ltd Production of ethylene polymer composition
US4547551A (en) * 1982-06-22 1985-10-15 Phillips Petroleum Company Ethylene polymer blends and process for forming film
US4461873A (en) * 1982-06-22 1984-07-24 Phillips Petroleum Company Ethylene polymer blends
CA1231702A (en) * 1983-06-06 1988-01-19 John A. Ewen Process and catalyst for producing reactor blend polyolefins
US4935474A (en) * 1983-06-06 1990-06-19 Exxon Research & Engineering Company Process and catalyst for producing polyethylene having a broad molecular weight distribution
US4530914A (en) * 1983-06-06 1985-07-23 Exxon Research & Engineering Co. Process and catalyst for producing polyethylene having a broad molecular weight distribution
US4937299A (en) * 1983-06-06 1990-06-26 Exxon Research & Engineering Company Process and catalyst for producing reactor blend polyolefins
US5324800A (en) 1983-06-06 1994-06-28 Exxon Chemical Patents Inc. Process and catalyst for polyolefin density and molecular weight control
US4808561A (en) 1985-06-21 1989-02-28 Exxon Chemical Patents Inc. Supported polymerization catalyst
US4939217A (en) * 1987-04-03 1990-07-03 Phillips Petroleum Company Process for producing polyolefins and polyolefin catalysts
US5064797A (en) * 1987-04-03 1991-11-12 Phillips Petroleum Company Process for producing polyolefins and polyolefin catalysts
US4794096A (en) 1987-04-03 1988-12-27 Fina Technology, Inc. Hafnium metallocene catalyst for the polymerization of olefins
US4975403A (en) * 1987-09-11 1990-12-04 Fina Technology, Inc. Catalyst systems for producing polyolefins having a broad molecular weight distribution
US4952714A (en) * 1988-06-22 1990-08-28 Exxon Chemical Patents Inc. Non-aqueous process for the preparation of alumoxanes
US5001244A (en) * 1988-06-22 1991-03-19 Exxon Chemical Patents Inc. Metallocene, hydrocarbylaluminum and hydrocarbylboroxine olefin polymerization catalyst
US4892851A (en) 1988-07-15 1990-01-09 Fina Technology, Inc. Process and catalyst for producing syndiotactic polyolefins
US5155080A (en) 1988-07-15 1992-10-13 Fina Technology, Inc. Process and catalyst for producing syndiotactic polyolefins
KR930002411B1 (ko) 1988-09-14 1993-03-30 미쓰이세끼유 가가꾸고오교오 가부시끼가이샤 벤젠불용성 유기알루미늄 옥시화합물 및 그 제조방법
US5043515A (en) * 1989-08-08 1991-08-27 Shell Oil Company Ethylene oligomerization catalyst and process
DE3840772A1 (de) * 1988-12-03 1990-06-07 Hoechst Ag Verfahren zur herstellung einer heterogenen metallocenkatalysatorkomponente
IT8919252A0 (it) * 1989-01-31 1989-01-31 Ilano Catalizzatori per la polimerizzazione di olefine.
DE3907964A1 (de) * 1989-03-11 1990-09-13 Hoechst Ag Verfahren zur herstellung eines syndiotaktischen polyolefins
DE3922546A1 (de) 1989-07-08 1991-01-17 Hoechst Ag Verfahren zur herstellung von cycloolefinpolymeren
IT1231774B (it) * 1989-08-03 1991-12-21 Enichem Anic Spa Catalizzatore e procedimento per la polimerizzazione e per la copolimerizzazione di alfa olefine.
US5026798A (en) * 1989-09-13 1991-06-25 Exxon Chemical Patents Inc. Process for producing crystalline poly-α-olefins with a monocyclopentadienyl transition metal catalyst system
US5057475A (en) * 1989-09-13 1991-10-15 Exxon Chemical Patents Inc. Mono-Cp heteroatom containing group IVB transition metal complexes with MAO: supported catalyst for olefin polymerization
US5117020A (en) * 1989-10-30 1992-05-26 Fina Research, S.A. Process for the preparation of metallocenes
US5032562A (en) * 1989-12-27 1991-07-16 Mobil Oil Corporation Catalyst composition and process for polymerizing polymers having multimodal molecular weight distribution
US5032651A (en) * 1990-05-29 1991-07-16 Phillips Petroleum Company Method for producing olefin polymer blends utilizing a chromium-zirconium dual catalyst system
US5082677A (en) * 1990-07-19 1992-01-21 Avi Bear Packaging means and method for shipping pastries
US5436305A (en) * 1991-05-09 1995-07-25 Phillips Petroleum Company Organometallic fluorenyl compounds, preparation, and use
US5451649A (en) * 1991-05-09 1995-09-19 Phillips Petroleum Company Organometallic fluorenyl compounds, preparation, and use
ES2082274T3 (es) * 1991-05-27 1996-03-16 Hoechst Ag Procedimiento para la preparacion de poliolefinas sindiotacticas con amplia distribucion de masas moleculares.
DE59209897D1 (de) * 1991-05-27 2001-04-26 Targor Gmbh Verfahren zur Herstellung von Polyolefinen mit breiter Molmassenverteilung
KR930006091A (ko) * 1991-09-18 1993-04-20 제이 이이 휘립프스 폴리에틸렌 블렌드 및 그로부터 제조된 필름, 병 또는 파이프
CA2078366A1 (en) * 1991-09-18 1993-03-19 Joel L. Martin Polyethylene blends
US5281679A (en) 1991-11-07 1994-01-25 Exxon Chemical Patents Inc. Catalyst and method of broadening polymer molecular weight distribution and increasing polymer tensile impact strength and products made thereof
JP3153000B2 (ja) 1992-06-11 2001-04-03 三菱化学株式会社 α‐オレフィン重合体の製造法
DE4333128A1 (de) * 1993-09-29 1995-03-30 Hoechst Ag Verfahren zur Herstellung von Polyolefinen
FI945959A7 (fi) * 1993-12-21 1995-06-22 Targor Gmbh Metalloseenejä ja niiden käyttö katalyytteinä
US5498581A (en) * 1994-06-01 1996-03-12 Phillips Petroleum Company Method for making and using a supported metallocene catalyst system
US8089993B2 (en) 2008-09-09 2012-01-03 Nec Laboratories America, Inc. Sliceable router with packet over optical OFDM transmission
US9214393B2 (en) 2012-04-02 2015-12-15 Taiwan Semiconductor Manufacturing Co., Ltd. Surface tension modification using silane with hydrophobic functional group for thin film deposition

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NO952835D0 (no) 1995-07-17
DE69532461D1 (de) 2004-02-26
HU218866B (hu) 2000-12-28
HUT72277A (en) 1996-04-29
US5534473A (en) 1996-07-09
FI953456A7 (fi) 1996-03-14
TW357157B (en) 1999-05-01
CN1123287A (zh) 1996-05-29
ZA957695B (en) 1996-04-15
CA2153520C (en) 1999-08-31
NO310363B1 (no) 2001-06-25
ATE258194T1 (de) 2004-02-15
SK112495A3 (en) 1996-04-03
SG54082A1 (en) 1998-11-16
US5594078A (en) 1997-01-14
FI953456L (fi) 1996-03-14
BR9504008A (pt) 1996-09-24
EP0705851A2 (en) 1996-04-10
ES2210267T3 (es) 2004-07-01
KR100377078B1 (ko) 2003-06-18
HU9502155D0 (en) 1995-09-28
EP0705851B1 (en) 2004-01-21
JPH08100018A (ja) 1996-04-16
EP0705851A3 (en) 1997-03-05
CZ235195A3 (en) 1996-04-17
AU677128B2 (en) 1997-04-10
PL310392A1 (en) 1996-03-18
BG99794A (bg) 1996-06-28
EP0705851B9 (en) 2004-08-11
AU3037195A (en) 1996-04-04
FI953456A0 (fi) 1995-07-17
NO952835L (no) 1996-03-14
CN1053676C (zh) 2000-06-21
CA2153520A1 (en) 1996-03-14
DE69532461T2 (de) 2004-10-21

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