DE3751495D1 - Hafnium-Metalocen-Katalysator für Olefinpolymerisation. - Google Patents

Hafnium-Metalocen-Katalysator für Olefinpolymerisation.

Info

Publication number
DE3751495D1
DE3751495D1 DE3751495T DE3751495T DE3751495D1 DE 3751495 D1 DE3751495 D1 DE 3751495D1 DE 3751495 T DE3751495 T DE 3751495T DE 3751495 T DE3751495 T DE 3751495T DE 3751495 D1 DE3751495 D1 DE 3751495D1
Authority
DE
Germany
Prior art keywords
catalyst
hafnium
olefin polymerization
alumoxane
discovered
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Fee Related
Application number
DE3751495T
Other languages
English (en)
Other versions
DE3751495T2 (de
Inventor
John A Ewen
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Fina Technology Inc
Original Assignee
Fina Technology Inc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
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First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=26710837&utm_source=***_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=DE3751495(D1) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Application filed by Fina Technology Inc filed Critical Fina Technology Inc
Application granted granted Critical
Publication of DE3751495D1 publication Critical patent/DE3751495D1/de
Publication of DE3751495T2 publication Critical patent/DE3751495T2/de
Anticipated expiration legal-status Critical
Expired - Fee Related legal-status Critical Current

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F10/00Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00Polymerisation catalysts
    • C08F4/42Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44Metals; 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
    • C08F4/60Metals; 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 together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62Refractory metals or compounds thereof
    • C08F4/64Titanium, zirconium, hafnium or compounds thereof
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F110/00Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F110/04Monomers containing three or four carbon atoms
    • C08F110/06Propene
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00Polymerisation catalysts
    • C08F4/42Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44Metals; 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
    • C08F4/60Metals; 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 together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62Refractory metals or compounds thereof
    • C08F4/64Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/65912Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with an organoaluminium compound
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00Polymerisation catalysts
    • C08F4/42Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44Metals; 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
    • C08F4/60Metals; 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 together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62Refractory metals or compounds thereof
    • C08F4/64Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/6592Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring
    • C08F4/65922Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring containing at least two cyclopentadienyl rings, fused or not
    • C08F4/65927Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring containing at least two cyclopentadienyl rings, fused or not two cyclopentadienyl rings being mutually bridged
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10STECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S526/00Synthetic resins or natural rubbers -- part of the class 520 series
    • Y10S526/943Polymerization with metallocene catalysts

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
DE3751495T 1987-04-03 1987-09-21 Hafnium-Metalocen-Katalysator für Olefinpolymerisation. Expired - Fee Related DE3751495T2 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US3434187A 1987-04-03 1987-04-03
US07/096,075 US4794096A (en) 1987-04-03 1987-09-11 Hafnium metallocene catalyst for the polymerization of olefins

Publications (2)

Publication Number Publication Date
DE3751495D1 true DE3751495D1 (de) 1995-10-05
DE3751495T2 DE3751495T2 (de) 1996-03-07

Family

ID=26710837

Family Applications (1)

Application Number Title Priority Date Filing Date
DE3751495T Expired - Fee Related DE3751495T2 (de) 1987-04-03 1987-09-21 Hafnium-Metalocen-Katalysator für Olefinpolymerisation.

Country Status (9)

Country Link
US (1) US4794096A (de)
EP (1) EP0284707B1 (de)
JP (1) JP2583909B2 (de)
KR (1) KR950008154B1 (de)
CN (1) CN1016425B (de)
AT (1) ATE127128T1 (de)
CA (1) CA1302384C (de)
DE (1) DE3751495T2 (de)
ES (1) ES2076934T3 (de)

Families Citing this family (366)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1988008432A1 (en) * 1987-04-20 1988-11-03 Mitsui Petrochemical Industries, Ltd. Olefin polymerization catalyst and process for polymerizing olefin
JP2618384B2 (ja) * 1986-12-27 1997-06-11 三井石油化学工業株式会社 オレフイン重合用固体触媒およびその製法
DE3789666T2 (de) * 1986-12-30 1994-08-04 Mitsui Petrochemical Ind Fester katalysator für die olefinpolymerisation und verfahren zu dessen herstellung.
ATE133690T1 (de) 1987-04-03 1996-02-15 Fina Technology Metallocen-katalysatorsysteme für die polymersation von olefinen, mit einer silizium- hydrocarbyl-brücke.
US5206199A (en) * 1987-04-20 1993-04-27 Mitsui Petrochemical Industries, Ltd. Catalyst for polymerizing an olefin and process for polymerizing an olefin
DE3726067A1 (de) * 1987-08-06 1989-02-16 Hoechst Ag Verfahren zur herstellung von 1-olefinpolymeren
DE3726325A1 (de) * 1987-08-07 1989-02-16 Hoechst Ag Verfahren zur herstellung eines olefinpolymers
US4975403A (en) * 1987-09-11 1990-12-04 Fina Technology, Inc. Catalyst systems for producing polyolefins having a broad molecular weight distribution
US5026797A (en) * 1987-10-22 1991-06-25 Mitsubishi Petrochemical Co., Ltd. Process for producing ethylene copolymers
JP2587251B2 (ja) * 1987-11-09 1997-03-05 チッソ株式会社 立体規則性オレフィン重合体製造用触媒
DE3742934A1 (de) * 1987-12-18 1989-06-29 Hoechst Ag Verfahren zur herstellung einer chiralen, stereorigiden metallocen-verbindung
DE3743320A1 (de) * 1987-12-21 1989-06-29 Hoechst Ag 1-olefinstereoblockpolymerwachs und verfahren zu seiner herstellung
DE3808268A1 (de) * 1988-03-12 1989-09-21 Hoechst Ag Verfahren zur herstellung eines 1-olefinpolymers
DE3808267A1 (de) * 1988-03-12 1989-09-21 Hoechst Ag Verfahren zur herstellung von 1-olefinpolymeren
IL89525A0 (en) * 1988-03-21 1989-09-10 Exxon Chemical Patents Inc Silicon-bridged transition metal compounds
US5017714A (en) * 1988-03-21 1991-05-21 Exxon Chemical Patents Inc. Silicon-bridged transition metal compounds
US5120867A (en) * 1988-03-21 1992-06-09 Welborn Jr Howard C Silicon-bridged transition metal compounds
JP2720392B2 (ja) * 1988-07-12 1998-03-04 三井化学株式会社 オレフィン重合用触媒およびオレフィンの重合方法
US5155080A (en) * 1988-07-15 1992-10-13 Fina Technology, Inc. Process and catalyst for producing syndiotactic polyolefins
US5243002A (en) * 1988-07-15 1993-09-07 Fina Technology, Inc. Process and catalyst for producing syndiotactic polymers
US5158920A (en) * 1988-07-15 1992-10-27 Fina Technology, Inc. Process for producing stereospecific polymers
US5223468A (en) * 1988-07-15 1993-06-29 Fina Technology, Inc. Process and catalyst for producing syndiotactic polymers
US5225500A (en) * 1988-07-15 1993-07-06 Fina Technology, Inc. Process and catalyst for producing syndiotactic polyolefins
US5223467A (en) * 1988-07-15 1993-06-29 Fina Technology, Inc. Process and catalyst for producing syndiotactic polymers
US5162278A (en) * 1988-07-15 1992-11-10 Fina Technology, Inc. Non-bridged syndiospecific metallocene catalysts and polymerization process
DE3825814A1 (de) * 1988-07-29 1990-02-01 Hoechst Ag Verfahren zur herstellung von l-olefinpolymeren
DE3826075A1 (de) * 1988-07-30 1990-02-01 Hoechst Ag 1-olefin-isoblockpolymer und verfahren zu seiner herstellung
DE3836059A1 (de) * 1988-10-22 1990-05-03 Hoechst Ag Verfahren zur herstellung eines ethylen-propylen-copolymers
JP2835729B2 (ja) * 1988-10-24 1998-12-14 チッソ株式会社 オレフィン重合体の製造方法
US5639842A (en) * 1988-12-26 1997-06-17 Mitsui Petrochemical Industries, Ltd. Ethylene random copolymers
WO1990007526A1 (en) * 1988-12-26 1990-07-12 Mitsui Petrochemical Industries, Ltd. Olefin copolymer and production thereof
US5218071A (en) * 1988-12-26 1993-06-08 Mitsui Petrochemical Industries, Ltd. Ethylene random copolymers
JP2571280B2 (ja) * 1989-01-24 1997-01-16 三井石油化学工業株式会社 エチレン系共重合体およびその製造方法
KR930009208B1 (ko) * 1988-12-26 1993-09-24 마쓰이 세끼유 가가꾸 고오교오 가부시끼가이샤 올레핀 공중합체 및 그의 제조방법
DE3904468A1 (de) * 1989-02-15 1990-08-16 Hoechst Ag Polypropylenwachs und verfahren zu seiner herstellung
DE3904469A1 (de) * 1989-02-15 1990-08-16 Hoechst Ag Verfahren zur herstellung eines statistischen propylen-copolymers
US5441920A (en) * 1989-03-21 1995-08-15 Exxon Chemical Patents Inc. Silicon-bridged transition metal compounds
DE3916553A1 (de) 1989-05-20 1990-11-22 Hoechst Ag Syndio- isoblockpolymer und verfahren zu seiner herstellung
DE3922546A1 (de) * 1989-07-08 1991-01-17 Hoechst Ag Verfahren zur herstellung von cycloolefinpolymeren
US5004820A (en) * 1989-08-07 1991-04-02 Massachusetts Institute Of Technology Preparation of chiral metallocene dihalides
US6025448A (en) 1989-08-31 2000-02-15 The Dow Chemical Company Gas phase polymerization of olefins
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
US7041841B1 (en) 1989-09-13 2006-05-09 Exxonmobil Chemical Patents Inc. Process for producing crystalline poly-α-olefins with a monocyclopentadienyl transition metal catalyst system
US5763549A (en) * 1989-10-10 1998-06-09 Fina Technology, Inc. Cationic metallocene catalysts based on organoaluminum anions
US5036034A (en) * 1989-10-10 1991-07-30 Fina Technology, Inc. Catalyst for producing hemiisotactic polypropylene
US5387568A (en) * 1989-10-30 1995-02-07 Fina Technology, Inc. Preparation of metallocene catalysts for polymerization of olefins
US5117020A (en) * 1989-10-30 1992-05-26 Fina Research, S.A. Process for the preparation of metallocenes
EP0426643B1 (de) * 1989-10-30 1995-12-27 Fina Research S.A. Verfahren zur Herstellung von Metallocenen
US5104956A (en) * 1989-12-19 1992-04-14 Board Of Trustees Of The Leland Stanford Junior Univ. Stereoregular cyclopolymers and method
US5208304A (en) * 1989-12-19 1993-05-04 Board Of Trustees, Leland Stanford Junior University Stereoregular cyclopolymers and method
DE4005947A1 (de) * 1990-02-26 1991-08-29 Basf Ag Loesliche katalysatorsysteme zur polymerisation von c(pfeil abwaerts)2(pfeil abwaerts)- bis c(pfeil abwaerts)1(pfeil abwaerts)(pfeil abwaerts)0(pfeil abwaerts)-alk-1-enen
US5516739A (en) * 1990-04-20 1996-05-14 The University Of North Carolina At Chapel Hill Late transition metal catalysts for the co- and terpolymerization of olefin and alkyne monomers with carbon monoxide
DE4015254A1 (de) * 1990-05-12 1991-11-14 Hoechst Ag Verfahren zur herstellung eines polyolefins
DE4017331A1 (de) * 1990-05-30 1991-12-05 Hoechst Ag Verfahren zur herstellung eines polyolefins
US6538080B1 (en) 1990-07-03 2003-03-25 Bp Chemicals Limited Gas phase polymerization of olefins
US5066631A (en) * 1990-10-16 1991-11-19 Ethyl Corporation Hydrocarbon solutions of alkylaluminoxane compounds
EP0485823B1 (de) * 1990-11-12 1995-03-08 Hoechst Aktiengesellschaft 2-Substituierte Bisindenylmetallocene, Verfahren zu ihrer Herstellung und ihre Verwendung als Katalysatoren bei der Olefinpolymerisation
WO1992012162A1 (en) * 1990-12-27 1992-07-23 Exxon Chemical Patents Inc. An amido transition metal compound and a catalyst system for the production of isotactic polypropylene
US5087788A (en) * 1991-03-04 1992-02-11 Ethyl Corporation Preparation of high purity vinylindene olefin
EP0729977B1 (de) 1991-03-09 2002-09-04 Basell Polyolefine GmbH Metallocen und Katalysator
US5191132A (en) * 1991-05-09 1993-03-02 Phillips Petroleum Company Cyclopentadiene type compounds and method for making
US5393911A (en) * 1991-05-09 1995-02-28 Phillips Petroleum Company Cyclopentadiene type compounds and method for making
CA2067525C (en) * 1991-05-09 1998-09-15 Helmut G. Alt Organometallic fluorenyl compounds, preparation and use
US5436305A (en) * 1991-05-09 1995-07-25 Phillips Petroleum Company Organometallic fluorenyl compounds, preparation, and use
US5401817A (en) * 1991-05-09 1995-03-28 Phillips Petroleum Company Olefin polymerization using silyl-bridged metallocenes
DE4120009A1 (de) * 1991-06-18 1992-12-24 Basf Ag Loesliche katalysatorsysteme zur herstellung von polyalk-1-enen mit hohen molmassen
CA2072476C (en) * 1991-06-27 2002-09-03 Yoshio Tajima Catalysts components for polymerization of olefins
US5387567A (en) * 1991-06-27 1995-02-07 Nippon Oil Co., Ltd. Catalyst components for polymerization of olefins
US5594078A (en) 1991-07-23 1997-01-14 Phillips Petroleum Company Process for producing broad molecular weight polyolefin
JP2988071B2 (ja) * 1991-10-14 1999-12-06 東ソー株式会社 芳香族ビニル化合物重合用触媒および芳香族ビニル化合物重合体の製造方法
US5525695A (en) * 1991-10-15 1996-06-11 The Dow Chemical Company Elastic linear interpolymers
DE4139263A1 (de) * 1991-11-29 1993-06-03 Basf Ag Katalysatorsysteme zur polymerisation von c(pfeil abwaerts)2(pfeil abwaerts)- bis c(pfeil abwaerts)1(pfeil abwaerts)(pfeil abwaerts)0(pfeil abwaerts)-alkenen
TW304963B (de) * 1992-01-27 1997-05-11 Hoechst Ag
US5378672A (en) * 1992-03-04 1995-01-03 Fina Technology, Inc. Methods and systems for multi-component catalyst formulation
US5330948A (en) * 1992-03-31 1994-07-19 Northwestern University Homogeneous catalysts for stereoregular olefin polymerization
DE4211086A1 (de) * 1992-04-03 1993-10-07 Basf Ag Katalysatorsysteme zur Polymerisation von C¶2¶- bis C¶1¶¶0¶-Alk-1-enen
JP3167415B2 (ja) * 1992-04-30 2001-05-21 オリンパス光学工業株式会社 固相免疫検査における抗原細胞の保存方法
US5308817A (en) * 1992-05-18 1994-05-03 Fina Technology, Inc. Metallocene catalyst component with good catalyst efficiency after aging
US5710222A (en) * 1992-06-22 1998-01-20 Fina Technology, Inc. Method for controlling the melting points and molecular weights of syndiotactic polyolefins using metallocene catalyst systems
ES2114978T3 (es) * 1992-08-03 1998-06-16 Targor Gmbh Procedimiento para la obtencion de un polimero de olefina bajo empleo de metalocenos con ligandos indenilo de substitucion especial.
EP0586777B1 (de) * 1992-08-31 1999-04-28 Fina Research S.A. Verfahren zur Herstellung von flüssigen statistischen Copolymerisaten des Typs Ethylen
JPH07507095A (ja) * 1992-11-25 1995-08-03 ザ・ボード・オブ・トラスティーズ・オブ・ザ・リーランド・スタンフォード・ジュニア・ユニバーシティ チーグラー・ナッタ触媒で官能化した単量体の重合
US5449650A (en) * 1992-12-08 1995-09-12 Mitsubishi Petrochemical Company Limited Catalyst components for polymerization of olefins and use thereof
US5420220A (en) * 1993-03-25 1995-05-30 Mobil Oil Corporation LLDPE films
US5602067A (en) * 1992-12-28 1997-02-11 Mobil Oil Corporation Process and a catalyst for preventing reactor fouling
US5608019A (en) * 1992-12-28 1997-03-04 Mobil Oil Corporation Temperature control of MW in olefin polymerization using supported metallocene catalyst
US5332706A (en) * 1992-12-28 1994-07-26 Mobil Oil Corporation Process and a catalyst for preventing reactor fouling
US5459117A (en) * 1993-08-27 1995-10-17 Ewen; John A. Doubly-conformationally locked, stereorigid catalysts for the preparation of tactiospecific polymers
US5631202A (en) 1993-09-24 1997-05-20 Montell Technology Company B.V. Stereospecific metallocene catalysts with stereolocking α-CP substituents
US5455741A (en) * 1993-10-26 1995-10-03 Pulse Engineering, Inc. Wire-lead through hole interconnect device
CA2174430A1 (en) * 1993-11-08 1995-05-18 Subrahmanyam Cheruvu Process for the polymerization or copolymerization of ethylene
US5614456A (en) * 1993-11-15 1997-03-25 Mobil Oil Corporation Catalyst for bimodal molecular weight distribution ethylene polymers and copolymers
SG85578A1 (en) * 1993-11-18 2002-01-15 Mobil Oil Corp Process for the polymerization or copolymerization of ethylene
US5496781A (en) * 1994-05-16 1996-03-05 Phillips Petroleum Company Metallocene catalyst systems, preparation, and use
US5541272A (en) 1994-06-03 1996-07-30 Phillips Petroleum Company High activity ethylene selective metallocenes
US5707913A (en) 1994-06-15 1998-01-13 Basf Aktiengesellschaft Amidinato catalyst systems for the polymerization of olefins
US5561216A (en) * 1994-07-01 1996-10-01 University Of North Carolina At Chapel Hill Late transition metal catalysts for the CO- and terpolymerization of olefin and alkyne monomers with carbon monoxide
JP3352555B2 (ja) 1994-12-01 2002-12-03 日本ポリオレフィン株式会社 オレフィン類重合用触媒
ES2116188B1 (es) * 1994-12-30 1999-04-01 Repsol Quimica Sa Proceso de obtencion de poliolefinas con distribuciones de pesos moleculares anchas, bimodales o multimodales.
US5922819A (en) * 1995-02-24 1999-07-13 Basf Aktiengesellschaft Process for producing polymers of vinyl aromatic compounds using polymer-containing catalyst systems
EP0743324B1 (de) * 1995-05-16 2002-09-11 Univation Technologies LLC Herstellung von Polyethylen unter Verwendung eines stereoisomeren Metallocens
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
US5750454A (en) * 1995-05-31 1998-05-12 Nippon Oil Co., Ltd. Catalyst composition and process for the production of olefinic polymers
US6407177B1 (en) * 1995-06-07 2002-06-18 Fina Technology, Inc. Polypropylene blend
US5882750A (en) * 1995-07-03 1999-03-16 Mobil Oil Corporation Single reactor bimodal HMW-HDPE film resin with improved bubble stability
US6403772B1 (en) * 1995-09-11 2002-06-11 Montell Technology Company, Bv Open-pentadienyl metallocenes, precursors thereof and polymerization catalysts therefrom
US6486089B1 (en) 1995-11-09 2002-11-26 Exxonmobil Oil Corporation Bimetallic catalyst for ethylene polymerization reactions with uniform component distribution
DE19542356A1 (de) 1995-11-14 1997-05-15 Basf Ag Verfahren zur Herstellung von Copolymerisaten aus vinylaromatischen und olefinischen Verbindungen durch Dispersionspolymerisation in Gegenwart von Metallocenkatalysatorsystemen
DE19546096A1 (de) * 1995-12-11 1997-06-12 Basf Ag Verfahren zur Herstellung von Polymerisaten von vinylaromatischen Verbindungen in einer Stufe unter Verwendung von Doppelschneckenextrudern
US5679814A (en) * 1995-12-11 1997-10-21 Albemarle Corporation Purification of metallocenes
DE19546095A1 (de) * 1995-12-11 1997-06-12 Basf Ag Verfahren zur Herstellung von Copolymerisaten von vinylaromatischen Verbindungen in einer Stufe unter Verwendung von Doppelschneckenextrudern
US5908903A (en) 1995-12-27 1999-06-01 Basf Aktiengesellschaft Metallocene catalyst systems containing lewis bases
DE19602543A1 (de) 1996-01-25 1997-07-31 Basf Ag Verfahren zur Herstellung von Polymerisaten von C¶2¶- bis C¶1¶¶0¶-Alkenen in Gegenwart von Metallocenkomplexen mit kationisch funktionalisierten Cyclopentadienylliganden
DE19608814A1 (de) 1996-03-07 1997-10-02 Hoechst Ag Verfahren zur Herstellung von Indenen
US6417130B1 (en) 1996-03-25 2002-07-09 Exxonmobil Oil Corporation One pot preparation of bimetallic catalysts for ethylene 1-olefin copolymerization
DE19615953A1 (de) * 1996-04-22 1997-10-23 Basf Ag Verfahren zur Herstellung von Polymerisaten von Alk-1-enen in Gegenwart eines geträgerten Metallocenkatalysatorsystems und eines Antistatikums
DE19616523A1 (de) * 1996-04-25 1997-11-06 Basf Ag Polymerisationskatalysatoren mit beta-Diketiminat-Liganden
DE19617230A1 (de) 1996-04-30 1997-11-06 Basf Ag Oxidierte Metallocen-Polyolefin-Wachse
DE19618007A1 (de) * 1996-05-04 1997-11-06 Basf Ag Verfahren zur Wiedergewinnung von Metallocenkomplexen
DE19621838A1 (de) * 1996-05-31 1997-12-04 Basf Ag Verfahren zur Herstellung von Polymerisaten von C¶2¶- bis C¶1¶¶2¶-Alkenen unter Zusatz eines Reaktionsverzögerers
DE19621969A1 (de) * 1996-05-31 1997-12-04 Basf Ag Verfahren zur Herstellung von kristallinen Polymerisaten durch Dispersionspolymerisation in Gegenwart von Metallocenkatalysatorsystemen
US5710299A (en) * 1996-06-27 1998-01-20 Albemarle Corporation Production of bridged metallocene complexes and intermediates therefor
DE59703441D1 (de) 1996-07-04 2001-05-31 Basf Ag Verfahren zur herstellung von geträgerten übergangsmetallkatalysatoren
EP0912244A4 (de) * 1996-07-15 2001-09-12 Mobil Oil Corp Mit comonomer vorbehandelter bimetallischer katalysator zum blasformen und filme
WO1998008881A1 (de) 1996-08-26 1998-03-05 Basf Aktiengesellschaft Sternpolymere und verfahren zu deren herstellung
DE19635503A1 (de) 1996-09-02 1998-03-05 Basf Ag Weißbrucharme, zähmodifizierte Propylenpolymerisate
DE19637669A1 (de) 1996-09-16 1998-03-19 Hoechst Ag Verfahren zur Herstellung einer methylenverbrückten Biscyclopentadienylverbindung
US5760262A (en) * 1996-09-17 1998-06-02 Albemarle Corporation Enhanced production of bridged hafnocenes
DE19642353A1 (de) * 1996-10-14 1998-04-16 Basf Ag Katalysatorsysteme, enthaltend Metallkomplexe mit adamantanähnlicher Struktur
US5936108A (en) * 1996-10-17 1999-08-10 Albemarle Corporation Metallocene synthesis
US5780660A (en) * 1996-11-07 1998-07-14 Albemarle Corporation Zirconocene ismerization process
RU2194708C2 (ru) * 1996-11-15 2002-12-20 Монтелл Текнолоджи Компани Б.В. Металлоцен, лиганд, каталитическая система, способ полимеризации
DE19653079A1 (de) * 1996-12-19 1998-06-25 Basf Ag Verfahren zur Gasphasenpolymerisation von C¶2¶-C¶8¶-Alk-1-enen mittels Ziegler -Natta- oder Metallocen-Katalysatorsystemen
US6005463A (en) * 1997-01-30 1999-12-21 Pulse Engineering Through-hole interconnect device with isolated wire-leads and component barriers
EP0856525B1 (de) * 1997-01-30 2003-12-17 Fina Technology, Inc. Selektive Wirkung von Metallocen-Katalysatoren für die Herstellung von isotaktischen Polyolefinen
US5807800A (en) * 1997-02-11 1998-09-15 Fina Technology, Inc. Process for producing stereospecific polymers
DE19709866A1 (de) 1997-03-11 1998-09-17 Basf Ag Geträgertes Katalysatorsystem zur Polymerisation von Alk-1-enen
DE19716239A1 (de) 1997-04-18 1998-10-22 Basf Ag Verfahren zur Polymerisation von alpha-Olefinen in der Gasphase
US6160072A (en) * 1997-05-02 2000-12-12 Ewen; John A. Process for polymerizing tactioselective polyolefins in condensed phase using titanocenes
DE19723003A1 (de) 1997-06-02 1998-12-03 Basf Ag Polymermischung
US6586646B1 (en) 1997-06-20 2003-07-01 Pennzoil-Quaker State Company Vinylidene-containing polymers and uses thereof
US6124513A (en) 1997-06-20 2000-09-26 Pennzoil-Quaker State Company Ethylene-alpha-olefin polymers, processes and uses
US6051525A (en) * 1997-07-14 2000-04-18 Mobil Corporation Catalyst for the manufacture of polyethylene with a broad or bimodal molecular weight distribution
US6153551A (en) * 1997-07-14 2000-11-28 Mobil Oil Corporation Preparation of supported catalyst using trialkylaluminum-metallocene contact products
US6074590A (en) * 1997-07-28 2000-06-13 Fina Technology, Inc. Process of making a bicomponent fiber
US5905162A (en) * 1997-08-12 1999-05-18 Albemarle Corporation Enhanced production of bridged hafnocenes
US6159612A (en) * 1997-08-25 2000-12-12 Mobil Oil Corporation Multi-layer films with syndiotactic barrier layer containing a wax
DE19741497A1 (de) * 1997-09-19 1999-03-25 Basf Ag Pfropfcopolymere
US5908594A (en) * 1997-09-24 1999-06-01 Fina Technology, Inc. Process of making polypropylene fiber
US6090325A (en) 1997-09-24 2000-07-18 Fina Technology, Inc. Biaxially-oriented metallocene-based polypropylene films
DE19745047A1 (de) 1997-10-11 1999-04-15 Basf Ag Polymermischung mit guter Verarbeitbarkeit
US5958566A (en) * 1997-10-17 1999-09-28 Fina Technology, Inc. Metal bond strength in polyolefin films
US5997679A (en) * 1997-10-17 1999-12-07 Fina Technology, Inc. Heat-seal strength in polyolefin films
US6265512B1 (en) 1997-10-23 2001-07-24 3M Innovative Company Elastic polypropylenes and catalysts for their manufacture
US6242545B1 (en) 1997-12-08 2001-06-05 Univation Technologies Polymerization catalyst systems comprising substituted hafinocenes
US8497330B2 (en) 1997-12-08 2013-07-30 Univation Technologies, Llc Methods for polymerization using spray dried and slurried catalyst
US6207093B1 (en) 1998-04-24 2001-03-27 Fina Technology, Inc. Compositions for improved orientation processing
US5965759A (en) * 1998-09-23 1999-10-12 Albemarle Corporation Catalytic process for isomerizing metallocenes
US6270912B1 (en) 1999-02-25 2001-08-07 Mobil Oil Corporation Multi-layer films with core layer of metallocene-catalyzed polypropylene
US6432860B1 (en) * 1999-03-22 2002-08-13 Fina Technology, Inc. Supported metallocene catalysts
US6410124B1 (en) 1999-03-30 2002-06-25 Exxonmobil Oil Corporation Films with improved metallizable surfaces
EP1041180A1 (de) * 1999-03-30 2000-10-04 Fina Research S.A. Polypropylenfasern
US6416699B1 (en) 1999-06-09 2002-07-09 Fina Technology, Inc. Reduced shrinkage in metallocene isotactic polypropylene fibers
DE19927766A1 (de) 1999-06-17 2000-12-21 Basf Ag Trägerkatalysator zur Olefinpolymerisation
DE19957384A1 (de) 1999-11-29 2001-05-31 Targor Gmbh Hochmolekulares Polypropylen mit breiter Molekulargewichtsverteilung und geringer isotaktischer Sequenzlänge
US6878782B2 (en) * 1999-12-01 2005-04-12 General Electric Thermoset composition, method, and article
US7235192B2 (en) 1999-12-01 2007-06-26 General Electric Company Capped poly(arylene ether) composition and method
US6905637B2 (en) 2001-01-18 2005-06-14 General Electric Company Electrically conductive thermoset composition, method for the preparation thereof, and articles derived therefrom
BR0016590A (pt) * 1999-12-21 2002-09-10 Basell Polyolefine Gmbh Composição semicristalina de polìmero de propileno, processo para preparar a mesma, uso da mesma, pelìcula, fibra ou moldagem, e, pelìcula biaxialmente estirada
DE19962129A1 (de) * 1999-12-21 2001-06-28 Targor Gmbh Verfahren zur Herstellung eines Katalysatorfeststoffs zur Olefinpolymerisation
US7041617B2 (en) 2004-01-09 2006-05-09 Chevron Phillips Chemical Company, L.P. Catalyst compositions and polyolefins for extrusion coating applications
DE10026579A1 (de) * 2000-05-30 2001-12-06 Basell Polyolefine Gmbh Verfahren zur Herstellung von für das Faserspinnen geeigneten Propylenpolymerisaten
ITMI20012085A1 (it) 2000-10-17 2003-04-09 Ciba Sc Holding Ag Polpropilene metallocene stabilizzato
US6936675B2 (en) 2001-07-19 2005-08-30 Univation Technologies, Llc High tear films from hafnocene catalyzed polyethylenes
EP1300423A1 (de) * 2001-09-27 2003-04-09 Atofina Research S.A. Katalysatorsystem aus einer Mischung von Katalysatorbestandteilen zur Herstellung einer Polyolefinmischung
KR20050035183A (ko) 2001-11-30 2005-04-15 엑손모빌 케미칼 패턴츠 인코포레이티드 비-단일 부위/단일 부위 촉매 복합물을 이용하여 제조된에틸렌/알파-올레핀 공중합체, 이의 제조 방법 및 용도
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
US6733719B2 (en) * 2002-01-14 2004-05-11 Sunoco Inc. (R&M) Polypropylene biaxially oriented film
US7025919B2 (en) * 2002-03-28 2006-04-11 Fina Technology, Inc. Syndiotactic polypropylene fibers
US6758994B2 (en) * 2002-03-28 2004-07-06 Fina Technology, Inc. Method of producing polypropylene tapes
US6998431B2 (en) 2002-03-28 2006-02-14 Fina Technology, Inc. Polymerization process
US6824721B2 (en) * 2002-03-29 2004-11-30 Fina Technology, Inc. Polypropylene fibers
US20030215588A1 (en) * 2002-04-09 2003-11-20 Yeager Gary William Thermoset composition, method, and article
US6878327B2 (en) * 2002-04-19 2005-04-12 Fina Technology, Inc. Process of making polypropylene fibers
US20030236365A1 (en) * 2002-06-24 2003-12-25 Fina Technology, Inc. Polyolefin production with a high performance support for a metallocene catalyst system
US6773818B2 (en) 2002-09-06 2004-08-10 Exxonmobil Oil Corporation Metallized, metallocene-catalyzed, polypropylene films
US8008412B2 (en) 2002-09-20 2011-08-30 Exxonmobil Chemical Patents Inc. Polymer production at supersolution conditions
DE60336074D1 (de) * 2002-10-11 2011-03-31 Univ Connecticut Mischungen von amorphen und semikristallinen polymeren mit formgedächtniseigenscchaften
US7294681B2 (en) 2002-10-15 2007-11-13 Exxonmobil Chemical Patents Inc. Mutliple catalyst system for olefin polymerization and polymers produced therefrom
US7550528B2 (en) 2002-10-15 2009-06-23 Exxonmobil Chemical Patents Inc. Functionalized olefin polymers
US7223822B2 (en) 2002-10-15 2007-05-29 Exxonmobil Chemical Patents Inc. Multiple catalyst and reactor system for olefin polymerization and polymers produced therefrom
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
US6855783B2 (en) * 2003-04-11 2005-02-15 Fina Technology, Inc. Supported metallocene catalysts
US6846561B1 (en) 2003-08-06 2005-01-25 Fina Technology, Inc. Bicomponent fibers of isotactic and syndiotactic polypropylene
US6878787B2 (en) * 2003-08-26 2005-04-12 Fina Technology, Inc. Polyamide supported metallocene catalysts
US7211536B2 (en) * 2004-10-22 2007-05-01 Fina Technology, Inc. Supported metallocene catalysts and their use in producing stereospecific polymers
US20050182210A1 (en) 2004-02-17 2005-08-18 Natarajan Muruganandam De-foaming spray dried catalyst slurries
US20070155921A1 (en) * 2004-03-24 2007-07-05 Basell Polyolefine Gmbh Flexible prolylene copolymer compositions having a high transparency
WO2005105864A1 (en) * 2004-04-16 2005-11-10 Exxonmobil Chemical Patents Inc. Heterocyclic substituted metallocene compounds for olefin polymerization
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
US7683140B2 (en) 2004-05-20 2010-03-23 Univation Technologies, Llc Method for determining temperature value indicative of resin stickiness from data generated by polymerization reaction monitoring
US7754830B2 (en) 2004-05-20 2010-07-13 Univation Technologies, Llc Polymerization reaction monitoring with determination of induced condensing agent concentration for preventing discontinuity events
US7294599B2 (en) 2004-06-25 2007-11-13 Chevron Phillips Chemical Co. Acidic activator-supports and catalysts for olefin polymerization
US20060009603A1 (en) * 2004-07-09 2006-01-12 David Young Fibrillation-resistant polypropylene tape
US20070202285A1 (en) * 2004-12-15 2007-08-30 Fina Technology, Inc. Articles having improved clarity, prepared from propylene-ethylene copolymers
US7241850B2 (en) * 2004-12-15 2007-07-10 Fina Technology, Inc. Polypropylene having improved clarity and articles prepared therefrom
WO2006065844A2 (en) * 2004-12-16 2006-06-22 Exxonmobil Chemical Patents Inc. Process for producing substituted metallocene compounds for olefin polymerization
US7410927B2 (en) * 2005-04-13 2008-08-12 Chevron Phillips Chemical Company, Lp Catalysts for olefin polymerization
US7413812B2 (en) 2005-04-26 2008-08-19 Fina Technology, Inc. Polypropylene article and method of preparing polypropylene article
US7081285B1 (en) 2005-04-29 2006-07-25 Fina Technology, Inc. Polyethylene useful for blown films and blow molding
US7078467B1 (en) * 2005-06-14 2006-07-18 Univation Technologies, Llc Single catalyst low, medium and high density polyethylenes
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
US20070045894A1 (en) * 2005-08-31 2007-03-01 Mcleod Michael A Process for producing polyolefin films
US7868197B2 (en) 2005-12-14 2011-01-11 Exxonmobil Chemical Patents Inc. Halogen substituted heteroatom-containing metallocene compounds for olefin polymerization
US7763562B2 (en) * 2005-12-14 2010-07-27 Exxonmobil Chemical Patents Inc. Heteroatom bridged metallocene compounds for olefin polymerization
US7910783B2 (en) 2005-12-14 2011-03-22 Exxonmobil Chemical Patents Inc. Preparation of substituted bridged indenyl and related ligands
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
US20070235896A1 (en) * 2006-04-06 2007-10-11 Fina Technology, Inc. High shrink high modulus biaxially oriented films
AU2007293505A1 (en) 2006-09-07 2008-03-13 Univation Technologies, Llc Methods for determining temperature value indicative of resin stickiness from data generated by polymerization reaction monitoring
CA2662793A1 (en) 2006-09-07 2008-03-13 Univation Technologies, Llc Methods for on-line determination of degree of resin stickiness using a model for depression of melt initiation temperature
US8242237B2 (en) 2006-12-20 2012-08-14 Exxonmobil Chemical Patents Inc. Phase separator and monomer recycle for supercritical polymerization process
US7473751B2 (en) * 2007-01-22 2009-01-06 Fina Technology, Inc. Biaxially-oriented metallocene-based polypropylene films having reduced thickness
US8058200B2 (en) * 2007-05-17 2011-11-15 Chevron Phillips Chemical Company, L.P. Catalysts for olefin polymerization
EP2160419B1 (de) 2007-06-04 2013-11-13 ExxonMobil Chemical Patents Inc. Homogene propylenpolymerisation unter superlösungsbedingungen
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
EP2112175A1 (de) 2008-04-16 2009-10-28 ExxonMobil Chemical Patents Inc. Aktivator für Metallocene, der einen oder mehrere halogensubstituierte heterocyklische Liganden enthält, die an ein Alumoxan koordiniert sind
US7863210B2 (en) 2007-12-28 2011-01-04 Chevron Phillips Chemical Company Lp Nano-linked metallocene catalyst compositions and their polymer products
US8012900B2 (en) * 2007-12-28 2011-09-06 Chevron Phillips Chemical Company, L.P. Nano-linked metallocene catalyst compositions and their polymer products
US8080681B2 (en) 2007-12-28 2011-12-20 Chevron Phillips Chemical Company Lp Nano-linked metallocene catalyst compositions and their polymer products
US7812104B2 (en) * 2008-01-18 2010-10-12 Exxonmobil Chemical Patents Inc. Production of propylene-based polymers
US8318875B2 (en) 2008-01-18 2012-11-27 Exxonmobil Chemical Patents Inc. Super-solution homogeneous propylene polymerization and polypropylenes made therefrom
US20090202770A1 (en) * 2008-02-08 2009-08-13 Fengkui Li Polypropylene/polyisobutylene blends and films prepared from same
US11208514B2 (en) 2008-03-20 2021-12-28 Chevron Phillips Chemical Company Lp Silica-coated alumina activator-supports for metallocene catalyst compositions
US7884163B2 (en) * 2008-03-20 2011-02-08 Chevron Phillips Chemical Company Lp Silica-coated alumina activator-supports for metallocene catalyst compositions
US8759446B2 (en) * 2008-06-30 2014-06-24 Fina Technology, Inc. Compatibilized polypropylene and polylactic acid blends and methods of making and using same
US8545971B2 (en) * 2008-06-30 2013-10-01 Fina Technology, Inc. Polymeric compositions comprising polylactic acid and methods of making and using same
US8268913B2 (en) * 2008-06-30 2012-09-18 Fina Technology, Inc. Polymeric blends and methods of using same
US7884165B2 (en) * 2008-07-14 2011-02-08 Chevron Phillips Chemical Company Lp Half-metallocene catalyst compositions and their polymer products
US20100087602A1 (en) * 2008-10-08 2010-04-08 Fina Technology, Inc. Long chain branched polypropylene for cast film applications
US8114946B2 (en) 2008-12-18 2012-02-14 Chevron Phillips Chemical Company Lp Process for producing broader molecular weight distribution polymers with a reverse comonomer distribution and low levels of long chain branches
US20110256632A1 (en) 2009-01-08 2011-10-20 Univation Technologies, Llc Additive for Polyolefin Polymerization Processes
WO2010080871A1 (en) 2009-01-08 2010-07-15 Univation Technologies, Llc Additive for gas phase polymerization processes
US8309485B2 (en) 2009-03-09 2012-11-13 Chevron Phillips Chemical Company Lp Methods for producing metal-containing sulfated activator-supports
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
US7919639B2 (en) * 2009-06-23 2011-04-05 Chevron Phillips Chemical Company Lp Nano-linked heteronuclear metallocene catalyst compositions and their polymer products
US9289739B2 (en) 2009-06-23 2016-03-22 Chevron Philips Chemical Company Lp Continuous preparation of calcined chemically-treated solid oxides
ES2582396T3 (es) * 2009-06-29 2016-09-12 Chevron Phillips Chemical Company Lp Sistemas catalíticos duales de metaloceno para disminuir el índice de fluidez y aumentar la velocidad de producción de polímero
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.
BRPI1015361A2 (pt) 2009-07-23 2018-02-20 Univation Tech Llc sistema de reação de polimerização
WO2011078923A1 (en) 2009-12-23 2011-06-30 Univation Technologies, Llc Methods for producing catalyst systems
US8383754B2 (en) 2010-04-19 2013-02-26 Chevron Phillips Chemical Company Lp Catalyst compositions for producing high Mz/Mw polyolefins
US8288487B2 (en) 2010-07-06 2012-10-16 Chevron Phillips Chemical Company Lp Catalysts for producing broad molecular weight distribution polyolefins in the absence of added hydrogen
US8932975B2 (en) 2010-09-07 2015-01-13 Chevron Phillips Chemical Company Lp Catalyst systems and methods of making and using same
US8501651B2 (en) 2010-09-24 2013-08-06 Chevron Phillips Chemical Company Lp Catalyst systems and polymer resins having improved barrier properties
US8828529B2 (en) 2010-09-24 2014-09-09 Chevron Phillips Chemical Company Lp Catalyst systems and polymer resins having improved barrier properties
US8609793B2 (en) 2010-10-07 2013-12-17 Chevron Phillips Chemical Company Lp Catalyst systems containing a bridged metallocene
US8637616B2 (en) 2010-10-07 2014-01-28 Chevron Philips Chemical Company Lp Bridged metallocene catalyst systems with switchable hydrogen and comonomer effects
US8629292B2 (en) 2010-10-07 2014-01-14 Chevron Phillips Chemical Company Lp Stereoselective synthesis of bridged metallocene complexes
US8309748B2 (en) 2011-01-25 2012-11-13 Chevron Phillips Chemical Company Lp Half-metallocene compounds and catalyst compositions
US8618229B2 (en) 2011-03-08 2013-12-31 Chevron Phillips Chemical Company Lp Catalyst compositions containing transition metal complexes with thiolate ligands
US8907031B2 (en) 2011-04-20 2014-12-09 Chevron Phillips Chemical Company Lp Imino carbene compounds and derivatives, and catalyst compositions made therefrom
US8431729B2 (en) 2011-08-04 2013-04-30 Chevron Phillips Chemical Company Lp High activity catalyst compositions containing silicon-bridged metallocenes with bulky substituents
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
US8785576B2 (en) 2011-12-28 2014-07-22 Chevron Phillips Chemical Company Lp Catalyst compositions for the polymerization of olefins
US8791217B2 (en) 2011-12-28 2014-07-29 Chevron Phillips Chemical Company Lp Catalyst systems for production of alpha olefin oligomers and polymers
MX2014011850A (es) 2012-04-02 2014-11-21 Chevron Phillips Chemical Co Sistemas catalizadores que contienen un metaloceno puenteado.
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
US8865846B2 (en) 2012-09-25 2014-10-21 Chevron Phillips Chemical Company Lp Metallocene and half sandwich dual catalyst systems for producing broad molecular weight distribution polymers
US8821800B2 (en) 2012-10-18 2014-09-02 Chevron Phillips Chemical Company Lp System and method for catalyst preparation
US8895679B2 (en) 2012-10-25 2014-11-25 Chevron Phillips Chemical Company Lp Catalyst compositions and methods of making and using same
US8937139B2 (en) 2012-10-25 2015-01-20 Chevron Phillips Chemical Company Lp Catalyst compositions and methods of making and using same
US10221263B2 (en) 2012-11-01 2019-03-05 Univation Technologies, Llc Mixed compatible Ziegler-Natta / chromium catalysts for improved polymer products
US9006367B2 (en) 2012-11-07 2015-04-14 Chevron Phillips Chemical Company Lp Low density polyolefin resins and films made therefrom
US8912285B2 (en) 2012-12-06 2014-12-16 Chevron Phillips Chemical Company Lp Catalyst system with three metallocenes for producing broad molecular weight distribution polymers
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
US8680218B1 (en) 2013-01-30 2014-03-25 Chevron Phillips Chemical Company Lp Methods for controlling dual catalyst olefin polymerizations with an organozinc compound
US8703886B1 (en) 2013-02-27 2014-04-22 Chevron Phillips Chemical Company Lp Dual activator-support catalyst systems
US8623973B1 (en) 2013-03-08 2014-01-07 Chevron Phillips Chemical Company Lp Activator supports impregnated with group VIII transition metals for polymer property control
US9346897B2 (en) 2013-05-14 2016-05-24 Chevron Phillips Chemical Company Lp Peroxide treated metallocene-based polyolefins with improved melt strength
US9023959B2 (en) 2013-07-15 2015-05-05 Chevron Phillips Chemical Company Lp Methods for producing fluorided-chlorided silica-coated alumina activator-supports and catalyst systems containing the same
US8957168B1 (en) 2013-08-09 2015-02-17 Chevron Phillips Chemical Company Lp Methods for controlling dual catalyst olefin polymerizations with an alcohol compound
US9102768B2 (en) 2013-08-14 2015-08-11 Chevron Phillips Chemical Company Lp Cyclobutylidene-bridged metallocenes and catalyst systems containing the same
US9156970B2 (en) 2013-09-05 2015-10-13 Chevron Phillips Chemical Company Lp Higher density polyolefins with improved stress crack resistance
US9181370B2 (en) 2013-11-06 2015-11-10 Chevron Phillips Chemical Company Lp Low density polyolefin resins with low molecular weight and high molecular weight components, and films made therefrom
WO2015077100A2 (en) 2013-11-19 2015-05-28 Chevron Phillips Chemical Company Lp Boron-bridged bis-indenyl metallocene catalyst systems and polymers produced therefrom
EP3071609B1 (de) 2013-11-19 2018-01-31 Chevron Phillips Chemical Company LP Katalysatorsysteme mit borverbrückten cyclopentadienyl-fluorenyl-metallocenverbindungen mit einem alkenylsubstituenten
US9217049B2 (en) 2013-11-19 2015-12-22 Chevron Phillips Chemical Company Lp Dual catalyst systems for producing polymers with a broad molecular weight distribution and a uniform short chain branch distribution
US9540465B2 (en) 2013-11-19 2017-01-10 Chevron Phillips Chemical Company Lp Boron-bridged metallocene catalyst systems and polymers produced therefrom
US10246528B2 (en) 2014-01-09 2019-04-02 Chevron Phillips Chemical Company Lp Chromium (III) catalyst systems with activator-supports
US9169337B2 (en) 2014-03-12 2015-10-27 Chevron Phillips Chemical Company Lp Polymers with improved ESCR for blow molding applications
US9273170B2 (en) 2014-03-12 2016-03-01 Chevron Phillips Chemical Company Lp Polymers with improved toughness and ESCR for large-part blow molding applications
US9394387B2 (en) 2014-05-15 2016-07-19 Chevron Phillips Chemical Company Lp Synthesis of aryl coupled bis phenoxides and their use in olefin polymerization catalyst systems with activator-supports
BR112016027380B1 (pt) 2014-05-22 2021-08-10 Chevron Phillips Chemical Company Lp Processo de polimerização e composição de catalisador
US9441063B2 (en) 2014-10-09 2016-09-13 Chevron Phillips Chemical Company Lp Titanium phosphinimide and titanium iminoimidazolidide catalyst systems with activator-supports
SG11201705607QA (en) 2015-01-21 2017-08-30 Univation Tech Llc Methods for controlling polymer chain scission
CN107107433B (zh) 2015-01-21 2019-09-13 尤尼威蒂恩技术有限责任公司 用于聚烯烃中的凝胶减少的方法
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
CN107864635B (zh) 2015-05-11 2021-06-25 格雷斯公司 制备改性粘土的方法、所制备的改性粘土及其用途
WO2017007640A1 (en) 2015-07-08 2017-01-12 Chevron Phillips Chemical Company Lp Ziegler-natta-metallocene dual catalyst systems with activator-supports
US9732300B2 (en) 2015-07-23 2017-08-15 Chevron Phillipa Chemical Company LP Liquid propylene oligomers and methods of making same
US9493589B1 (en) 2015-09-09 2016-11-15 Chevron Phillips Chemical Company Lp Polymers with improved ESCR for blow molding applications
US9650459B2 (en) 2015-09-09 2017-05-16 Chevron Phillips Chemical Company Lp Methods for controlling die swell in dual catalyst olefin polymerization systems
US9845367B2 (en) 2015-09-24 2017-12-19 Chevron Phillips Chemical Company Lp Heterogeneous Ziegler-Natta catalysts with fluorided silica-coated alumina
US9758599B2 (en) 2015-09-24 2017-09-12 Chevron Phillips Chemical Company Lp Heterogeneous Ziegler-Natta catalysts with fluorided silica-coated alumina
US9540457B1 (en) 2015-09-24 2017-01-10 Chevron Phillips Chemical Company Lp Ziegler-natta—metallocene dual catalyst systems with activator-supports
US10883197B2 (en) 2016-01-12 2021-01-05 Chevron Phillips Chemical Company Lp High melt flow polypropylene homopolymers for fiber applications
US9505856B1 (en) 2016-01-13 2016-11-29 Chevron Phillips Chemical Company Lp Methods for making fluorided chromium (VI) catalysts, and polymerization processes using the same
WO2017201304A1 (en) 2016-05-20 2017-11-23 Chevron Phillips Chemical Company Lp Low pressure process for preparing low-density polyethylene
US9758540B1 (en) 2016-05-25 2017-09-12 Chevron Phillips Chemical Company Lp Bicyclic bridged metallocene compounds and polymers produced therefrom
US9758600B1 (en) 2016-05-25 2017-09-12 Chevron Phillips Chemical Company Lp Bicyclic bridged metallocene compounds and polymers produced therefrom
US9951158B2 (en) 2016-08-12 2018-04-24 Chevron Phillips Chemical Company Lp Process for reducing the light oligomer content of polypropylene oils
JP6967073B2 (ja) 2016-10-28 2021-11-17 フイナ・テクノロジー・インコーポレーテツドFina Technology, Incorporated Boppに応用するためのポリプロピレン中の結晶度を下げる作用剤の使用
US10000594B2 (en) 2016-11-08 2018-06-19 Chevron Phillips Chemical Company Lp Dual catalyst system for producing LLDPE copolymers with a narrow molecular weight distribution and improved processability
US10240102B2 (en) 2017-03-16 2019-03-26 Chevron Phillips Chemical Company, Lp Lubricant compositions containing hexene-based oligomers
US10221258B2 (en) 2017-03-17 2019-03-05 Chevron Phillips Chemical Company Lp Methods for restoring metallocene solids exposed to air
US10005865B1 (en) 2017-04-07 2018-06-26 Chevron Phillips Chemical Company Lp Methods for controlling molecular weight and molecular weight distribution
US10000595B1 (en) 2017-04-07 2018-06-19 Chevron Phillips Chemical Company Lp Catalyst systems containing low valent titanium compounds and polymers produced therefrom
US10428091B2 (en) 2017-04-07 2019-10-01 Chevron Phillips Chemical Company Lp Catalyst systems containing low valent titanium-aluminum complexes and polymers produced therefrom
US10697889B2 (en) 2017-07-21 2020-06-30 Chevron Phillips Chemical Company Lp Methods for determining transition metal compound concentrations in multicomponent liquid systems
US10030086B1 (en) 2017-07-21 2018-07-24 Chevron Phillips Chemical Company Lp Methods for determining transition metal compound concentrations in multicomponent liquid systems
US10358506B2 (en) 2017-10-03 2019-07-23 Chevron Phillips Chemical Company Lp Dual catalyst system for producing LLDPE copolymers with improved processability
US10300460B1 (en) 2017-11-17 2019-05-28 Chevron Phillips Chemical Company L.P. Aqueous methods for titanating a chromium/silica catalyst
US10259893B1 (en) 2018-02-20 2019-04-16 Chevron Phillips Chemical Company Lp Reinforcement of a chromium/silica catalyst with silicate oligomers
US10507445B2 (en) 2018-03-29 2019-12-17 Chevron Phillips Chemical Company Lp Methods for determining transition metal compound concentrations in multicomponent liquid systems
US10679734B2 (en) 2018-03-29 2020-06-09 Chevron Phillips Chemical Company Lp Methods for determining transition metal compound concentrations in multicomponent liquid systems
WO2020056119A1 (en) 2018-09-14 2020-03-19 Fina Technology, Inc. Polyethylene and controlled rheology polypropylene polymer blends and methods of use
KR20210063321A (ko) 2018-09-17 2021-06-01 셰브론 필립스 케미컬 컴퍼니 엘피 크롬 촉매의 광 처리, 관련 촉매 제조 시스템 및 중합 공정
EP3856796A1 (de) 2018-09-24 2021-08-04 Chevron Phillips Chemical Company LP Verfahren zur herstellung von geträgerten chromkatalysatoren mit erhöhter polymerisationsaktivität
US11420196B2 (en) 2018-09-27 2022-08-23 Chevron Phillips Chemical Company Lp Processes for producing fluorided solid oxides and uses thereof in metallocene-based catalyst systems
US10961331B2 (en) 2018-12-19 2021-03-30 Chevron Phillips Chemical Company Lp Ethylene homopolymers with a reverse short chain branch distribution
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
US11014997B2 (en) 2019-05-16 2021-05-25 Chevron Phillips Chemical Company Lp Dual catalyst system for producing high density polyethylenes with long chain branching
US11186656B2 (en) 2019-05-24 2021-11-30 Chevron Phillips Chemical Company Lp Preparation of large pore silicas and uses thereof in chromium catalysts for olefin polymerization
US11478781B2 (en) 2019-06-19 2022-10-25 Chevron Phillips Chemical Company Lp Ziegler-Natta catalysts prepared from solid alkoxymagnesium halide supports
US11377541B2 (en) 2019-07-26 2022-07-05 Chevron Phillips Chemical Company Lp Blow molding polymers with improved cycle time, processability, and surface quality
US11028258B2 (en) 2019-08-19 2021-06-08 Chevron Phillips Chemical Company Lp Metallocene catalyst system for producing LLDPE copolymers with tear resistance and low haze
WO2021055184A1 (en) 2019-09-16 2021-03-25 Chevron Phillips Chemical Company Lp Chromium-based catalysts and processes for converting alkanes into higher and lower aliphatic hydrocarbons
CN114401936A (zh) 2019-09-16 2022-04-26 切弗朗菲利浦化学公司 铬催化从烃生产醇
US11667777B2 (en) 2019-10-04 2023-06-06 Chevron Phillips Chemical Company Lp Bimodal polyethylene copolymers
US11186665B2 (en) 2019-10-04 2021-11-30 Chevron Phillips Chemical Company Lp Catalyst composition and method for preparing polyethylene
WO2021154204A1 (en) 2020-01-27 2021-08-05 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
US11325995B2 (en) 2020-02-21 2022-05-10 Chevron Phillips Chemical Company Lp Metallocene catalysts for polyethylene
US11339279B2 (en) 2020-04-01 2022-05-24 Chevron Phillips Chemical Company Lp Dual catalyst system for producing LLDPE and MDPE copolymers with long chain branching for film applications
US11267919B2 (en) 2020-06-11 2022-03-08 Chevron Phillips Chemical Company Lp Dual catalyst system for producing polyethylene with long chain branching for blow molding applications
WO2022056146A1 (en) 2020-09-14 2022-03-17 Chevron Phillips Chemical Company Lp Transition metal-catalyzed production of alcohol and carbonyl compounds from hydrocarbons
US11578156B2 (en) 2020-10-20 2023-02-14 Chevron Phillips Chemical Company Lp Dual metallocene polyethylene with improved processability for lightweight blow molded products
US11124586B1 (en) 2020-11-09 2021-09-21 Chevron Phillips Chemical Company Lp Particle size control of metallocene catalyst systems in loop slurry polymerization reactors
CA3204719A1 (en) 2020-12-08 2022-06-16 Chevron Phillips Chemical Company Lp Particle size control of supported chromium catalysts in loop slurry polymerization reactors
US11125680B1 (en) 2021-01-14 2021-09-21 Chevron Phillips Chemical Company Lp Methods for determining the activity of an activated chemically-treated solid oxide in olefin polymerizations
MX2023008719A (es) 2021-01-28 2023-08-02 Chevron Phillips Chemical Co Lp Copolimeros de polietileno bimodales.
US11584806B2 (en) 2021-02-19 2023-02-21 Chevron Phillips Chemical Company Lp Methods for chromium catalyst activation using oxygen-enriched fluidization gas
JP2024518327A (ja) 2021-04-26 2024-05-01 フイナ・テクノロジー・インコーポレーテツド 薄シングルサイト触媒ポリマーシート
EP4402182A1 (de) 2021-09-13 2024-07-24 Chevron Phillips Chemical Company Lp Hydrozyklonmodifizierung von katalysatorsystemkomponenten zur verwendung in olefinpolymerisationen
US11999814B2 (en) 2021-12-16 2024-06-04 Chevron Phillips Chemical Company Lp Modifications of sulfated bentonites and uses thereof in metallocene catalyst systems for olefin polymerization
US20230227592A1 (en) 2022-01-14 2023-07-20 Chevron Phillips Chemical Company Lp Dual metallocene bimodal hdpe resins with improved stress crack resistance
US20230340166A1 (en) 2022-04-26 2023-10-26 Chevron Phillips Chemical Company Lp Aqueous methods for titanating a chromium/silica catalyst with an alkali metal
US11912809B2 (en) 2022-06-02 2024-02-27 Chevron Phillips Chemical Company Lp High porosity fluorided silica-coated alumina activator-supports and uses thereof in metallocene-based catalyst systems for olefin polymerization
WO2023239560A1 (en) 2022-06-09 2023-12-14 Formosa Plastics Corporaton, U.S.A. Clay composite support-activators and catalyst compositions
US20240218089A1 (en) 2022-12-15 2024-07-04 Chevron Phillips Chemical Company Lp Oligomerization of alpha olefins using supported metallocene catalysts in selective production of vinylidene dimers

Family Cites Families (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3007725A1 (de) * 1980-02-29 1981-09-17 Hansjörg Prof. Dr. 2000 Hamburg Sinn Verfahren zur herstellung von polyethylen, polypropylen und copolymeren
US4411821A (en) * 1981-02-23 1983-10-25 E. I. Du Pont De Nemours And Company 1-Olefin polymerization catalyst
DE3127133A1 (de) * 1981-07-09 1983-01-27 Hoechst Ag, 6000 Frankfurt Verfahren zur herstellung von polyolefinen und deren copolymerisaten
US4497906A (en) * 1982-02-16 1985-02-05 Sumitomo Chemical Company, Limited Solid catalyst component for olefin polymerization
MX167872B (es) * 1983-06-06 1993-04-20 Exxon Research Engineering Co Proceso y catalizador para producir poliolefinas dmezclas del reactor
US4530914A (en) * 1983-06-06 1985-07-23 Exxon Research & Engineering Co. Process and catalyst for producing polyethylene having a broad molecular weight distribution
US4522982A (en) * 1983-06-06 1985-06-11 Exxon Research & Engineering Co. Isotactic-stereoblock polymers of alpha-olefins and process for producing the same
ZA844157B (en) * 1983-06-06 1986-01-29 Exxon Research Engineering Co Process and catalyst for polyolefin density and molecular weight control
JPH06811B2 (ja) * 1984-04-11 1994-01-05 出光興産株式会社 ポリオレフインの製造方法
DE3443087A1 (de) * 1984-11-27 1986-05-28 Hoechst Ag, 6230 Frankfurt Verfahren zur herstellung von polyolefinen
DE3508887A1 (de) * 1985-03-13 1986-09-25 Hoechst Ag, 6230 Frankfurt Verfahren zur herstellung von optisch aktiven polyolefinen
US4701432A (en) * 1985-11-15 1987-10-20 Exxon Chemical Patents Inc. Supported polymerization catalyst
IL80888A (en) * 1985-12-12 1991-12-12 Exxon Chemical Patents Inc Olefin polymerization catalysts,their preparation and use thereof
US4665047A (en) * 1986-08-15 1987-05-12 Shell Oil Company Stabilization of metallocene/aluminoxane catalysts
JP2618384B2 (ja) * 1986-12-27 1997-06-11 三井石油化学工業株式会社 オレフイン重合用固体触媒およびその製法
DE3789666T2 (de) * 1986-12-30 1994-08-04 Mitsui Petrochemical Ind Fester katalysator für die olefinpolymerisation und verfahren zu dessen herstellung.

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US4794096A (en) 1988-12-27
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JPS63251405A (ja) 1988-10-18
DE3751495T2 (de) 1996-03-07
KR880012652A (ko) 1988-11-28
CN1016425B (zh) 1992-04-29
KR950008154B1 (ko) 1995-07-25
ATE127128T1 (de) 1995-09-15
CA1302384C (en) 1992-06-02
CN87106984A (zh) 1988-10-19
JP2583909B2 (ja) 1997-02-19

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