KR100282561B1 - 촉매계의 제조방법, 올레핀의 (공)중합법과 최소한 하나의 올레핀의 (공)중합체 - Google Patents
촉매계의 제조방법, 올레핀의 (공)중합법과 최소한 하나의 올레핀의 (공)중합체 Download PDFInfo
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- KR100282561B1 KR100282561B1 KR1019930010095A KR930010095A KR100282561B1 KR 100282561 B1 KR100282561 B1 KR 100282561B1 KR 1019930010095 A KR1019930010095 A KR 1019930010095A KR 930010095 A KR930010095 A KR 930010095A KR 100282561 B1 KR100282561 B1 KR 100282561B1
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- South Korea
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- neutral metallocene
- group
- polymerization
- general formula
- process according
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- Expired - Fee Related
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Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
- C08F4/62—Refractory metals or compounds thereof
- C08F4/64—Titanium, zirconium, hafnium or compounds thereof
- C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
- C08F4/6592—Component 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
- C08F4/65922—Component 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
- C08F4/62—Refractory metals or compounds thereof
- C08F4/639—Component covered by group C08F4/62 containing a transition metal-carbon bond
- C08F4/63908—Component covered by group C08F4/62 containing a transition metal-carbon bond in combination with an ionising compound other than alumoxane, e.g. (C6F5)4B-X+
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
- C08F4/62—Refractory metals or compounds thereof
- C08F4/639—Component covered by group C08F4/62 containing a transition metal-carbon bond
- C08F4/63912—Component covered by group C08F4/62 containing a transition metal-carbon bond in combination with an organoaluminium compound
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
- C08F4/62—Refractory metals or compounds thereof
- C08F4/639—Component covered by group C08F4/62 containing a transition metal-carbon bond
- C08F4/63916—Component covered by group C08F4/62 containing a transition metal-carbon bond supported on a carrier, e.g. silica, MgCl2, polymer
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
- C08F4/62—Refractory metals or compounds thereof
- C08F4/639—Component covered by group C08F4/62 containing a transition metal-carbon bond
- C08F4/6392—Component covered by group C08F4/62 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring
- C08F4/63922—Component covered by group C08F4/62 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
- C08F4/62—Refractory metals or compounds thereof
- C08F4/64—Titanium, zirconium, hafnium or compounds thereof
- C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
- C08F4/65908—Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with an ionising compound other than alumoxane, e.g. (C6F5)4B-X+
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
- C08F4/62—Refractory metals or compounds thereof
- C08F4/64—Titanium, zirconium, hafnium or compounds thereof
- C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
- C08F4/65916—Component covered by group C08F4/64 containing a transition metal-carbon bond supported on a carrier, e.g. silica, MgCl2, polymer
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| BE9200526A BE1005957A5 (fr) | 1992-06-05 | 1992-06-05 | Procede de preparation d'un systeme catalytique, procede de (co)polymerisation d'olefines et (co)polymeres d'au moins une olefine. |
| BE09200526 | 1992-06-05 | ||
| BE9200526 | 1992-06-05 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| KR940000484A KR940000484A (ko) | 1994-01-03 |
| KR100282561B1 true KR100282561B1 (ko) | 2001-02-15 |
Family
ID=3886306
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| KR1019930010095A Expired - Fee Related KR100282561B1 (ko) | 1992-06-05 | 1993-06-04 | 촉매계의 제조방법, 올레핀의 (공)중합법과 최소한 하나의 올레핀의 (공)중합체 |
Country Status (11)
| Country | Link |
|---|---|
| US (3) | US5612271A (https=) |
| EP (2) | EP0573120B1 (https=) |
| JP (1) | JP3429026B2 (https=) |
| KR (1) | KR100282561B1 (https=) |
| AT (2) | ATE258191T1 (https=) |
| BE (1) | BE1005957A5 (https=) |
| CA (1) | CA2097777C (https=) |
| DE (2) | DE69333399T2 (https=) |
| ES (2) | ES2125941T3 (https=) |
| RU (1) | RU2117677C1 (https=) |
| TW (1) | TW286321B (https=) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2013077512A1 (ko) * | 2011-11-24 | 2013-05-30 | 삼성토탈 주식회사 | 올레핀 중합 및 공중합용 촉매 및 이를 사용하는 올레핀 중합 또는 공중합 방법 |
Families Citing this family (171)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| BE1006880A3 (fr) * | 1993-03-01 | 1995-01-17 | Solvay | Precurseur solide d'un systeme catalytique pour la polymerisation d'olefines, procede pour sa preparation, systeme catalytique comprenant ce precurseur solide et procede de polymerisation d'olefines en presence de ce systeme catalytique. |
| ES2156153T3 (es) * | 1993-06-15 | 2001-06-16 | Idemitsu Kosan Co | Procedimiento de produccion de polimero olefinico, y catalizador para la polimerizacion de una olefina. |
| US5498582A (en) * | 1993-12-06 | 1996-03-12 | Mobil Oil Corporation | Supported metallocene catalysts for the production of polyolefins |
| US6008307A (en) * | 1994-04-28 | 1999-12-28 | Exxon Chemical Patents Inc | Process for producing olefin polymers using cationic catalysts |
| US6291389B1 (en) | 1994-04-28 | 2001-09-18 | Exxonmobil Chemical Patents Inc. | Cationic polymerization catalysts |
| DE4431838A1 (de) * | 1994-09-07 | 1996-03-14 | Basf Ag | Geträgerte Metallocen-Katalysatorsysteme |
| DE4431837A1 (de) * | 1994-09-07 | 1996-03-14 | Basf Ag | Geträgerte Metallocen-Katalysatorsysteme |
| 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. |
| JP2000517349A (ja) * | 1996-03-27 | 2000-12-26 | ザ ダウ ケミカル カンパニー | 分散した触媒活性剤による溶液重合法 |
| DE19617229A1 (de) * | 1996-04-30 | 1997-11-06 | Basf Ag | Verfahren zur Herstellung von niedermolekularen Ethylenpolymerisaten im Hochdruck |
| BR9917674B1 (pt) * | 1998-05-18 | 2012-06-12 | processo para produzir uma composiÇço de catalisador para polimerizar monâmeros. | |
| US6107230A (en) * | 1998-05-18 | 2000-08-22 | Phillips Petroleum Company | Compositions that can produce polymers |
| US6300271B1 (en) * | 1998-05-18 | 2001-10-09 | Phillips Petroleum Company | Compositions that can produce polymers |
| US6165929A (en) | 1998-05-18 | 2000-12-26 | Phillips Petroleum Company | Compositions that can produce polymers |
| US6291386B1 (en) * | 1999-05-25 | 2001-09-18 | Equistar Chemicals, Lp | Process for the in-situ preparation of single-site transition metal catalysts and polymerization process |
| US6355594B1 (en) * | 1999-09-27 | 2002-03-12 | Phillips Petroleum Company | Organometal catalyst compositions |
| US6395666B1 (en) * | 1999-09-29 | 2002-05-28 | Phillips Petroleum Company | Organometal catalyst compositions |
| US6395847B2 (en) | 1999-11-19 | 2002-05-28 | Exxonmobil Chemical Patents Inc. | Supported organometallic catalysts and their use in olefin polymerization |
| US6750302B1 (en) | 1999-12-16 | 2004-06-15 | Phillips Petroleum Company | Organometal catalyst compositions |
| US6524987B1 (en) * | 1999-12-22 | 2003-02-25 | Phillips Petroleum Company | Organometal catalyst compositions |
| US6555495B2 (en) * | 2000-12-06 | 2003-04-29 | Univation Technologies, Llc | Catalyst support method and polymerization with supported catalysts |
| TWI300782B (en) * | 2002-08-29 | 2008-09-11 | Ineos Europe Ltd | Supported polymerisation catalysts |
| US7700707B2 (en) | 2002-10-15 | 2010-04-20 | Exxonmobil Chemical Patents Inc. | Polyolefin adhesive compositions and articles made therefrom |
| US7541402B2 (en) | 2002-10-15 | 2009-06-02 | Exxonmobil Chemical Patents Inc. | Blend functionalized polyolefin adhesive |
| US7223822B2 (en) | 2002-10-15 | 2007-05-29 | Exxonmobil Chemical Patents Inc. | Multiple catalyst and reactor system for olefin polymerization and polymers produced therefrom |
| WO2004046214A2 (en) | 2002-10-15 | 2004-06-03 | Exxonmobil Chemical Patents Inc. | Multiple catalyst system for olefin polymerization and polymers produced therefrom |
| US7550528B2 (en) | 2002-10-15 | 2009-06-23 | Exxonmobil Chemical Patents Inc. | Functionalized olefin polymers |
| US7119153B2 (en) * | 2004-01-21 | 2006-10-10 | Jensen Michael D | Dual metallocene catalyst for producing film resins with good machine direction (MD) elmendorf tear strength |
| SG151310A1 (en) | 2004-03-17 | 2009-04-30 | Dow Global Technologies Inc | Catalyst composition comprising shuttling agent for ethylene copolymer formation |
| SG151301A1 (en) | 2004-03-17 | 2009-04-30 | Dow Global Technologies Inc | Catalyst composition comprising shuttling agent for ethylene multi- block copolymer formation |
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| CN102321201B (zh) | 2004-06-16 | 2013-06-26 | 陶氏环球技术有限责任公司 | 选择聚合改性剂的方法 |
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| US9410009B2 (en) | 2005-03-17 | 2016-08-09 | Dow Global Technologies Llc | Catalyst composition comprising shuttling agent for tactic/ atactic multi-block copolymer formation |
| MX2007011340A (es) | 2005-03-17 | 2007-10-03 | Dow Global Technologies Inc | Composicion de catalizador que comprende un agente de transporte para la formacion de copolimero de bloques multiples regio-irregular. |
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| JP5507263B2 (ja) | 2007-03-07 | 2014-05-28 | ダウ グローバル テクノロジーズ エルエルシー | 固定化されている担持された遷移金属錯体 |
| ITMI20070877A1 (it) | 2007-05-02 | 2008-11-03 | Dow Global Technologies Inc | Processo per la produzione di copolimeri a blocchi multipli con l'utilizzo di solventi polari |
| ITMI20070878A1 (it) | 2007-05-02 | 2008-11-03 | Dow Global Technologies Inc | Processo per la polimerizzazine di polimeri tattici con l'uso di catalizzatori chirali |
| ES2435568T3 (es) | 2007-11-19 | 2013-12-20 | Dow Global Technologies Llc | Copolímeros de propileno-alfa-olefina con ramificación de cadena larga |
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| CN102421807B (zh) | 2009-03-06 | 2015-03-18 | 陶氏环球技术有限责任公司 | 催化剂、制备催化剂的方法、制备聚烯烃组合物的方法和聚烯烃组合物 |
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| US8877672B2 (en) | 2013-01-29 | 2014-11-04 | Chevron Phillips Chemical Company Lp | Catalyst compositions and methods of making and using same |
| CN105189566A (zh) | 2013-01-30 | 2015-12-23 | 尤尼威蒂恩技术有限责任公司 | 制造具有改进的流动的催化剂组合物的方法 |
| KR20200096700A (ko) * | 2013-07-09 | 2020-08-12 | 다우 글로벌 테크놀로지스 엘엘씨 | 개선된 펠렛 유동능을 갖는 에틸렌/알파-올레핀 인터폴리머 |
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| 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 |
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| JP3115595B2 (ja) * | 1990-07-24 | 2000-12-11 | 三井化学株式会社 | α―オレフィンの重合触媒及びそれを用いたポリ―α―オレフィンの製造方法 |
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| JP2951763B2 (ja) * | 1991-08-27 | 1999-09-20 | 三井化学株式会社 | メタロセン化合物溶液及びその保存方法 |
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| JPH05301919A (ja) * | 1992-04-27 | 1993-11-16 | Tosoh Corp | オレフィン重合用触媒及びオレフィンの重合方法 |
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- 1993-06-01 AT AT98201013T patent/ATE258191T1/de not_active IP Right Cessation
- 1993-06-01 DE DE69333399T patent/DE69333399T2/de not_active Expired - Fee Related
- 1993-06-01 TW TW082104364A patent/TW286321B/zh active
- 1993-06-01 EP EP93201560A patent/EP0573120B1/fr not_active Expired - Lifetime
- 1993-06-01 DE DE69321877T patent/DE69321877T2/de not_active Expired - Fee Related
- 1993-06-01 EP EP98201013A patent/EP0857735B1/fr not_active Expired - Lifetime
- 1993-06-01 ES ES93201560T patent/ES2125941T3/es not_active Expired - Lifetime
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- 1993-06-04 KR KR1019930010095A patent/KR100282561B1/ko not_active Expired - Fee Related
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- 1993-06-07 JP JP13612193A patent/JP3429026B2/ja not_active Expired - Fee Related
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- 1996-11-25 US US08/754,174 patent/US5817725A/en not_active Expired - Fee Related
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2013077512A1 (ko) * | 2011-11-24 | 2013-05-30 | 삼성토탈 주식회사 | 올레핀 중합 및 공중합용 촉매 및 이를 사용하는 올레핀 중합 또는 공중합 방법 |
Also Published As
| Publication number | Publication date |
|---|---|
| KR940000484A (ko) | 1994-01-03 |
| CA2097777A1 (fr) | 1993-12-06 |
| EP0857735A2 (fr) | 1998-08-12 |
| DE69321877T2 (de) | 1999-06-10 |
| EP0573120A1 (fr) | 1993-12-08 |
| US6555632B1 (en) | 2003-04-29 |
| EP0857735B1 (fr) | 2004-01-21 |
| ES2125941T3 (es) | 1999-03-16 |
| ES2213872T3 (es) | 2004-09-01 |
| EP0857735A3 (fr) | 2000-07-26 |
| EP0573120B1 (fr) | 1998-11-04 |
| BE1005957A5 (fr) | 1994-04-05 |
| DE69333399T2 (de) | 2004-12-09 |
| RU2117677C1 (ru) | 1998-08-20 |
| JPH0632830A (ja) | 1994-02-08 |
| ATE258191T1 (de) | 2004-02-15 |
| JP3429026B2 (ja) | 2003-07-22 |
| TW286321B (https=) | 1996-09-21 |
| DE69321877D1 (de) | 1998-12-10 |
| CA2097777C (fr) | 2003-12-30 |
| DE69333399D1 (de) | 2004-02-26 |
| ATE172991T1 (de) | 1998-11-15 |
| US5612271A (en) | 1997-03-18 |
| US5817725A (en) | 1998-10-06 |
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