DK0619325T3 - Katalysator og fremgangsmåde til fremstilling af polyalkener - Google Patents
Katalysator og fremgangsmåde til fremstilling af polyalkenerInfo
- Publication number
- DK0619325T3 DK0619325T3 DK93870064T DK93870064T DK0619325T3 DK 0619325 T3 DK0619325 T3 DK 0619325T3 DK 93870064 T DK93870064 T DK 93870064T DK 93870064 T DK93870064 T DK 93870064T DK 0619325 T3 DK0619325 T3 DK 0619325T3
- Authority
- DK
- Denmark
- Prior art keywords
- metallocenes
- catalyst
- transition metal
- cyclopentadienyls
- polyalkenes
- Prior art date
Links
Classifications
-
- 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
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
-
- 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
- C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F110/02—Ethene
-
- 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
- C08F4/63904—Component covered by group C08F4/62 containing a transition metal-carbon bond in combination with another component of C08F4/62
-
- 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
-
- Y—GENERAL 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
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S526/00—Synthetic resins or natural rubbers -- part of the class 520 series
- Y10S526/905—Polymerization in presence of transition metal containing catalyst in presence of hydrogen
-
- Y—GENERAL 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
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S526/00—Synthetic resins or natural rubbers -- part of the class 520 series
- Y10S526/943—Polymerization 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)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP93870064A EP0619325B1 (fr) | 1993-04-07 | 1993-04-07 | Procédé pour la préparation de catalysateurs de polyoléfines |
US08/224,604 US5719241A (en) | 1993-04-07 | 1994-04-07 | Process for producing polyolefins and polyolefin catalyst |
Publications (1)
Publication Number | Publication Date |
---|---|
DK0619325T3 true DK0619325T3 (da) | 2001-12-03 |
Family
ID=26134956
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
DK93870064T DK0619325T3 (da) | 1993-04-07 | 1993-04-07 | Katalysator og fremgangsmåde til fremstilling af polyalkener |
Country Status (10)
Country | Link |
---|---|
US (2) | US5719241A (fr) |
EP (1) | EP0619325B1 (fr) |
JP (1) | JP4049403B2 (fr) |
AT (1) | ATE204884T1 (fr) |
CA (1) | CA2120813C (fr) |
DE (1) | DE69330674T2 (fr) |
DK (1) | DK0619325T3 (fr) |
ES (1) | ES2163404T3 (fr) |
HU (1) | HU220239B (fr) |
PT (1) | PT619325E (fr) |
Families Citing this family (102)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CA2181413A1 (fr) * | 1995-07-18 | 1998-01-18 | Edwar S. Shamshoum | Methode pour la propagation syndiotactique des olefines |
US6239058B1 (en) * | 1995-07-18 | 2001-05-29 | Fina Technology, Inc. | Process for activating a metallocene catalyst supported on silica |
DE69633436T3 (de) † | 1995-07-24 | 2016-06-16 | Mitsui Chemicals, Inc. | Ethylen-Copolymer-Zusammensetzung |
FR2746672B1 (fr) * | 1996-04-02 | 1998-04-24 | Atochem Elf Sa | Composante catalytique et son utilisation en polymerisation des olefines |
WO1997042237A1 (fr) * | 1996-05-03 | 1997-11-13 | Dsm N.V. | Procede pour fabriquer des polyolefines ayant des repartitions larges des poids moleculaires |
US6759499B1 (en) * | 1996-07-16 | 2004-07-06 | Exxonmobil Chemical Patents Inc. | Olefin polymerization process with alkyl-substituted metallocenes |
US6583227B2 (en) * | 1996-09-04 | 2003-06-24 | Exxonmobil Chemical Patents Inc. | Propylene polymers for films |
US5847059A (en) * | 1996-12-20 | 1998-12-08 | Fina Technology, Inc. | Catalyst yield from supported metallocene catalysts |
US6180736B1 (en) | 1996-12-20 | 2001-01-30 | Exxon Chemical Patents Inc | High activity metallocene polymerization process |
EP0878486B1 (fr) * | 1997-02-21 | 2006-01-25 | Council of Scientific and Industrial Research | Procédé pour la préparation d'un catalyseur métallocène supporté |
GB9712663D0 (en) * | 1997-06-16 | 1997-08-20 | Borealis As | Process |
US6268447B1 (en) | 1998-12-18 | 2001-07-31 | Univation Technologies, L.L.C. | Olefin polymerization catalyst |
US6103657A (en) | 1997-07-02 | 2000-08-15 | Union Carbide Chemicals & Plastics Technology Corporation | Catalyst for the production of olefin polymers |
US6677265B1 (en) | 1997-12-08 | 2004-01-13 | Albemarle Corporation | Process of producing self-supported catalysts |
DE69907785T2 (de) | 1998-03-09 | 2004-02-12 | Basell Poliolefine Italia S.P.A. | Mehrstufiges Verfahren zur Olefinpolymerisation |
US6245868B1 (en) | 1998-05-29 | 2001-06-12 | Univation Technologies | Catalyst delivery method, a catalyst feeder and their use in a polymerization process |
EP1144465A2 (fr) * | 1998-12-18 | 2001-10-17 | Univation Technologies LLC | Systeme catalytique de polymerisation d'olefine, procede de polymerisation et polymere ainsi obtenu |
KR100438130B1 (ko) * | 1998-12-18 | 2004-07-02 | 유니베이션 테크놀로지즈, 엘엘씨 | 올레핀 중합촉매시스템, 중합방법 및 이로부터 생산된폴리머 |
US6303719B1 (en) * | 1998-12-18 | 2001-10-16 | Univation Technologies | Olefin polymerization catalyst system |
US20010047065A1 (en) * | 1999-06-03 | 2001-11-29 | Sun-Chueh Kao | Method for preparing a supported catalyst system and its use in a polymerization process |
US6482905B1 (en) | 1999-08-16 | 2002-11-19 | Phillips Petroleum Company | Unsymmetric unbridged bis-indenyl metallocenes and their use |
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 |
US6395666B1 (en) * | 1999-09-29 | 2002-05-28 | Phillips Petroleum Company | Organometal catalyst compositions |
TW526209B (en) * | 1999-10-21 | 2003-04-01 | Asahi Chemical Ind | Method for producing an olefin homopolymer or an olefin copolymer |
AU763705B2 (en) * | 1999-10-22 | 2003-07-31 | Univation Technologies Llc | Start up methods for multiple catalyst systems |
HUP0203789A2 (en) | 1999-12-16 | 2003-04-28 | Phillips Petroleum Co | Organometal compound catalyst |
US6384161B1 (en) * | 1999-12-30 | 2002-05-07 | Phillips Petroleum Company | Method and catalyst system for producing polyolefins with broadened molecular weight distributions |
US7041617B2 (en) | 2004-01-09 | 2006-05-09 | Chevron Phillips Chemical Company, L.P. | Catalyst compositions and polyolefins for extrusion coating applications |
EP1138702A1 (fr) | 2000-03-30 | 2001-10-04 | Fina Research S.A. | Polyéthylène préparé à l'aide d'un catalyseur métallocène pour fabriquer des containers plastiques brillants |
EP1138604A1 (fr) * | 2000-03-30 | 2001-10-04 | Fina Research S.A. | Récipients brillants en matière plastique |
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 |
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US6605675B2 (en) | 2000-12-04 | 2003-08-12 | Univation Technologies, Llc | Polymerization process |
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US6777367B2 (en) | 2001-02-13 | 2004-08-17 | Fina Technology, Inc. | Method for the preparation of metallocene catalysts |
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US11208514B2 (en) | 2008-03-20 | 2021-12-28 | Chevron Phillips Chemical Company Lp | Silica-coated alumina activator-supports for metallocene catalyst compositions |
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EP2348057A1 (fr) | 2010-01-21 | 2011-07-27 | INEOS Manufacturing Belgium NV | Nouveaux polymères |
US8148470B1 (en) | 2010-11-19 | 2012-04-03 | Exxonmobil Chemical Patents Inc. | Processes for making multimodal molecular weight distribution polyolefins |
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 |
WO2014078919A1 (fr) | 2012-11-26 | 2014-05-30 | Braskem S.A. | Catalyseur métallocène supporté sur support hybride, procédé d'obtention de celui-ci, procédé de polymérisation pour l 'obtention d'un homopolymère ou d'un copolymère d'éthylène à distribution de masse molaire large ou bimodale, utilisation du catalyseur de métallocène supporté et polymère d'éthylène à distribution de masse molaire large ou bimodale |
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 |
ES2752705T3 (es) | 2014-04-02 | 2020-04-06 | Univation Tech Llc | Composiciones de continuidad y método de polimerización de olefinas que las emplea |
CA2978925C (fr) | 2015-03-10 | 2023-08-22 | Univation Technologies, Llc | Compositions de catalyseur sechees par pulverisation, procedes de preparation et d'utilisation dans des procedes de polymerisation d'olefines |
US10519256B2 (en) | 2015-04-27 | 2019-12-31 | Univation Technologies, Llc | Supported catalyst compositions having improved flow properties and preparation thereof |
KR102064990B1 (ko) | 2016-03-11 | 2020-03-02 | 주식회사 엘지화학 | 에틸렌 슬러리 중합용 혼성 담지 촉매 시스템 및 이를 이용한 에틸렌 중합체의 제조 방법 |
KR101800866B1 (ko) * | 2016-04-26 | 2017-12-21 | 대림산업 주식회사 | 용융강도가 높은 멀티모달 폴리올레핀 수지 및 이로부터 제조되는 성형체 |
KR101706073B1 (ko) * | 2016-04-27 | 2017-02-13 | 한화케미칼 주식회사 | 혼성 담지 메탈로센 촉매를 이용한 고밀도 에틸렌계 중합체 및 제조방법 |
CN107987192B (zh) * | 2016-10-26 | 2021-07-02 | 中国石油化工股份有限公司 | 一种负载型茂金属催化剂及其应用 |
US10759879B2 (en) | 2017-09-26 | 2020-09-01 | Nichia Corporation | Alkyl metalloxane compound and method for producing the same |
US11098139B2 (en) * | 2018-02-28 | 2021-08-24 | Chevron Phillips Chemical Company Lp | Advanced quality control tools for manufacturing bimodal and multimodal polyethylene resins |
KR102372974B1 (ko) * | 2019-04-05 | 2022-03-10 | 한화솔루션 주식회사 | 혼성 촉매 조성물, 이를 포함하는 촉매 및 이들의 제조방법 |
CN110655597A (zh) * | 2019-10-09 | 2020-01-07 | 营口风光新材料股份有限公司 | MgCl2/硅胶载体负载茂金属催化剂的制备方法及应用 |
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US4935474A (en) * | 1983-06-06 | 1990-06-19 | Exxon Research & Engineering Company | Process and catalyst for producing polyethylene having a broad molecular weight distribution |
US4897455A (en) * | 1985-06-21 | 1990-01-30 | Exxon Chemical Patents Inc. | Polymerization process |
US4752597A (en) * | 1985-12-12 | 1988-06-21 | Exxon Chemical Patents Inc. | New polymerization catalyst |
US4659685A (en) * | 1986-03-17 | 1987-04-21 | The Dow Chemical Company | Heterogeneous organometallic catalysts containing a supported titanium compound and at least one other supported organometallic compound |
US4658078A (en) * | 1986-08-15 | 1987-04-14 | Shell Oil Company | Vinylidene olefin process |
JPH0742301B2 (ja) * | 1987-02-14 | 1995-05-10 | 三井石油化学工業株式会社 | 微粒子状アルミノオキサン、その製法およびその用途 |
US5064797A (en) * | 1987-04-03 | 1991-11-12 | Phillips Petroleum Company | Process for producing polyolefins and polyolefin catalysts |
IT1237398B (it) * | 1989-01-31 | 1993-06-01 | Ausimont Srl | Catalizzatori per la polimerizzazione di olefine. |
JP2566829B2 (ja) * | 1989-08-03 | 1996-12-25 | 日本石油株式会社 | ポリオレフィンの製造方法 |
MY107639A (en) * | 1990-04-18 | 1996-05-30 | Mitsui Chemicals Incorporated | Process for the preparation of an ethylene copolymer and an olefin polymer, and catalyst for olefin polymeri -zation |
US5087788A (en) * | 1991-03-04 | 1992-02-11 | Ethyl Corporation | Preparation of high purity vinylindene olefin |
DE69226564T3 (de) * | 1991-05-20 | 2004-04-08 | Mitsui Chemicals, Inc. | Katalysator und Verfahren für Olefinpolymerisation |
EP0516458B2 (fr) * | 1991-05-31 | 2007-12-19 | Mitsui Chemicals, Inc. | Composant solide de catalyseur, catalyseur et procédé de polymérisation d'oléfines |
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 |
-
1993
- 1993-04-07 DK DK93870064T patent/DK0619325T3/da active
- 1993-04-07 ES ES93870064T patent/ES2163404T3/es not_active Expired - Lifetime
- 1993-04-07 PT PT93870064T patent/PT619325E/pt unknown
- 1993-04-07 AT AT93870064T patent/ATE204884T1/de not_active IP Right Cessation
- 1993-04-07 EP EP93870064A patent/EP0619325B1/fr not_active Expired - Lifetime
- 1993-04-07 DE DE69330674T patent/DE69330674T2/de not_active Expired - Lifetime
-
1994
- 1994-04-06 JP JP09075694A patent/JP4049403B2/ja not_active Expired - Fee Related
- 1994-04-07 HU HU9400991A patent/HU220239B/hu not_active IP Right Cessation
- 1994-04-07 US US08/224,604 patent/US5719241A/en not_active Expired - Lifetime
- 1994-04-07 CA CA002120813A patent/CA2120813C/fr not_active Expired - Fee Related
-
1995
- 1995-06-02 US US08/459,526 patent/US6541413B1/en not_active Expired - Lifetime
Also Published As
Publication number | Publication date |
---|---|
CA2120813A1 (fr) | 1994-10-08 |
HU220239B (hu) | 2001-11-28 |
HUT67821A (en) | 1995-05-29 |
JPH06322014A (ja) | 1994-11-22 |
PT619325E (pt) | 2002-02-28 |
US5719241A (en) | 1998-02-17 |
ATE204884T1 (de) | 2001-09-15 |
EP0619325B1 (fr) | 2001-08-29 |
EP0619325A1 (fr) | 1994-10-12 |
HU9400991D0 (en) | 1994-06-28 |
ES2163404T3 (es) | 2002-02-01 |
DE69330674T2 (de) | 2002-07-04 |
CA2120813C (fr) | 2006-07-25 |
US6541413B1 (en) | 2003-04-01 |
JP4049403B2 (ja) | 2008-02-20 |
DE69330674D1 (de) | 2001-10-04 |
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