ATE289868T1 - Verfahren zur olefinpolymerisation, das die nicht-hydrolytische herstellung von aluminoxan umfasst - Google Patents
Verfahren zur olefinpolymerisation, das die nicht-hydrolytische herstellung von aluminoxan umfasstInfo
- Publication number
- ATE289868T1 ATE289868T1 AT96944390T AT96944390T ATE289868T1 AT E289868 T1 ATE289868 T1 AT E289868T1 AT 96944390 T AT96944390 T AT 96944390T AT 96944390 T AT96944390 T AT 96944390T AT E289868 T1 ATE289868 T1 AT E289868T1
- Authority
- AT
- Austria
- Prior art keywords
- aluminoxane
- composition
- carbon
- olefin polymerization
- hydrolytic
- Prior art date
Links
- 238000000034 method Methods 0.000 title abstract 2
- 150000001336 alkenes Chemical class 0.000 title 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 title 1
- 238000006116 polymerization reaction Methods 0.000 title 1
- 239000000203 mixture Substances 0.000 abstract 6
- 150000001875 compounds Chemical class 0.000 abstract 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 abstract 2
- 229910052760 oxygen Inorganic materials 0.000 abstract 2
- 239000001301 oxygen Substances 0.000 abstract 2
- 239000002243 precursor Substances 0.000 abstract 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 abstract 1
- 125000005234 alkyl aluminium group Chemical group 0.000 abstract 1
- 229910002092 carbon dioxide Inorganic materials 0.000 abstract 1
- 239000001569 carbon dioxide Substances 0.000 abstract 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 abstract 1
- 230000003301 hydrolyzing effect Effects 0.000 abstract 1
- 150000002576 ketones Chemical class 0.000 abstract 1
- 230000009466 transformation Effects 0.000 abstract 1
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 abstract 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/12—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides
- B01J31/14—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides of aluminium or boron
- B01J31/143—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides of aluminium or boron of aluminium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/1616—Coordination complexes, e.g. organometallic complexes, immobilised on an inorganic support, e.g. ship-in-a-bottle type catalysts
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2282—Unsaturated compounds used as ligands
- B01J31/2295—Cyclic compounds, e.g. cyclopentadienyls
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
- C07F5/06—Aluminium compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
- C07F5/06—Aluminium compounds
- C07F5/061—Aluminium compounds with C-aluminium linkage
- C07F5/066—Aluminium compounds with C-aluminium linkage compounds with Al linked to an element other than Al, C, H or halogen (this includes Al-cyanide linkage)
- C07F5/068—Aluminium compounds with C-aluminium linkage compounds with Al linked to an element other than Al, C, H or halogen (this includes Al-cyanide linkage) preparation of alum(in)oxanes
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/40—Complexes comprising metals of Group IV (IVA or IVB) as the central metal
- B01J2531/48—Zirconium
-
- 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
- C08F4/619—Component covered by group C08F4/60 containing a transition metal-carbon bond
- C08F4/61912—Component covered by group C08F4/60 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
- C08F4/619—Component covered by group C08F4/60 containing a transition metal-carbon bond
- C08F4/61916—Component covered by group C08F4/60 containing a transition metal-carbon bond supported on a carrier, e.g. silica, MgCl2, polymer
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Inorganic Chemistry (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Toxicology (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
- Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
- Polymerization Catalysts (AREA)
- Catalysts (AREA)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US08/576,892 US5831109A (en) | 1995-12-22 | 1995-12-22 | Polyalkylaluminoxane compositions formed by non-hydrolytic means |
| PCT/US1996/019980 WO1997023288A1 (en) | 1995-12-22 | 1996-12-18 | Polyalkylaluminoxane compositions formed by non-hydrolytic means |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| ATE289868T1 true ATE289868T1 (de) | 2005-03-15 |
Family
ID=24306444
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| AT96944390T ATE289868T1 (de) | 1995-12-22 | 1996-12-18 | Verfahren zur olefinpolymerisation, das die nicht-hydrolytische herstellung von aluminoxan umfasst |
Country Status (12)
| Country | Link |
|---|---|
| US (1) | US5831109A (de) |
| EP (1) | EP0966322B1 (de) |
| JP (1) | JP4112005B2 (de) |
| KR (1) | KR100417968B1 (de) |
| CN (1) | CN1093138C (de) |
| AT (1) | ATE289868T1 (de) |
| AU (1) | AU1421097A (de) |
| DE (1) | DE69634424T2 (de) |
| ES (1) | ES2238701T3 (de) |
| HK (1) | HK1018419A1 (de) |
| TW (1) | TW581768B (de) |
| WO (1) | WO1997023288A1 (de) |
Families Citing this family (40)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6159889A (en) * | 1997-12-09 | 2000-12-12 | Union Carbide Chemicals & Plastics Technology Corporation | Unbridged monocyclopentadienyl metal complex catalyst and a process for polyolefin production |
| US5962362A (en) | 1997-12-09 | 1999-10-05 | Union Carbide Chemicals & Plastics Technology Corporation | Unbridged monocyclopentadienyl metal complex catalyst and a process for polyolefin production |
| US6127302A (en) * | 1997-12-09 | 2000-10-03 | Union Carbide Chemicals & Plastics Technology Corporation | Unbridged monocyclopentadienyl metal complex catalyst and a process for polyolefin production |
| US6153550A (en) * | 1997-12-18 | 2000-11-28 | Mobile Oil Corporation | Olefin polymerization catalyst based on metallocene complexes and perfluorinated oligoaryl derivatives of aluminates |
| US6015766A (en) * | 1997-12-18 | 2000-01-18 | Mobil Oil Corporation | Catalyst systems for olefin polymerization based on metallocene complexes and oligoalkylaluminates with sterically hindered alkyl groups as cocatalysts |
| US6013820A (en) * | 1998-03-18 | 2000-01-11 | Albemarle Corporation | Alkylaluminoxane compositions and their preparation |
| US6936306B1 (en) | 1998-03-30 | 2005-08-30 | William Marsh Rice University | Chemical control over ceramic porosity using carboxylate-alumoxanes |
| US6369183B1 (en) | 1998-08-13 | 2002-04-09 | Wm. Marsh Rice University | Methods and materials for fabrication of alumoxane polymers |
| US7220804B1 (en) | 2000-10-13 | 2007-05-22 | Univation Technologies, Llc | Method for preparing a catalyst system and its use in a polymerization process |
| US6518445B1 (en) | 2000-12-15 | 2003-02-11 | Albemarle Corporation | Methylaluminoxane compositions, enriched solutions of such compositions, and the preparation thereof |
| WO2003062140A2 (en) | 2002-01-24 | 2003-07-31 | William Marsh Rice University | Organic acid-feooh (ferroxane) particles and ferroxane-derived ceramics and ceramic membranes |
| EP1348722A1 (de) * | 2002-03-25 | 2003-10-01 | SOLVAY POLYOLEFINS EUROPE - BELGIUM (Société Anonyme) | Verfahren zur Polymerisation von Olefinen |
| US6933046B1 (en) | 2002-06-12 | 2005-08-23 | Tda Research, Inc. | Releasable corrosion inhibitor compositions |
| US7244498B2 (en) | 2002-06-12 | 2007-07-17 | Tda Research, Inc. | Nanoparticles modified with multiple organic acids |
| US6887517B1 (en) | 2002-06-12 | 2005-05-03 | Tda Research | Surface modified particles by multi-step Michael-type addition and process for the preparation thereof |
| US6986943B1 (en) | 2002-06-12 | 2006-01-17 | Tda Research, Inc. | Surface modified particles by multi-step addition and process for the preparation thereof |
| US7193100B2 (en) * | 2003-12-31 | 2007-03-20 | Albemarle Corporation | Haloaluminoxane compositions, their preparation, and their use in catalysis |
| JP4476657B2 (ja) * | 2004-03-22 | 2010-06-09 | 東ソー・ファインケム株式会社 | ポリメチルアルミノキサン調製物、その製造方法、重合触媒およびオレフィン類の重合方法 |
| FR2917308B1 (fr) * | 2007-06-18 | 2009-12-04 | Centre Nat Rech Scient | Systeme catalytique, procede de fabrication et utilisation |
| JP5611833B2 (ja) | 2008-11-11 | 2014-10-22 | 東ソー・ファインケム株式会社 | 固体状ポリメチルアルミノキサン組成物およびその製造方法 |
| WO2011078923A1 (en) | 2009-12-23 | 2011-06-30 | Univation Technologies, Llc | Methods for producing catalyst systems |
| CN102869684B (zh) * | 2010-05-11 | 2015-12-02 | 东曹精细化工株式会社 | 固体状载体-聚甲基铝氧烷复合体、其制造方法、烯烃类的聚合催化剂和聚烯烃类的制造方法 |
| CA2737713C (en) * | 2011-04-20 | 2018-10-30 | Nova Chemicals Corporation | Activation for oligomerization |
| CN103182156B (zh) * | 2011-12-28 | 2016-04-06 | 中国石油天然气股份有限公司 | 烷基铝生产过程中危险废弃物的回收处理方法 |
| WO2013146337A1 (ja) | 2012-03-28 | 2013-10-03 | 東ソー・ファインケム株式会社 | 小粒径固体状ポリメチルアルミノキサン組成物の製造方法 |
| CN109369830A (zh) * | 2012-07-11 | 2019-02-22 | 亚培烯科技（杭州）有限公司 | 固体活化剂体系及其制备方法 |
| CN107722148B (zh) * | 2013-02-08 | 2021-06-08 | 三井化学株式会社 | 固体状聚铝氧烷组合物、烯烃聚合用催化剂、烯烃聚合物的制造方法 |
| EP3063155B1 (de) * | 2013-10-28 | 2017-09-20 | Akzo Nobel Chemicals International B.V. | Verfahren zur herstellung von aluminoxanen durch hydrolyse von alkylaluminium mit allylalkoholen |
| US10323047B2 (en) | 2015-04-24 | 2019-06-18 | Akzo Nobel Chemicals International B.V. | Process to prepare aluminoxanes |
| EP3441406A4 (de) * | 2016-04-05 | 2020-01-08 | Tosoh Finechem Corporation | Feste pmao-zusammensetzung und verfahren zur herstellung davon |
| JP6940939B2 (ja) * | 2016-09-21 | 2021-09-29 | 大日本印刷株式会社 | パターン形成方法及び凹凸構造体の製造方法 |
| US11161922B2 (en) | 2017-10-31 | 2021-11-02 | Exxonmobil Chemical Patents Inc. | Toluene free silica supported single-site metallocene catalysts from in-situ supported MAO formation in aliphatic solvents |
| US11021552B2 (en) * | 2017-10-31 | 2021-06-01 | Exxonmobil Chemical Patents Inc. | Toluene free silica supported single-site metallocene catalysts from in-situ supported alumoxane formation in aliphatic solvents |
| JP7216958B2 (ja) * | 2019-02-28 | 2023-02-02 | 国立大学法人広島大学 | 高純度固体アルミノキサン及びその製造方法 |
| US20220275113A1 (en) * | 2019-09-30 | 2022-09-01 | Lg Chem, Ltd. | Method for Purifying Polyalkylaluminoxane-Containing Solution Using Hydroxy Group-Containing Compound and Catalyst Composition Using the Same |
| CN111662398A (zh) * | 2020-06-19 | 2020-09-15 | 上海东化环境工程有限公司 | 一种改性烷基铝氧烷、制备方法及用于聚烯烃聚合反应的催化剂 |
| EP4247820A1 (de) | 2020-11-23 | 2023-09-27 | ExxonMobil Chemical Patents Inc. | <smallcaps/>?in-situ ?verbessertes verfahren zur herstellung eines katalysators aus geformtem alumoxan |
| EP4247821A1 (de) | 2020-11-23 | 2023-09-27 | ExxonMobil Chemical Patents Inc. | Nicht-hydrolytische herstellung von smac und katalysatoren |
| US20230416418A1 (en) | 2020-11-23 | 2023-12-28 | Exxonmobil Chemical Patents Inc. | Metallocene polypropylene prepared using aromatic solvent-free supports |
| WO2022108971A1 (en) | 2020-11-23 | 2022-05-27 | Exxonmobil Chemical Patents Inc. | Toluene free supported methylalumoxane precursor |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3240383A1 (de) * | 1982-11-02 | 1984-05-03 | Hoechst Ag, 6230 Frankfurt | Verfahren zur herstellung von oligomeren aluminoxanen |
| CA1304746C (en) * | 1987-08-31 | 1992-07-07 | The Dow Chemical Company | Preparation of polyhydrocarbylaluminoxanes |
| US5066631A (en) * | 1990-10-16 | 1991-11-19 | Ethyl Corporation | Hydrocarbon solutions of alkylaluminoxane compounds |
| US5235081A (en) * | 1992-03-18 | 1993-08-10 | Ethyl Corporation | Method of removing gel forming materials from methylaluminoxanes |
| JPH0730091B2 (ja) * | 1991-09-06 | 1995-04-05 | 東ソー・アクゾ株式会社 | アルミノキサン類の製造方法 |
| US5329032A (en) * | 1992-03-18 | 1994-07-12 | Akzo Chemicals Inc. | Polymethylaluminoxane of enhanced solution stability |
| US5728855A (en) * | 1995-10-19 | 1998-03-17 | Akzo Nobel Nv | Modified polyalkylaluminoxane composition formed using reagent containing carbon-oxygen double bond |
-
1995
- 1995-12-22 US US08/576,892 patent/US5831109A/en not_active Expired - Lifetime
-
1996
- 1996-12-18 AU AU14210/97A patent/AU1421097A/en not_active Abandoned
- 1996-12-18 ES ES96944390T patent/ES2238701T3/es not_active Expired - Lifetime
- 1996-12-18 WO PCT/US1996/019980 patent/WO1997023288A1/en active IP Right Grant
- 1996-12-18 CN CN96180050A patent/CN1093138C/zh not_active Expired - Lifetime
- 1996-12-18 DE DE69634424T patent/DE69634424T2/de not_active Expired - Lifetime
- 1996-12-18 JP JP52373997A patent/JP4112005B2/ja not_active Expired - Lifetime
- 1996-12-18 EP EP96944390A patent/EP0966322B1/de not_active Expired - Lifetime
- 1996-12-18 KR KR10-1998-0704892A patent/KR100417968B1/ko not_active IP Right Cessation
- 1996-12-18 AT AT96944390T patent/ATE289868T1/de not_active IP Right Cessation
-
1997
- 1997-05-06 TW TW086106014A patent/TW581768B/zh not_active IP Right Cessation
-
1999
- 1999-08-17 HK HK99103575A patent/HK1018419A1/xx not_active IP Right Cessation
Also Published As
| Publication number | Publication date |
|---|---|
| HK1018419A1 (en) | 1999-12-24 |
| AU1421097A (en) | 1997-07-17 |
| JP4112005B2 (ja) | 2008-07-02 |
| KR100417968B1 (ko) | 2004-03-19 |
| TW581768B (en) | 2004-04-01 |
| CN1209080A (zh) | 1999-02-24 |
| EP0966322B1 (de) | 2005-03-02 |
| DE69634424T2 (de) | 2006-05-11 |
| KR19990076769A (ko) | 1999-10-15 |
| JP2000505785A (ja) | 2000-05-16 |
| DE69634424D1 (de) | 2005-04-07 |
| EP0966322A4 (de) | 2000-06-28 |
| ES2238701T3 (es) | 2005-09-01 |
| CN1093138C (zh) | 2002-10-23 |
| US5831109A (en) | 1998-11-03 |
| WO1997023288A1 (en) | 1997-07-03 |
| EP0966322A1 (de) | 1999-12-29 |
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