DK0730574T3 - Fremgangsmåder og katalysatorsammensætninger til hydrocyanering af monoolefiner - Google Patents
Fremgangsmåder og katalysatorsammensætninger til hydrocyanering af monoolefinerInfo
- Publication number
- DK0730574T3 DK0730574T3 DK95901801T DK95901801T DK0730574T3 DK 0730574 T3 DK0730574 T3 DK 0730574T3 DK 95901801 T DK95901801 T DK 95901801T DK 95901801 T DK95901801 T DK 95901801T DK 0730574 T3 DK0730574 T3 DK 0730574T3
- Authority
- DK
- Denmark
- Prior art keywords
- monoolefins
- pct
- hydrocyanation
- methods
- sec
- Prior art date
Links
- 239000000203 mixture Substances 0.000 title abstract 3
- 150000005673 monoalkenes Chemical class 0.000 title abstract 3
- 238000005669 hydrocyanation reaction Methods 0.000 title abstract 2
- 239000003054 catalyst Substances 0.000 title 1
- 238000000034 method Methods 0.000 title 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 abstract 2
- 239000012018 catalyst precursor Substances 0.000 abstract 2
- 239000002841 Lewis acid Substances 0.000 abstract 1
- -1 acyclic aliphatic monoolefins Chemical class 0.000 abstract 1
- 125000004185 ester group Chemical group 0.000 abstract 1
- 150000007517 lewis acids Chemical class 0.000 abstract 1
- 239000003446 ligand Substances 0.000 abstract 1
- 229910052759 nickel Inorganic materials 0.000 abstract 1
- 125000002560 nitrile group Chemical group 0.000 abstract 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-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
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1845—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing phosphorus
- B01J31/185—Phosphites ((RO)3P), their isomeric phosphonates (R(RO)2P=O) and RO-substitution derivatives thereof
-
- 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
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
-
- 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
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C253/00—Preparation of carboxylic acid nitriles
- C07C253/08—Preparation of carboxylic acid nitriles by addition of hydrogen cyanide or salts thereof to unsaturated compounds
- C07C253/10—Preparation of carboxylic acid nitriles by addition of hydrogen cyanide or salts thereof to unsaturated compounds to compounds containing carbon-to-carbon double bonds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C255/00—Carboxylic acid nitriles
- C07C255/01—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms
- C07C255/02—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms of an acyclic and saturated carbon skeleton
- C07C255/03—Mononitriles
-
- 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
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/30—Addition reactions at carbon centres, i.e. to either C-C or C-X multiple bonds
- B01J2231/32—Addition reactions to C=C or C-C triple bonds
- B01J2231/323—Hydrometalation, e.g. bor-, alumin-, silyl-, zirconation or analoguous reactions like carbometalation, hydrocarbation
-
- 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
- B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
- B01J2531/0261—Complexes comprising ligands with non-tetrahedral chirality
- B01J2531/0266—Axially chiral or atropisomeric ligands, e.g. bulky biaryls such as donor-substituted binaphthalenes, e.g. "BINAP" or "BINOL"
-
- 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
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/84—Metals of the iron group
- B01J2531/847—Nickel
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US15734293A | 1993-11-23 | 1993-11-23 | |
| US19896394A | 1994-02-18 | 1994-02-18 | |
| PCT/US1994/012794 WO1995014659A1 (fr) | 1993-11-23 | 1994-11-07 | Procedes et compositions de catalyseurs pour hydrocyanuration de mono-olefines |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DK0730574T3 true DK0730574T3 (da) | 1999-05-25 |
Family
ID=26854028
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DK95901801T DK0730574T3 (da) | 1993-11-23 | 1994-11-07 | Fremgangsmåder og katalysatorsammensætninger til hydrocyanering af monoolefiner |
Country Status (14)
| Country | Link |
|---|---|
| US (2) | US5688986A (fr) |
| EP (1) | EP0730574B1 (fr) |
| JP (1) | JP3553952B2 (fr) |
| KR (1) | KR100263138B1 (fr) |
| CN (2) | CN1082946C (fr) |
| AT (1) | ATE169902T1 (fr) |
| BR (1) | BR9408151A (fr) |
| CA (1) | CA2177135C (fr) |
| DE (1) | DE69412635T2 (fr) |
| DK (1) | DK0730574T3 (fr) |
| ES (1) | ES2122515T3 (fr) |
| GR (1) | GR3027731T3 (fr) |
| TW (1) | TW457244B (fr) |
| WO (1) | WO1995014659A1 (fr) |
Families Citing this family (106)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| ATE196745T1 (de) | 1994-04-14 | 2000-10-15 | Du Pont | Nickel und phosphinebidentat enthaltende katalysatorzusammen- setzungen zur hydrocyanierung von monoolefinen |
| TW315370B (fr) * | 1994-10-07 | 1997-09-11 | Du Pont | |
| IN187044B (fr) * | 1995-01-27 | 2002-01-05 | Du Pont | |
| US5821378A (en) * | 1995-01-27 | 1998-10-13 | E. I. Du Pont De Nemours And Company | Hydrocyanation of diolefins and isomerization of nonconjugated 2-alkyl-3-monoalkenenitriles |
| FR2743010B1 (fr) * | 1995-12-29 | 1998-02-20 | Rhone Poulenc Fibres | Procede de preparation par hydrogenation de catalyseurs a base de metal de transition et de phosphine |
| DE19652273A1 (de) | 1996-12-16 | 1998-06-18 | Basf Ag | Monoolefinische C¶5¶-Mononitrile, Verfahren zu ihrer Herstellung und ihre Verwendung |
| US5847191A (en) * | 1997-07-29 | 1998-12-08 | E. I. Du Pont De Nemours And Company | Process for the hydrocyanation of monoolefins using bidentate phosphite ligands and zero-valent nickel |
| US6121184A (en) * | 1997-07-29 | 2000-09-19 | E. I. Du Pont De Nemours And Company | Supported bis(phosphorus) ligands |
| ZA986369B (en) * | 1997-07-29 | 2000-01-17 | Du Pont | Hydrocyanation of diolefins and isomerization of nonconjugated 2-alkyl-3-monoalkenenitriles. |
| US6229052B1 (en) | 1998-05-29 | 2001-05-08 | E. I. Du Pont De Nemours And Company | Hydroformylation of olefins using supported bis(phosphorus) ligands |
| DE19825212A1 (de) | 1998-06-05 | 1999-12-09 | Basf Ag | Katalysator, umfassend einen Komplex eines Metalls der VIII. Nebengruppe auf Basis eines zweizähnigen Phosphonitliganden und Verfahren zur Herstellung von Nitrilen |
| US6579997B1 (en) | 1999-07-21 | 2003-06-17 | Uab Research Foundation | Metallacrown ether catalysts for hydroformylation |
| US6048996A (en) * | 1999-08-26 | 2000-04-11 | E. I. Du Pont De Nemours And Company | Insoluble promoters for nickel-catalyzed hydrocyanation of monoolefins |
| CN100360496C (zh) | 1999-09-20 | 2008-01-09 | 因维斯塔技术有限公司 | 多齿亚磷酸酯配体、含有这类配体的催化组合物和使用这类催化组合物的催化方法 |
| US6515161B1 (en) | 1999-09-20 | 2003-02-04 | E. I. Du Pont De Nemours And Company | Hydroformylation process utilizing multidentate phosphite ligands |
| US6284865B1 (en) | 1999-09-20 | 2001-09-04 | E. I. Du Pont De Nemours And Company | Polymeric phosphite composition and hydrocyanation of unsaturated organic compounds and the isomerization of unsaturated nitriles |
| US6420611B1 (en) | 1999-09-20 | 2002-07-16 | E. I. Du Pont De Nemours And Company | Composition comprising polymeric phosphite |
| US6380421B1 (en) | 1999-09-20 | 2002-04-30 | E. I. Du Pont De Nemours And Company | Multidentate phosphite ligands, catalytic compositions containing such ligands and catalytic processes utilizing such catalytic compositions |
| DE10136488A1 (de) * | 2001-07-27 | 2003-02-06 | Basf Ag | Ni(O) enthaltendes Katalysatorsystem |
| US6893996B2 (en) | 2001-11-26 | 2005-05-17 | Invista North America S.A.R.L. | Process for the preparation of a nickel/phosphorous ligand catalyst for olefin hydrocyanation |
| TW593251B (en) | 2001-11-26 | 2004-06-21 | Du Pont | Process for preparing 3,3',5,5',6,6'-hexaalkyl-2,2'-biphenols, 3,3',4,4',5,5'-hexaalkyl-2,2'-biphenols and 3,3',4,4',5,5',6,6'-octaalkyl-2,2'-biphenols |
| US6489517B1 (en) | 2001-11-26 | 2002-12-03 | E. I. Du Pont De Nemours And Company | Process for preparing 3,3′,6,6′-tetraalkyl-2,2′-biphenols and 3,3′,6,6′-tetraalkyl-5,5′-dihalo-2,2′-biphenols |
| US6660876B2 (en) | 2001-11-26 | 2003-12-09 | E. I. Du Pont De Nemours And Company | Phosphorus-containing compositions and their use in hydrocyanation, isomerization and hydroformylation reactions |
| CN1289539C (zh) | 2001-11-26 | 2006-12-13 | 因维斯塔技术有限公司 | 载体上的双(磷)配体及其在催化中的应用 |
| US7196033B2 (en) * | 2001-12-14 | 2007-03-27 | Huntsman Petrochemical Corporation | Advances in amination catalysis |
| AR038161A1 (es) * | 2002-01-24 | 2004-12-29 | Basf Ag | Procedimiento para separar acidos de mezclas de reaccion quimicas con la ayuda de liquidos ionicos |
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| CN100418974C (zh) | 2002-10-15 | 2008-09-17 | 联合碳化化学及塑料技术公司 | 双螯合配体及其在羰基化方法中的用途 |
| US6906218B2 (en) | 2002-12-18 | 2005-06-14 | Invista North America S.A.R.L. | Cyclohexane derivatives and methods for their preparation |
| FR2849027B1 (fr) * | 2002-12-23 | 2005-01-21 | Rhodia Polyamide Intermediates | Procede de synthese de composes comprenant des fonctions nitriles a partir de composes a insaturations ethyleniques |
| US6936171B2 (en) * | 2003-01-08 | 2005-08-30 | Invista North America S.A.R.L. | Process for catalyst recovery from hydrocyanation product mixtures |
| US6897329B2 (en) * | 2003-01-14 | 2005-05-24 | Invista North America S.A.R.L. | Process for the preparation of nickel/phosphorous ligand catalyst for olefin hydrocyanation |
| FR2850966B1 (fr) | 2003-02-10 | 2005-03-18 | Rhodia Polyamide Intermediates | Procede de fabrication de composes dinitriles |
| US6844289B2 (en) * | 2003-04-08 | 2005-01-18 | Invista North America S.A.R.L. | Process for the preparation of a nickel/phosphorous ligand catalyst |
| FR2854891B1 (fr) | 2003-05-12 | 2006-07-07 | Rhodia Polyamide Intermediates | Procede de preparation de dinitriles |
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| DE10360771A1 (de) * | 2003-12-23 | 2005-07-28 | Oxeno Olefinchemie Gmbh | Verfahren zur Herstellung von dreiwertigen Organophosphor-Verbindungen |
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| EP2322503B1 (fr) | 2005-10-18 | 2014-12-31 | Invista Technologies S.à.r.l. | Procédé de fabrication de 3-aminopentanenitrile |
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| EP2164587B1 (fr) | 2007-06-13 | 2018-04-04 | INVISTA Textiles (U.K.) Limited | Procédé pour améliorer la qualité de l'adiponitrile |
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| US9458185B2 (en) | 2012-02-10 | 2016-10-04 | The Regents Of The University Of California | First row metal-based catalysts for hydosilylation |
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| DE102013219510A1 (de) | 2012-10-12 | 2014-04-17 | Evonik Degussa Gmbh | Gemisch von Bisphosphiten und dessen Verwendung als Katalysatorgemisch in der Hydroformylierung |
| DE102013219506A1 (de) | 2012-10-12 | 2014-04-17 | Evonik Degussa Gmbh | Unsymmetrisches Bisphosphit |
| EP2928598A1 (fr) | 2012-12-07 | 2015-10-14 | Invista Technologies S.à.r.l. | Composition pour une solubilité améliorée de nickel-ligand |
| CN105531257B (zh) | 2013-07-17 | 2019-12-17 | 英威达纺织(英国)有限公司 | 通过蒸馏将溶剂与镍催化剂分离 |
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| CN103739516B (zh) * | 2014-01-06 | 2016-04-27 | 重庆中平紫光科技发展有限公司 | 一种利用2-甲基-3-丁烯腈的异构化液合成己二腈的方法 |
| DE102014202499A1 (de) | 2014-02-12 | 2015-08-13 | Evonik Degussa Gmbh | Verfahren zur Herstellung von 6,6'-((3,3'-di-tert-butyl-5,5'-dimethoxy-[1,1'-biphenyl]-2,2'-diyl)bis(oxy))bis(2,4,8,10-tetramethyldibenzo[d,f][1,3,2]dioxaphosphepin |
| US9914700B2 (en) | 2014-06-27 | 2018-03-13 | Invista North America S.A R.L. | Enhanced extraction of impurities from mixture comprising nitriles |
| EP3160933B1 (fr) | 2014-06-27 | 2018-08-15 | INVISTA Textiles (U.K.) Limited | Procédé intégré de production de nitrile par une extraction liquide-liquide améliorée |
| EP3029050B1 (fr) * | 2014-12-04 | 2018-02-28 | Evonik Degussa GmbH | Bisphosphites présentant une unité de naphtyle-phényle en tant que composant périphérique |
| TWI709568B (zh) | 2015-09-30 | 2020-11-11 | 美商陶氏科技投資公司 | 用於製造有機磷化合物的方法 |
| PL3318569T3 (pl) | 2016-11-08 | 2020-03-31 | Evonik Degussa Gmbh | Bisfosfoniany z jednostkami 2,4-tert.-butylofenylu i ich zastosowanie jako ligandów w hydroformylowaniu |
| EP3318570B1 (fr) | 2016-11-08 | 2019-08-07 | Evonik Degussa GmbH | Acide phosphoreux-p,p'-[5,5',6,6'-tétraméthyl-3,3'-bis(1-éthyléthyl)[1,1'-biphényl]-2,2'-diyl] p,p,p',p'-tétrakis (2,4-diméthylphényl)-ester dans l'hydroformylation |
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| CN110845364B (zh) * | 2019-11-28 | 2023-02-03 | 湘潭大学 | 一种以甲酰胺为氰源的腈类化合物的制备方法 |
| CN114644652A (zh) * | 2022-04-22 | 2022-06-21 | 广东欧凯新材料有限公司 | 一种大位阻双苯酚化合物及其双膦配体的制备方法 |
| EP4499302A1 (fr) | 2022-05-23 | 2025-02-05 | INVISTA Textiles (U.K.) Limited | Ligands de phosphite multidentates, compositions catalytiques contenant de tels ligands et procédés catalytiques utilisant de telles compositions catalytiques |
| US20250296076A1 (en) | 2022-05-23 | 2025-09-25 | Inv Nylon Chemicals Americas, Llc | Multidentate phosphite ligands, catalytic compositions containing such ligands, and catalytic processes utilizing such catalytic compositions |
| US20260015318A1 (en) * | 2022-08-02 | 2026-01-15 | Inv Nylon Chemicals Americas, Llc | Processes for producing nitriles and phosphorus-containing catalysts for use in such processes |
| WO2024028720A1 (fr) | 2022-08-02 | 2024-02-08 | Inv Nylon Chemicals Americas, Llc | Ligands phosphites bidentés, compositions catalytiques contenant de tels ligands, et procédés catalytiques mettant en oeuvre de telles compositions catalytiques |
| CN119095858A (zh) | 2022-08-02 | 2024-12-06 | 英威达纺织(英国)有限公司 | 双齿亚磷酸酯配体、含有此类配体的催化组合物以及利用此类催化组合物的催化方法 |
| EP4499653A1 (fr) | 2022-08-02 | 2025-02-05 | INVISTA Textiles (U.K.) Limited | Ligands de phosphite bidenté, compositions catalytiques contenant de tels ligands et procédés catalytiques utilisant de telles compositions catalytiques |
| EP4499658B1 (fr) | 2022-08-02 | 2025-12-10 | INVISTA Textiles (U.K.) Limited | Ligands de phosphite bidentate, compositions catalytiques contenant de tels ligands, et processus catalytiques utilisant de telles compositions catalytiques |
| WO2024028717A1 (fr) | 2022-08-02 | 2024-02-08 | Inv Nylon Chemicals Americas, Llc | Ligands contenant de l'arsenic, compositions catalytiques contenant de tels ligands et procédés catalytiques mettant en oeuvre de telles compositions catalytiques |
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-
1994
- 1994-11-07 CA CA002177135A patent/CA2177135C/fr not_active Expired - Fee Related
- 1994-11-07 CN CN94194862A patent/CN1082946C/zh not_active Expired - Lifetime
- 1994-11-07 DK DK95901801T patent/DK0730574T3/da active
- 1994-11-07 US US08/424,351 patent/US5688986A/en not_active Expired - Lifetime
- 1994-11-07 KR KR1019960702713A patent/KR100263138B1/ko not_active Expired - Fee Related
- 1994-11-07 DE DE69412635T patent/DE69412635T2/de not_active Expired - Lifetime
- 1994-11-07 BR BR9408151A patent/BR9408151A/pt not_active IP Right Cessation
- 1994-11-07 AT AT95901801T patent/ATE169902T1/de not_active IP Right Cessation
- 1994-11-07 CN CNB011170700A patent/CN1145531C/zh not_active Expired - Lifetime
- 1994-11-07 WO PCT/US1994/012794 patent/WO1995014659A1/fr not_active Ceased
- 1994-11-07 ES ES95901801T patent/ES2122515T3/es not_active Expired - Lifetime
- 1994-11-07 EP EP95901801A patent/EP0730574B1/fr not_active Expired - Lifetime
- 1994-11-07 JP JP51508995A patent/JP3553952B2/ja not_active Expired - Fee Related
- 1994-11-08 TW TW083110338A patent/TW457244B/zh not_active IP Right Cessation
-
1996
- 1996-09-26 US US08/721,068 patent/US5723641A/en not_active Expired - Lifetime
-
1998
- 1998-08-26 GR GR980401912T patent/GR3027731T3/el unknown
Also Published As
| Publication number | Publication date |
|---|---|
| ATE169902T1 (de) | 1998-09-15 |
| CN1142224A (zh) | 1997-02-05 |
| CA2177135A1 (fr) | 1995-06-01 |
| JP3553952B2 (ja) | 2004-08-11 |
| ES2122515T3 (es) | 1998-12-16 |
| DE69412635D1 (de) | 1998-09-24 |
| EP0730574A1 (fr) | 1996-09-11 |
| CN1082946C (zh) | 2002-04-17 |
| KR100263138B1 (ko) | 2000-08-01 |
| BR9408151A (pt) | 1997-08-05 |
| GR3027731T3 (en) | 1998-11-30 |
| KR960705770A (ko) | 1996-11-08 |
| DE69412635T2 (de) | 1999-04-15 |
| US5723641A (en) | 1998-03-03 |
| TW457244B (en) | 2001-10-01 |
| US5688986A (en) | 1997-11-18 |
| WO1995014659A1 (fr) | 1995-06-01 |
| CN1327881A (zh) | 2001-12-26 |
| JPH09505586A (ja) | 1997-06-03 |
| CA2177135C (fr) | 2005-04-26 |
| CN1145531C (zh) | 2004-04-14 |
| EP0730574B1 (fr) | 1998-08-19 |
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