ES2133137T3 - Sistema de catalizador de carbonilacion. - Google Patents
Sistema de catalizador de carbonilacion.Info
- Publication number
- ES2133137T3 ES2133137T3 ES90200491T ES90200491T ES2133137T3 ES 2133137 T3 ES2133137 T3 ES 2133137T3 ES 90200491 T ES90200491 T ES 90200491T ES 90200491 T ES90200491 T ES 90200491T ES 2133137 T3 ES2133137 T3 ES 2133137T3
- Authority
- ES
- Spain
- Prior art keywords
- group
- formula
- catalyst system
- carbonilation
- ring
- 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 - Lifetime
Links
- 239000003054 catalyst Substances 0.000 title abstract 3
- -1 HYDROXYL GROUP Chemical group 0.000 abstract 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 abstract 2
- 150000002430 hydrocarbons Chemical group 0.000 abstract 2
- 230000002378 acidificating effect Effects 0.000 abstract 1
- 150000002367 halogens Chemical group 0.000 abstract 1
- 229910052757 nitrogen Inorganic materials 0.000 abstract 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen(.) Chemical compound [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 abstract 1
- 150000003003 phosphines Chemical class 0.000 abstract 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 abstract 1
- 150000003839 salts Chemical class 0.000 abstract 1
- 229930195735 unsaturated hydrocarbon Natural products 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/185—Phosphorus; Compounds thereof with iron group metals or platinum group metals
-
- 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
- B01J31/189—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 containing both nitrogen and phosphorus as complexing atoms, including e.g. phosphino moieties, in one at least bidentate or bridging ligand
-
- 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
- B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
-
- 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
- B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
- B01J31/2404—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/10—Preparation of carboxylic acids or their salts, halides or anhydrides by reaction with carbon monoxide
- C07C51/14—Preparation of carboxylic acids or their salts, halides or anhydrides by reaction with carbon monoxide on a carbon-to-carbon unsaturated bond in organic compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/36—Preparation of carboxylic acid esters by reaction with carbon monoxide or formates
- C07C67/38—Preparation of carboxylic acid esters by reaction with carbon monoxide or formates by addition to an unsaturated carbon-to-carbon bond
-
- 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
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
- C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table compounds of the platinum group
- C07F15/0013—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table compounds of the platinum group without a metal-carbon linkage
-
- 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
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
- C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table compounds of the platinum group
- C07F15/006—Palladium compounds
- C07F15/0066—Palladium compounds without a metal-carbon linkage
-
- 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
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/553—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having one nitrogen atom as the only ring hetero atom
- C07F9/576—Six-membered rings
- C07F9/58—Pyridine rings
-
- 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
- B01J2231/321—Hydroformylation, metalformylation, carbonylation or hydroaminomethylation
-
- 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
-
- 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
- B01J2531/82—Metals of the platinum group
- B01J2531/824—Palladium
-
- 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
- B01J31/1805—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 nitrogen
- B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Molecular Biology (AREA)
- General Health & Medical Sciences (AREA)
- Biochemistry (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
UN SISTEMA CATALIZADOR QUE COMPRENDE A) UNA FUENTE DE UN METAL DEL GRUPO VIII, Y B) UNA FOSFINA DE FORMULA GENERAL: EN LA QUE R1, R2 Y R3 ESTA SELECCIONADOS INDEPENDIENTEMENTE DE UN GRUPO ARILO SUSTITUIDO OPCIONALMENTE Y UN GRUPO DE LA FORMULA GENERAL: EN LA QUE CADA UNO DE A, X, Y Y Z ESTA INDEPENDIENTE SELECCIONADO DE UN ATOMO DE NITROGENO, UN GRUPO CH Y UN GRUPO DE LA FORMULA CR EN LA QUE R REPRESENTA UN GRUPO HIDROXILO, UN GRUPO AMINO, UN GRUPO AMIDO, UN GRUPO CIANO, UN GRUPO ARILO, UN GRUPO ARILOXI, UN ATOMO HALOGENO, UN GRUPO HIDROCARBILO SUSTITUIDO OPCIONALMENTE O UN GRUPO HIDROCARBILOXI SUSTITUIDO OPCIONALMENTE, SIENDO TAMBIEN POSIBLE QUE DOS GRUPOS CR CONTIGUOS FORMEN UN ANILLO, SUJETO A QUE POR LO MENOS UNO DE R1, R2, Y R3 REPRESENTE UN GRUPO DE LA FORMULA II EN LA QUE CUANDO MENOS UNO DE A Y Z REPRESENTA UN GRUPO DE LA FORMULA CR, O UNA SAL DE ADICION ACIDA DE LA MISMA. TAMBIEN SE DESVELAN FOSFINAS NUEVAS, Y EL USO DEL SISTEMA CATALIZADOR EN LA CARBONILACION SELECTIVA DE HIDROCARBUROS INSATURADOS.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB898904860A GB8904860D0 (en) | 1989-03-03 | 1989-03-03 | Process for the preparation of olefinically unsaturated compounds |
| GB909002508A GB9002508D0 (en) | 1990-02-05 | 1990-02-05 | Carbonylation catalyst system |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| ES2133137T3 true ES2133137T3 (es) | 1999-09-01 |
Family
ID=26295048
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| ES90200491T Expired - Lifetime ES2133137T3 (es) | 1989-03-03 | 1990-03-01 | Sistema de catalizador de carbonilacion. |
Country Status (11)
| Country | Link |
|---|---|
| US (1) | US5158921A (es) |
| EP (1) | EP0386833B1 (es) |
| JP (1) | JP3051986B2 (es) |
| KR (1) | KR0144567B1 (es) |
| CN (1) | CN1042400C (es) |
| AU (1) | AU624483B2 (es) |
| BR (1) | BR9000965A (es) |
| CA (1) | CA2011292C (es) |
| DE (1) | DE69033159T2 (es) |
| ES (1) | ES2133137T3 (es) |
| SG (1) | SG50547A1 (es) |
Families Citing this family (38)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB9111583D0 (en) * | 1991-05-30 | 1991-07-24 | Shell Int Research | Carbonylation catalyst system |
| US5258546A (en) * | 1991-05-30 | 1993-11-02 | Shell Oil Company | Carbonylation catalyst system |
| DE4141299C2 (de) * | 1991-12-14 | 2000-09-21 | Celanese Chem Europe Gmbh | Verfahren zur Herstellung von tertiären Phosphanen |
| CA2093470C (en) * | 1992-04-08 | 2003-12-09 | Peter Arnoldy | Carbonylation process using palladium phosphine catalyst |
| US5414109A (en) * | 1993-03-19 | 1995-05-09 | Shell Oil Company | Process for the carbonylation of acetylenically unsaturated compounds |
| BR9407279A (pt) * | 1993-08-19 | 1996-10-01 | Shell Int Research | Processo para a carbonilação de compostos acetilenicamente insaturados |
| CN1035114C (zh) * | 1994-04-26 | 1997-06-11 | 周毕华 | 柴油乳化剂 |
| US5719313A (en) * | 1995-03-16 | 1998-02-17 | Shell Oil Company | Carbonylation catalyst system and a process for the carbonylation of acetylenically unsaturated compounds |
| DE19548399A1 (de) * | 1995-12-22 | 1997-06-26 | Basf Ag | Rutheniumkomplexe mit einem chiralen, zweizähnigen Phosphinoxazolin-Liganden zur enantioselektiven Transferhydrierung von prochiralen Ketonen |
| TW414789B (en) * | 1996-03-26 | 2000-12-11 | Shell Int Research | Process for the carbonylation of acetylenically unsaturated compounds |
| DE19964298C2 (de) * | 1998-07-08 | 2003-01-23 | Dynea Chemicals Oy Helsinki | Verfahren zur Herstellung von substituierten Arylhalophosphinen |
| FI20002807A0 (fi) * | 2000-09-05 | 2000-12-20 | Neste Chemicals Oy | Menetelmä alkeenien hydroformyloimiseksi |
| US6660883B1 (en) * | 2000-09-14 | 2003-12-09 | Council Of Scientific And Industrial Research | Process for the preparation of 2-aryl propionic acids |
| DE10048874A1 (de) | 2000-09-29 | 2002-04-11 | Basf Ag | Katalysatorsystem und Verfahren zur Carbonylierung |
| DE10228293A1 (de) | 2001-07-28 | 2003-02-13 | Basf Ag | Verfahren zur Herstellung von Dialkylketonen |
| GB0218613D0 (en) * | 2002-08-10 | 2002-09-18 | Lucite Int Uk Ltd | Process for the carbonylation of ethylenically unsaturated compounds |
| TWI301481B (en) | 2002-08-10 | 2008-10-01 | Lucite Int Uk Ltd | A catalyst system |
| DE10313319A1 (de) * | 2003-03-25 | 2004-10-07 | Basf Ag | Verfahren zur Hydroformylierung |
| JP2007516197A (ja) | 2003-07-03 | 2007-06-21 | ルーサイト インターナショナル ユーケー リミテッド | エチレン性不飽和化合物のヒドロホルミル化方法 |
| GB0403592D0 (en) | 2004-02-18 | 2004-03-24 | Lucite Int Uk Ltd | A catalyst system |
| GB0411951D0 (en) * | 2004-05-28 | 2004-06-30 | Lucite Int Uk Ltd | Carbonylation of ester |
| GB0516556D0 (en) | 2005-08-12 | 2005-09-21 | Lucite Int Uk Ltd | Improved catalyst system |
| AU2006314268C1 (en) | 2005-11-17 | 2014-01-09 | Lucite International Uk Limited | Carbonylation of ethylenically unsaturated compounds |
| GB0607494D0 (en) | 2006-04-13 | 2006-05-24 | Lucite Int Uk Ltd | Metal complexes |
| GB2437930A (en) * | 2006-05-10 | 2007-11-14 | Lucite Int Uk Ltd | Mixing apparatus |
| US9809611B2 (en) * | 2006-12-02 | 2017-11-07 | Lucite International Uk Limited | Carbonylation ligands and their use in the carbonylation of ethylenically unsaturated compounds |
| GB0625518D0 (en) * | 2006-12-21 | 2007-01-31 | Lucite Int Uk Ltd | Carbonylation of conjugated dienes |
| GB0713624D0 (en) * | 2007-07-13 | 2007-08-22 | Lucite Int Uk Ltd | Improved solvent for catalyst system |
| EP2256102B1 (en) | 2008-03-25 | 2018-09-26 | Sumitomo Chemical Company, Limited | Process for production of alkoxycarbonyl compound |
| GB0812297D0 (en) * | 2008-07-04 | 2008-08-13 | Lucite Int Uk Ltd | Novel carbonylation ligand sand thier use of in the carbonylation of ethylenically unsaturated compounds |
| US20120309613A1 (en) | 2009-12-15 | 2012-12-06 | Lucite International Uk Limited | Carbonylation process |
| GB0921875D0 (en) | 2009-12-15 | 2010-01-27 | Lucite Int Uk Ltd | A continuous process for the carbonylation of ethylene |
| GB201000078D0 (en) | 2010-01-05 | 2010-02-17 | Lucite Int Uk Ltd | Process for the carbonylation of ethylenically unsaturated compounds, novel carbonylation ligands and catalyst systems incorporatng such ligands |
| CN102190583A (zh) * | 2010-03-08 | 2011-09-21 | 中国科学院成都有机化学有限公司 | 一种钯膦络合物催化乙炔羰基合成丙烯酸低碳醇酯的方法 |
| GB201122054D0 (en) | 2011-12-21 | 2012-02-01 | Lucite Int Uk Ltd | A continuous process for the carbonylation of ethylene |
| JP2013193992A (ja) | 2012-03-21 | 2013-09-30 | Sumitomo Chemical Co Ltd | メタクリル酸アルキルの製造方法 |
| DE102013210840A1 (de) * | 2013-06-11 | 2014-12-11 | Evonik Industries Ag | Synthese von a,ß-ungesättigten Carbonsäuren (Meth)acrylaten aus Olefinen und CO2 |
| CN104707663B (zh) * | 2013-12-11 | 2017-07-18 | 中国科学院大连化学物理研究所 | 一种有机配体聚合物载体及其制备方法 |
Family Cites Families (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4257973A (en) * | 1971-11-05 | 1981-03-24 | E. I. Du Pont De Nemours And Company | Process of making acids or esters from unsaturated compounds |
| US3887595A (en) * | 1973-03-05 | 1975-06-03 | Shell Oil Co | Carbonylation process |
| GB8432376D0 (en) * | 1984-12-21 | 1985-02-06 | Shell Int Research | Carbonylation of acetylenically unsaturated compounds |
| GB8501919D0 (en) * | 1985-01-25 | 1985-02-27 | Shell Int Research | Carbonylation of allenically unsaturated compounds |
| DE3685713D1 (de) * | 1985-10-18 | 1992-07-23 | Hoffmann La Roche | Chirale rhodium-diphosphinkomplexe fuer asymmetrische hydrierungen. |
| CA1305695C (en) * | 1986-08-22 | 1992-07-28 | Eit Drent | Catalyst compositions and process for olefin/co copolymerization |
| CA1331173C (en) * | 1986-12-05 | 1994-08-02 | Eit Drent | Process for the carbonylation of acetylenically unsaturated compounds |
| GB8705699D0 (en) * | 1987-03-11 | 1987-04-15 | Shell Int Research | Carbonylation of olefinically unsaturated compounds |
| US4880902A (en) * | 1987-08-27 | 1989-11-14 | Shell Oil Company | Copolymerization of carbon monoxide and olefin with diphosphine having heterocyclic substituents as catalyst |
-
1990
- 1990-02-28 US US07/486,566 patent/US5158921A/en not_active Expired - Lifetime
- 1990-02-28 KR KR1019900002672A patent/KR0144567B1/ko not_active Expired - Fee Related
- 1990-03-01 ES ES90200491T patent/ES2133137T3/es not_active Expired - Lifetime
- 1990-03-01 SG SG1996004691A patent/SG50547A1/en unknown
- 1990-03-01 AU AU50631/90A patent/AU624483B2/en not_active Ceased
- 1990-03-01 BR BR909000965A patent/BR9000965A/pt not_active Application Discontinuation
- 1990-03-01 EP EP90200491A patent/EP0386833B1/en not_active Expired - Lifetime
- 1990-03-01 CA CA002011292A patent/CA2011292C/en not_active Expired - Fee Related
- 1990-03-01 JP JP2047399A patent/JP3051986B2/ja not_active Expired - Lifetime
- 1990-03-01 DE DE69033159T patent/DE69033159T2/de not_active Expired - Fee Related
- 1990-03-03 CN CN90101124A patent/CN1042400C/zh not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JP3051986B2 (ja) | 2000-06-12 |
| EP0386833B1 (en) | 1999-06-16 |
| JPH02277551A (ja) | 1990-11-14 |
| KR900014032A (ko) | 1990-10-22 |
| EP0386833A1 (en) | 1990-09-12 |
| DE69033159T2 (de) | 1999-11-18 |
| CA2011292C (en) | 2000-09-19 |
| KR0144567B1 (ko) | 1998-07-15 |
| AU5063190A (en) | 1990-09-06 |
| DE69033159D1 (de) | 1999-07-22 |
| CN1045234A (zh) | 1990-09-12 |
| SG50547A1 (en) | 1998-07-20 |
| CN1042400C (zh) | 1999-03-10 |
| CA2011292A1 (en) | 1990-09-03 |
| US5158921A (en) | 1992-10-27 |
| BR9000965A (pt) | 1991-02-19 |
| AU624483B2 (en) | 1992-06-11 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| FG2A | Definitive protection |
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