DE68905452D1 - Hydroformylation von olefinen unter schwachem druck mit einem rhodium-katalysator. - Google Patents
Hydroformylation von olefinen unter schwachem druck mit einem rhodium-katalysator.Info
- Publication number
- DE68905452D1 DE68905452D1 DE8989420501T DE68905452T DE68905452D1 DE 68905452 D1 DE68905452 D1 DE 68905452D1 DE 8989420501 T DE8989420501 T DE 8989420501T DE 68905452 T DE68905452 T DE 68905452T DE 68905452 D1 DE68905452 D1 DE 68905452D1
- Authority
- DE
- Germany
- Prior art keywords
- hydroformylation
- low pressure
- rhodium catalyst
- olefins
- pressure olefins
- 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
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
- B01J31/1895—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 arsenic or antimony
-
- 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
-
- 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
- B01J31/2409—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring with more than one complexing phosphine-P atom
-
- 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
- B01J31/2442—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring comprising condensed ring systems
- B01J31/2447—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring comprising condensed ring systems and phosphine-P atoms as substituents on a ring of the condensed system or on a further attached ring
- B01J31/2452—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring comprising condensed ring systems and phosphine-P atoms as substituents on a ring of the condensed system or on a further attached ring with more than one complexing phosphine-P atom
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/49—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reaction with carbon monoxide
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/49—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reaction with carbon monoxide
- C07C45/50—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reaction with carbon monoxide by oxo-reactions
-
- 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
- B01J2231/20—Olefin oligomerisation or telomerisation
-
- 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
- B01J2531/0202—Polynuclearity
- B01J2531/0208—Bimetallic complexes, i.e. comprising one or more units of two metals, with metal-metal bonds but no all-metal (M)n rings, e.g. Cr2(OAc)4
-
- 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
- B01J2531/50—Complexes comprising metals of Group V (VA or VB) as the central metal
- B01J2531/54—Bismuth
-
- 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
- B01J2531/822—Rhodium
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US07/288,596 US4960949A (en) | 1988-12-22 | 1988-12-22 | Low pressure rhodium catalyzed hydroformylation of olefins |
Publications (2)
Publication Number | Publication Date |
---|---|
DE68905452D1 true DE68905452D1 (de) | 1993-04-22 |
DE68905452T2 DE68905452T2 (de) | 1993-10-21 |
Family
ID=23107800
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
DE89420501T Expired - Lifetime DE68905452T2 (de) | 1988-12-22 | 1989-12-20 | Hydroformylation von Olefinen unter schwachem Druck mit einem Rhodium-Katalysator. |
Country Status (8)
Country | Link |
---|---|
US (2) | US4960949A (de) |
EP (2) | EP0449966A1 (de) |
JP (1) | JP2859955B2 (de) |
AT (1) | ATE86885T1 (de) |
CA (1) | CA2004707A1 (de) |
DE (1) | DE68905452T2 (de) |
ES (1) | ES2039086T3 (de) |
WO (1) | WO1990006810A1 (de) |
Families Citing this family (51)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE4040315A1 (de) * | 1990-12-17 | 1992-06-25 | Hoechst Ag | Verfahren zur herstellung von aldehyden |
FR2671079B1 (fr) * | 1990-12-28 | 1994-06-03 | Elf Aquitaine | Procede d'hydrogenation de composes organiques et catalyseurs au ruthenium pour sa realisation. |
US5232989A (en) * | 1991-03-04 | 1993-08-03 | Monsanto Company | Functionalized polymers |
US5360938A (en) * | 1991-08-21 | 1994-11-01 | Union Carbide Chemicals & Plastics Technology Corporation | Asymmetric syntheses |
DE4242723A1 (de) * | 1992-12-17 | 1994-06-23 | Hoechst Ag | Verfahren zur Herstellung von Aldehyden |
GB2274457A (en) * | 1993-01-25 | 1994-07-27 | Shell Int Research | Hydroformylation of unsaturated carbonyl compounds |
US5332846A (en) * | 1993-06-01 | 1994-07-26 | Eastman Kodak Company | Hydroformylation process using novel phosphine-rhodium catalyst system |
US5488175A (en) * | 1993-09-16 | 1996-01-30 | Shell Oil Company | Hydroformylation process |
DE4431528A1 (de) * | 1994-09-03 | 1996-03-07 | Basf Ag | Verfahren zur Herstellung von n-Butyraldehyd und/oder n-Butanol |
GB9425911D0 (en) * | 1994-12-22 | 1995-02-22 | Ici Plc | Process for the carbonylation of olefins and catalyst system for use therein |
DE19619527A1 (de) * | 1996-05-15 | 1997-11-20 | Hoechst Ag | Katalysatorsysteme auf der Basis von Rhodium-Komplexverbindungen mit Diphosphin-Liganden und ihre Verwendung bei der Herstellung von Aldehyden |
DE19654908A1 (de) * | 1996-06-24 | 1998-01-29 | Hoechst Ag | Verfahren zur Herstellung von Aldehyden in Gegenwart eines neuen Katalysators |
US5912364A (en) * | 1996-10-21 | 1999-06-15 | Eastman Chemical Company | Process for the preparation of 3-methyltetrahydrofuran |
WO2003080632A1 (en) * | 2002-03-22 | 2003-10-02 | Kuraray Co., Ltd. | Bisphosphine, process for producing the same, and use thereof |
TWI301481B (en) * | 2002-08-10 | 2008-10-01 | Lucite Int Uk Ltd | A catalyst system |
US6664427B1 (en) * | 2002-08-29 | 2003-12-16 | E. I. Du Pont De Nemours And Company | Process for preparing aldehyde compounds |
EP1572609B1 (de) * | 2002-12-17 | 2007-08-15 | Shell Internationale Researchmaatschappij B.V. | Verfahren zur hydroformylierung von ethylenisch ungesättigten verbindungen in anwesenheit einer säure und eines tertiären monophosphins |
US7186868B2 (en) * | 2002-12-17 | 2007-03-06 | Shell Oil Company | Hydroformylation process for the conversion of an ethylenically unsaturated compound to an alcohol |
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 |
US6909019B1 (en) | 2004-05-25 | 2005-06-21 | Eastman Chemical Company | Process for preparing aldehydes |
GB0411951D0 (en) * | 2004-05-28 | 2004-06-30 | Lucite Int Uk Ltd | Carbonylation of ester |
KR100596365B1 (ko) * | 2004-06-12 | 2006-07-03 | 주식회사 엘지화학 | 인을 포함하는 촉매 조성물 및 이를 이용한히드로포르밀화 방법 |
US7446231B2 (en) | 2004-08-02 | 2008-11-04 | Union Carbide Chemicals & Plastics Technology Corporation | Stabilization of a hydroformylation process |
PL1863747T3 (pl) * | 2005-03-16 | 2017-06-30 | Perstorp Specialty Chemicals Ab | Sposób hydroformylowania o ulepszonej izo-selektywności |
GB0516556D0 (en) | 2005-08-12 | 2005-09-21 | Lucite Int Uk Ltd | Improved catalyst system |
MY154959A (en) | 2005-11-17 | 2015-08-28 | Lucite Int Uk Ltd | Carbonylation of ethylenically unsaturated compounds |
GB0607494D0 (en) | 2006-04-13 | 2006-05-24 | Lucite Int Uk Ltd | Metal complexes |
CN105153241B (zh) * | 2006-12-02 | 2020-05-15 | 卢西特国际英国有限公司 | 羰基化配体及其在羰基化烯键式不饱和化合物中的用途 |
GB0625518D0 (en) * | 2006-12-21 | 2007-01-31 | Lucite Int Uk Ltd | Carbonylation of conjugated dienes |
US7674937B2 (en) | 2008-05-28 | 2010-03-09 | Eastman Chemical Company | Hydroformylation catalysts |
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 |
US20100069679A1 (en) * | 2008-09-12 | 2010-03-18 | Eastman Chemical Company | Acetylene tolerant hydroformylation catalysts |
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 |
US9487475B2 (en) | 2012-11-09 | 2016-11-08 | Mitsui Chemicals, Inc. | Preparation method of aldehyde compound with limited amount of acrylonitrile |
KR101730280B1 (ko) * | 2012-11-09 | 2017-04-25 | 미쓰이 가가쿠 가부시키가이샤 | 알데하이드 화합물의 제조 방법 |
US9687837B1 (en) | 2016-08-31 | 2017-06-27 | Eastman Chemical Company | Stable hydroformylation catalyst for preparation of high N/Iso ratio aldehyde product |
US9975833B2 (en) | 2016-08-31 | 2018-05-22 | Eastman Chemical Company | Efficient catalyst for the formation of polyaryl hydrocarbons suitable as precursors for polydentate organophosphorus catalyst ligands |
CN111318308A (zh) * | 2018-12-17 | 2020-06-23 | 中国石油化工股份有限公司 | 催化剂组合物及其应用和醋酸乙烯酯氢甲酰化的方法 |
US12031091B2 (en) | 2019-05-24 | 2024-07-09 | Eastman Chemical Company | Recycle content cracked effluent |
US11365357B2 (en) | 2019-05-24 | 2022-06-21 | Eastman Chemical Company | Cracking C8+ fraction of pyoil |
EP3976732A4 (de) | 2019-05-24 | 2023-05-17 | Eastman Chemical Company | Mischung von kleinen mengen von pyrolyseöl zu einem flüssigkeitsstrom, der zu einen gas-cracker verarbeitet wird |
EP4004081A4 (de) | 2019-07-29 | 2023-08-02 | Eastman Chemical Company | Cyclobutandiolpolyester mit recycle-inhalt |
KR20220041177A (ko) | 2019-07-29 | 2022-03-31 | 이스트만 케미칼 컴파니 | 열분해 및 가메탄올분해로부터의 재활용된 단량체를 갖는 폴리에스테르의 제조 방법 |
US11319262B2 (en) | 2019-10-31 | 2022-05-03 | Eastman Chemical Company | Processes and systems for making recycle content hydrocarbons |
US11945998B2 (en) | 2019-10-31 | 2024-04-02 | Eastman Chemical Company | Processes and systems for making recycle content hydrocarbons |
WO2021092305A1 (en) | 2019-11-07 | 2021-05-14 | Eastman Chemical Company | Recycle content mixed esters and solvents |
KR20220093368A (ko) | 2019-11-07 | 2022-07-05 | 이스트만 케미칼 컴파니 | 재활용물 알파 올레핀 및 지방 알코올 |
US12195674B2 (en) | 2021-09-21 | 2025-01-14 | Eastman Chemical Company | Using spent caustic solution from pygas treatment to neutralize halogens from liquified waste plastic |
CN113996347A (zh) * | 2021-12-06 | 2022-02-01 | 万华化学集团股份有限公司 | 一种氢甲酰化催化剂组合物及烯丙醇氢甲酰化反应制备羟基丁醛的方法 |
CN115999539B (zh) * | 2022-12-15 | 2024-11-01 | 北京化工大学 | 一种负载型Rh/TiO2-P催化剂的制备方法及应用 |
Family Cites Families (20)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3239566A (en) * | 1960-07-22 | 1966-03-08 | Shell Oil Co | Hydroformylation of olefins |
US3527809A (en) * | 1967-08-03 | 1970-09-08 | Union Carbide Corp | Hydroformylation process |
US4138420A (en) * | 1976-01-19 | 1979-02-06 | Celanese Corporation | Hydroformylation catalysts |
US4277627A (en) * | 1977-01-25 | 1981-07-07 | Union Carbide Corporation | Hydroformylation process |
US4152344A (en) * | 1977-08-08 | 1979-05-01 | Celanese Corporation | Phosphino-ferrocene ligands |
US4215077A (en) * | 1978-02-09 | 1980-07-29 | Kuraray Co., Ltd. | Hydroformylation of olefins |
JPS54119407A (en) * | 1978-03-09 | 1979-09-17 | Agency Of Ind Science & Technol | Preparation of aldehydes |
JPS5626830A (en) * | 1979-08-10 | 1981-03-16 | Kuraray Co Ltd | Hydroformylation of lower olefin |
US4352947A (en) * | 1981-08-03 | 1982-10-05 | Gulf Research & Development Company | Process for producing ethanol |
US4612402A (en) * | 1982-03-29 | 1986-09-16 | Allied Corporation | Oxidation of olefins using rhodium nitro complex |
EP0203286B1 (de) * | 1985-03-27 | 1988-09-14 | Hoechst Aktiengesellschaft | Trägerkatalysator und Verfahren zur Herstellung von Monocarbonsäureanhydriden |
US4605781A (en) * | 1985-09-03 | 1986-08-12 | Celanese Corporation | Production of 2-methylbutanal |
US4748261A (en) * | 1985-09-05 | 1988-05-31 | Union Carbide Corporation | Bis-phosphite compounds |
US4694109A (en) * | 1986-06-13 | 1987-09-15 | Eastman Kodak Company | Chelate ligands for low pressure hydroformylation catalyst and process employing same |
US4760194A (en) * | 1987-02-18 | 1988-07-26 | Eastman Kodak Company | Low pressure hydroformylation catalyst employing unique ligands and process using same |
US4755624A (en) * | 1987-02-18 | 1988-07-05 | Eastman Kodak Company | Low pressure hydroformylation process |
US4742178A (en) * | 1986-11-10 | 1988-05-03 | Eastman Kodak Company | Low pressure hydroformylation of dienes |
EP0279018B1 (de) * | 1987-02-18 | 1992-01-29 | EASTMAN KODAK COMPANY (a New Jersey corporation) | Chelat-Ligandene für Tiefdruck-Hydroformylierungskatalysatoren und Verfahren zu ihrer Verwendung |
US4774362A (en) * | 1987-04-24 | 1988-09-27 | Eastmank Kodak Company | Chelating ligands and catalysts and processes employing the same |
US4873213A (en) * | 1988-08-12 | 1989-10-10 | Puckette Thomas A | Low pressure rhodium catalyzed hydroformylation of olefins |
-
1988
- 1988-12-22 US US07/288,596 patent/US4960949A/en not_active Expired - Lifetime
-
1989
- 1989-12-06 CA CA002004707A patent/CA2004707A1/en not_active Abandoned
- 1989-12-20 WO PCT/US1989/005722 patent/WO1990006810A1/en not_active Application Discontinuation
- 1989-12-20 JP JP2501600A patent/JP2859955B2/ja not_active Expired - Fee Related
- 1989-12-20 DE DE89420501T patent/DE68905452T2/de not_active Expired - Lifetime
- 1989-12-20 ES ES198989420501T patent/ES2039086T3/es not_active Expired - Lifetime
- 1989-12-20 EP EP90901435A patent/EP0449966A1/de active Pending
- 1989-12-20 AT AT89420501T patent/ATE86885T1/de active
- 1989-12-20 EP EP89420501A patent/EP0375573B1/de not_active Expired - Lifetime
-
1990
- 1990-02-23 US US07/483,839 patent/US5004823A/en not_active Expired - Lifetime
Also Published As
Publication number | Publication date |
---|---|
JP2859955B2 (ja) | 1999-02-24 |
WO1990006810A1 (en) | 1990-06-28 |
DE68905452T2 (de) | 1993-10-21 |
EP0449966A1 (de) | 1991-10-09 |
US5004823A (en) | 1991-04-02 |
EP0375573B1 (de) | 1993-03-17 |
ATE86885T1 (de) | 1993-04-15 |
CA2004707A1 (en) | 1990-06-22 |
ES2039086T3 (es) | 1993-08-16 |
JPH04502463A (ja) | 1992-05-07 |
US4960949A (en) | 1990-10-02 |
EP0375573A1 (de) | 1990-06-27 |
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