EA199800523A1 - Способ стабилизации органофосфитных лигандов в процессах, катализируемых комплексными катализаторами - Google Patents
Способ стабилизации органофосфитных лигандов в процессах, катализируемых комплексными катализаторамиInfo
- Publication number
- EA199800523A1 EA199800523A1 EA199800523A EA199800523A EA199800523A1 EA 199800523 A1 EA199800523 A1 EA 199800523A1 EA 199800523 A EA199800523 A EA 199800523A EA 199800523 A EA199800523 A EA 199800523A EA 199800523 A1 EA199800523 A1 EA 199800523A1
- Authority
- EA
- Eurasian Patent Office
- Prior art keywords
- organopolyphosphite ligand
- metal
- organophosphitic
- ligands
- stabilization
- Prior art date
Links
- 238000000034 method Methods 0.000 title abstract 6
- 239000003446 ligand Substances 0.000 title abstract 5
- 239000003054 catalyst Substances 0.000 title abstract 4
- 230000006641 stabilisation Effects 0.000 title 1
- 238000011105 stabilization Methods 0.000 title 1
- 230000009849 deactivation Effects 0.000 abstract 2
- 239000007795 chemical reaction product Substances 0.000 abstract 1
- 150000001875 compounds Chemical class 0.000 abstract 1
- 125000000623 heterocyclic group Chemical group 0.000 abstract 1
- 239000000047 product Substances 0.000 abstract 1
- 239000000376 reactant Substances 0.000 abstract 1
- 230000000087 stabilizing effect Effects 0.000 abstract 1
Classifications
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- 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
- C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
- C07F9/6571—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms
- C07F9/6574—Esters of oxyacids of phosphorus
- C07F9/65746—Esters of oxyacids of phosphorus the molecule containing more than one cyclic phosphorus atom
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- 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
- B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
- B01J31/0235—Nitrogen containing compounds
- B01J31/0244—Nitrogen containing compounds with nitrogen contained as ring member in aromatic compounds or moieties, e.g. pyridine
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- 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
- B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
- B01J31/0255—Phosphorus containing compounds
- B01J31/0257—Phosphorus acids or phosphorus acid esters
- B01J31/0259—Phosphorus acids or phosphorus acid esters comprising phosphorous acid (-ester) groups ((RO)P(OR')2) or the isomeric phosphonic acid (-ester) groups (R(R'O)2P=O), i.e. R= C, R'= C, H
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- 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
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- 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
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- 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
- B01J31/40—Regeneration or reactivation
- B01J31/4015—Regeneration or reactivation of catalysts containing metals
- B01J31/4023—Regeneration or reactivation of catalysts containing metals containing iron group metals, noble metals or copper
- B01J31/4038—Regeneration or reactivation of catalysts containing metals containing iron group metals, noble metals or copper containing noble metals
- B01J31/4046—Regeneration or reactivation of catalysts containing metals containing iron group metals, noble metals or copper containing noble metals containing rhodium
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- 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
- B01J31/40—Regeneration or reactivation
- B01J31/4015—Regeneration or reactivation of catalysts containing metals
- B01J31/4053—Regeneration or reactivation of catalysts containing metals with recovery of phosphorous catalyst system constituents
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- 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
- B01J38/00—Regeneration or reactivation of catalysts, in general
- B01J38/74—Regeneration or reactivation of catalysts, in general utilising ion-exchange
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- 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
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- 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
- C07C45/505—Asymmetric hydroformylation
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- 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
- C07F9/025—Purification; Separation; Stabilisation; Desodorisation of organo-phosphorus compounds
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- 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
- C07F9/06—Phosphorus compounds without P—C bonds
- C07F9/08—Esters of oxyacids of phosphorus
- C07F9/141—Esters of phosphorous acids
- C07F9/145—Esters of phosphorous acids with hydroxyaryl compounds
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- 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
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- 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
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- 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
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- 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
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- 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/582—Recycling of unreacted starting or intermediate materials
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- 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Engineering & Computer Science (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Biochemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- Inorganic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
Изобретение относится к способу стабилизации комплексного катализатора металл-органополифосфитный лиганд против деактивации в процессе, который включает реакцию одного или нескольких реагентов в присутствии комплексного катализатора металл-органополифосфитный лиганд и, необязательно, свободного органополифосфитного лиганда для получения потока продуктов реакции, содержащего один или несколько продуктов, где способ включает проведение указанного процесса в присутствии одного или нескольких свободных гетероциклических азотистых соединений в количестве, достаточном для того, чтобы предотвратить и/или уменьшить деактивацию комплексного катализатора металл-органополифосфитный лиганд.Международная заявка была опубликована вместе с отчетом о международном поиске.
Applications Claiming Priority (6)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US828995P | 1995-12-06 | 1995-12-06 | |
US828695P | 1995-12-06 | 1995-12-06 | |
US828495P | 1995-12-06 | 1995-12-06 | |
US876395P | 1995-12-06 | 1995-12-06 | |
US08/756,789 US5731472A (en) | 1995-12-06 | 1996-11-26 | Metal-ligand complex catalyzed processes |
PCT/US1996/019410 WO1997020798A1 (en) | 1995-12-06 | 1996-12-05 | Improved metal-ligand complex catalyzed processes |
Publications (2)
Publication Number | Publication Date |
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EA199800523A1 true EA199800523A1 (ru) | 1998-12-24 |
EA001483B1 EA001483B1 (ru) | 2001-04-23 |
Family
ID=27533265
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EA199800523A EA001483B1 (ru) | 1995-12-06 | 1996-12-05 | Способ стабилизации органофосфитных лигандов в процессах, катализируемых комплексными катализаторами |
Country Status (9)
Country | Link |
---|---|
US (1) | US5731472A (ru) |
EP (1) | EP0873292B1 (ru) |
CN (1) | CN1122655C (ru) |
BR (1) | BR9611858A (ru) |
CA (2) | CA2239606A1 (ru) |
CZ (1) | CZ175398A3 (ru) |
DE (1) | DE69618240T2 (ru) |
EA (1) | EA001483B1 (ru) |
WO (1) | WO1997020798A1 (ru) |
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US6090987A (en) * | 1998-07-06 | 2000-07-18 | Union Carbide Chemicals & Plastics Technology Corporation | Metal-ligand complex catalyzed processes |
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DE10048301A1 (de) | 2000-09-29 | 2002-04-11 | Oxeno Olefinchemie Gmbh | Stabilisierung von Rhodiumkatalysatoren für die Hydroformylierung von Olefinen |
DE10220801A1 (de) * | 2002-05-10 | 2003-11-20 | Oxeno Olefinchemie Gmbh | Verfahren zur Rhodium-katalysierten Hydroformylierung von Olefinen unter Reduzierung der Rhodiumverluste |
DE10349343A1 (de) * | 2003-10-23 | 2005-06-02 | Basf Ag | Stabilisierung von Hydroformylierungskatalysatoren auf Basis von Phosphoramiditliganden |
DE102005046250B4 (de) * | 2005-09-27 | 2020-10-08 | Evonik Operations Gmbh | Anlage zur Abtrennung von organischen Übergangsmetallkomplexkatalysatoren |
US8263630B2 (en) * | 2008-02-12 | 2012-09-11 | Bristol-Myers Squibb Company | 1,2,3-triazoles as 11-beta hydroxysteroid dehydrogenase type I inhibitors |
RU2541537C2 (ru) | 2009-03-31 | 2015-02-20 | Дау Текнолоджи Инвестментс Ллс | Способ гидроформилирования с помощью двойного открыто-концевого бисфосфитного лиганда |
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SA112330271B1 (ar) | 2011-04-18 | 2015-02-09 | داو تكنولوجى انفستمنتس ال ال سى | تخفيف التلوث في عمليات هيدروفورملة عن طريق إضافة الماء |
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JP6560248B2 (ja) | 2014-03-31 | 2019-08-14 | ダウ テクノロジー インベストメンツ リミティド ライアビリティー カンパニー | ヒドロホルミル化プロセス |
JP6694396B2 (ja) | 2014-05-14 | 2020-05-13 | ダウ テクノロジー インベストメンツ リミティド ライアビリティー カンパニー | 安定化された有機リン化合物 |
MY184826A (en) | 2014-12-04 | 2021-04-24 | Dow Technology Investments Llc | Hydroformylation process |
US10487020B2 (en) * | 2015-07-28 | 2019-11-26 | Dow Technology Investments Llc | Method for the preparation of a stabilized organophosphorous compound solution |
WO2017139543A1 (en) | 2016-02-11 | 2017-08-17 | Dow Technology Investments Llc | Processes for converting olefins to alcohols, ethers, or combinations thereof |
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JPS6027651B2 (ja) * | 1981-08-13 | 1985-06-29 | 工業技術院長 | アルカンポリオ−ルの製造方法 |
GB8334359D0 (en) * | 1983-12-23 | 1984-02-01 | Davy Mckee Ltd | Process |
JPS6153235A (ja) * | 1984-08-24 | 1986-03-17 | Agency Of Ind Science & Technol | エチレングリコ−ルの製造方法 |
DE3573772D1 (en) * | 1984-11-26 | 1989-11-23 | Mitsui Toatsu Chemicals | Preparation process of 2-chloropropionaldehyde |
US4827043A (en) * | 1988-01-22 | 1989-05-02 | Eastman Kodak Company | Impurity removal from carbon monoxide and/or hydrogen-containing streams |
US4935547A (en) * | 1988-08-19 | 1990-06-19 | Union Carbide Chemicals And Plastics Company Inc. | Homologation process making higher alcohols |
ATE107271T1 (de) * | 1989-04-06 | 1994-07-15 | Bp Chem Int Ltd | Verfahren zur herstellung von carbonsäuren. |
US5210318A (en) * | 1990-05-04 | 1993-05-11 | Union Carbide Chemicals & Plastics Technology Corporation | Catalysts and processes useful in producing 1,3-diols and/or 3-hydroxyldehydes |
DE4026406A1 (de) * | 1990-08-21 | 1992-02-27 | Basf Ag | Rhodiumhydroformylierungskatalysatoren mit bis-phosphit-liganden |
TW213465B (ru) * | 1991-06-11 | 1993-09-21 | Mitsubishi Chemicals Co Ltd | |
JPH05320087A (ja) * | 1992-05-21 | 1993-12-03 | Tosoh Corp | ヒドロキシブチルアルデヒド類の製法 |
US5288918A (en) * | 1992-09-29 | 1994-02-22 | Union Carbide Chemicals & Plastics Technology Corporation | Hydroformylation process |
JPH06262086A (ja) * | 1993-03-09 | 1994-09-20 | Daicel Chem Ind Ltd | アルデヒド合成用触媒及びアルデヒドの製造法 |
-
1996
- 1996-11-26 US US08/756,789 patent/US5731472A/en not_active Expired - Lifetime
- 1996-12-05 EP EP96943614A patent/EP0873292B1/en not_active Expired - Lifetime
- 1996-12-05 CZ CZ981753A patent/CZ175398A3/cs unknown
- 1996-12-05 CN CN96198724A patent/CN1122655C/zh not_active Expired - Lifetime
- 1996-12-05 WO PCT/US1996/019410 patent/WO1997020798A1/en not_active Application Discontinuation
- 1996-12-05 EA EA199800523A patent/EA001483B1/ru not_active IP Right Cessation
- 1996-12-05 BR BR9611858A patent/BR9611858A/pt not_active Application Discontinuation
- 1996-12-05 CA CA002239606A patent/CA2239606A1/en not_active Abandoned
- 1996-12-05 CA CA002239594A patent/CA2239594A1/en not_active Abandoned
- 1996-12-05 DE DE69618240T patent/DE69618240T2/de not_active Expired - Lifetime
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN116408147A (zh) * | 2023-04-10 | 2023-07-11 | 中国科学院兰州化学物理研究所 | 一种共价三嗪有机聚合物负载铑催化材料的制备及其应用 |
CN116408147B (zh) * | 2023-04-10 | 2023-09-29 | 中国科学院兰州化学物理研究所 | 一种共价三嗪有机聚合物负载铑催化材料的制备及其应用 |
Also Published As
Publication number | Publication date |
---|---|
EP0873292A1 (en) | 1998-10-28 |
CZ175398A3 (cs) | 1998-10-14 |
CN1220652A (zh) | 1999-06-23 |
EP0873292B1 (en) | 2001-12-19 |
US5731472A (en) | 1998-03-24 |
CA2239594A1 (en) | 1997-06-12 |
WO1997020798A1 (en) | 1997-06-12 |
CN1122655C (zh) | 2003-10-01 |
DE69618240D1 (de) | 2002-01-31 |
EA001483B1 (ru) | 2001-04-23 |
CA2239606A1 (en) | 1997-06-12 |
BR9611858A (pt) | 1999-05-04 |
DE69618240T2 (de) | 2002-06-13 |
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