CN105363493A - Method for improving storage stability of hydroformylation catalyst - Google Patents
Method for improving storage stability of hydroformylation catalyst Download PDFInfo
- Publication number
- CN105363493A CN105363493A CN201510933178.6A CN201510933178A CN105363493A CN 105363493 A CN105363493 A CN 105363493A CN 201510933178 A CN201510933178 A CN 201510933178A CN 105363493 A CN105363493 A CN 105363493A
- Authority
- CN
- China
- Prior art keywords
- catalyst
- rhodium
- ligand
- complex catalyst
- phosphite ester
- 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.)
- Pending
Links
Abstract
The invention relates to a method for improving the storage stability of a hydroformylation catalyst to mainly solve the problem of the prior art that the storage stability of a catalyst is poor. According to the technical scheme, at least one of a complex catalyst I and a complex catalyst II is adopted during olefin hydroformylation reaction, so that the problem of the prior art is solved. The method can be applied to olefin hydroformylation reaction.
Description
Technical field
The present invention relates to a kind of method improving olefin hydroformylation catalyst storage stability.
Background technology
Hydroformylation of olefin is important organic synthesis, plays a part very important in modern industry.Its product aldehyde is very useful chemical intermediate, can synthesize multiple important Chemical products, is the homogeneous catalysis process that production scale is maximum up to now.[Trzeciak,A.M.；Ziólkowski,J.J.Coord.Chem.Rev.1999,190-192,883-900.]。Since last century the seventies; the rhodium catalyst that phosphorus-containing ligand is modified has dominated the hydroformylation reaction research of alkene with the advantage that its high activity, outstanding selective and gentle reaction condition etc. are outstanding; become the catalyst of industrial hydroformylation technical process, hydroformylation process supplier common in the world as BASF, EvonikOXENO, Perstorp, DOW etc. all adopt phosphorus-containing ligand the rhodium catalyst modified.Wherein, the composition and structure of phosphorus-containing ligand is the key factor of phosphorus/rhodium catalysis system reaction efficiency, and it directly determines the important indicators such as the activity of catalyst, selective and service life.
The catalyst system of existing industrialization report mainly contains three classes at present: i.e. Rh/ triphenylphosphine (TPP) catalyst system, Rh/ water-soluble triphenyl phosphine (TPPS) and Rh/ bis-phosphite (Phosphite) catalyst system.Rh/TPP is the widely used catalyst system of current hydroformylation of propene synthesis butyraldehyde; but Problems existing be part consumption large (mol ratio of TPP and Rh is generally 200:1), product butyraldehyde just/different ratio not high (<20), in catalyst recycle process, easily there is the phenomenon that ligand decomposes, metal rhodium are separated out, cause the inactivation of catalyst.In Rh/TPPS catalyst system; water soluble ligand realizes the circulation of catalyst by being separated; but pure water soluble ligand not easily obtains; easily emulsion is there is on the contrary in course of reaction; cause results of industrial application not good, as Mitsubishi Chemical's 30,000 tons/year of Rh/TPPS butene hydroformylation devices were announced to stop production in 2000.
Take Rh as activated centre, the bidentate phosphite ester catalyst system that is part, industrial is be representative with the low pressure oxo catalyst OxoSelector30 of Davy/Dow, utilize phosphite ester larger sting corner effect, effectively can improve selective [vanderSlot, the S.C. of linear chain aldehyde; Duran, J.; Luten, J.; Kamer, P.C.J.; VanLeeuwen, P.W.N.M.Organometallics2002,21,3873-3883.], [Magee, M.P.; Luo, W.; Hersh, W.H.Organometallics2002,21,362-372], [than woods etc., Chinese patent CN1029774C].Although the more previous technology of Rh/ bidentate phosphite ester catalyst system has obvious advantage and started to be subject to the most attention of academia and industrial quarters, but owing to being difficult to the existence of trace oxygen or the water avoided in reaction system, easily cause catalyst oxidation or hydrolysis and decompose inactivation, and then make reactivity and selective rapid decline, improve stability while thus how ensureing catalyst activity and become research emphasis.
Patent CN1072691C improves the stability of bi-ester of phosphite storage by interpolation organic amine and slaine, but the organic amine added can aggravate the polycondensation of aldehyde compound in follow-up hydroformylation reaction; Patent CN103702758A replaces amine or epoxide by adding and is stored in synthesis gas and/or inert gas blanket gets off to realize the catalyst based storage in the downtime of bidentate phosphite ester and stabilisation, but the decomposition of still likely ingress of air aggravation bidentate phosphite ester in practical operation.Two kinds of methods all introduce novel substance in catalyst composition, indirectly promote the stability of part or catalyst, thus still needing a kind of method finding stability by directly promoting complex catalyst itself, even still can meet the stability of catalyst in the certain air atmosphere of contact.
In patent CN200610147735.2 and patent CN200810038223.1, by adding a small amount of phosphite ester ligand in rhodium (I)/triaryl phosphine system, the carbon monoxide-olefin polymeric obtained has advantages such as can improving the just different ratio of product, minimizing triphenylphosphine consumption, but effective molecular structure of the not mentioned complex compound catalyst that specifically works, the also technical problem deposited of unresolved catalyst and bidentate phosphite ester.
The present invention solves this problem targetedly.
Summary of the invention
Technical problem to be solved by this invention is the problem that in prior art, catalyst stable storage is bad, provides a kind of method of raising olefin hydroformylation catalyst storage stability newly.This catalyst has the good advantage of catalyst stable storage.
For solving the problem; the technical solution used in the present invention is as follows: a kind of method improving olefin hydroformylation catalyst storage stability; in hydroformylation of olefin; catalyst is at least one in complex catalyst I or complex catalyst II; described complex catalyst I comprises rhodium, bidentate phosphite ester, monophosphorus ligand, and its general structure is as follows:
Wherein:
(1) X is C
6-C
28replacement or unsubstituted organic divalence bridging arlydene;
(2) Y
1, Y
2, Z
1or Z
2for hydrogen, the tert-butyl group or methoxyl group;
(3) Ar
1-3for the aromatic group of 6-22 carbon atom, and described three Ar groups are identical or not identical; Described complex catalyst II comprises rhodium, bidentate phosphite ester, biphosphine ligand, and its general structure is as follows:
Wherein:
(1) X is C
6-C
28replacement or unsubstituted organic divalence bridging arlydene;
(2) Y
1, Y
2, Z
1or Z
2for hydrogen, the tert-butyl group or methoxyl group;
(3) n is the integer of 1-8, Ar
1-4for the aromatic group of 6-22 carbon atom, and described four Ar groups are identical or not identical.
In technique scheme, preferably, described monophosphorus ligand has following structural formula:
In technique scheme, preferably, described bidentate phosphite ester ligand has following structural formula:
In technique scheme, preferably, the structure of described complex catalyst I is as follows:
In technique scheme, preferably, described bidentate phosphine ligands has following structural formula:
In technique scheme, preferably, the structure of described complex catalyst II is as follows:
In technique scheme, preferably, complex catalyst I adds hot preparation by rhodium dicarbonyl acetylacetonate (I) and bidentate phosphite ester, monophosphorus ligand under synthesis gas atmosphere; The mol ratio of rhodium dicarbonyl acetylacetonate (I) and bidentate phosphite ester, monophosphorus ligand is 1:1-2:1-4; Complex catalyst II adds hot preparation by rhodium dicarbonyl acetylacetonate (I) and bidentate phosphite ester, biphosphine ligand under synthesis gas atmosphere; The mol ratio of rhodium dicarbonyl acetylacetonate (I) and bidentate phosphite ester, biphosphine ligand is 1:1-2:1-2.
In technique scheme, preferably, in described catalyst, complex catalyst I is 0-100:1 with the mol ratio of complex catalyst II.
In technique scheme, preferably, in complex catalyst I, the concentration of rhodium is 10 ~ 1500mg/L, and in complex catalyst II, the concentration of rhodium is 10 ~ 1500mg/L.
In technique scheme, more preferably, in complex catalyst I, the concentration of rhodium is 150 ~ 600mg/L, and in complex catalyst II, the concentration of rhodium is 150 ~ 600mg/L.
In the present invention, described alkene is ethene, propylene, butylene.
In the present invention, gained catalyst solution, under inert free gas protection, is deposited under room temperature, is passed through
31part in PNMR analytical reactions liquid system and the concentration of metal complex catalyst, follow the tracks of the stability of catalyst.Under the temperature conditions that industrial flash distillation is heated, pass through equally
31part in PNMR analytical reactions liquid system and the concentration of metal complex catalyst, follow the tracks of catalyst stability in a heated condition.
The present inventor finds in surprise, the molecular structure of rhodium/(bidentate phosphite ester-monophosphorus ligand) complex catalyst or rhodium/(bidentate phosphite ester-biphosphine ligand) complex catalyst is stable especially, long-time stable can be met deposit, even in air atmosphere, this complex molecules structure still long-time stable existence; For rhodium/(bidentate phosphite ester-monophosphorus ligand) complex catalyst, when rhodium/(bidentate phosphite ester-monophosphorus ligand) complex catalyst and bidentate phosphite ester, monophosphorus ligand coexist, this composition is still very stable, long storage time under inert free gas protection, except monophosphorus ligand partial oxidation, rhodium/(bidentate phosphite ester-monophosphorus ligand) complex catalyst and bidentate phosphite ester all very stable, have no obvious decomposition; Concentration deposited by described catalyst can maintain 2000 ~ 50000mg/L, achieves good technique effect.
Below by embodiment, the invention will be further elaborated, but be not limited only to the present embodiment.
Detailed description of the invention
The following example contributes to further illustrating the present invention, but does not form any restriction to the present invention.
1, hydroformylation reaction catalyst is complex catalyst I
Ligand L 1-14 has following structure:
Comparative example 1
Be equipped with in manometric stainless steel autoclave to 200mL in air atmosphere and add [Rh (acac) (CO)
2] (0.7mmol, 181mg) and the L12 bidentate phosphite ester ligand of 1.4mmol, and 70mL dry toluene, connect gas line, after replacing gas reactor three times with synthesis gas (hydrogen: carbon monoxide=1:1), stir with the mechanical agitator of Electromagnetic Drive, be heated to temperature 100 DEG C in still, passing into synthesis gas to stagnation pressure is 2.0MPa, at 100 DEG C, react 1h under the condition of 2.0MPa, obtained rhodium/(bidentate phosphite ester L12) complex catalyst, its structure is: HRh (L12) (CO)
2.
31pNMR (Toluene, 162MHz) δ 173.6ppm,
1j
rhP=239Hz;
1hNMR δ-11.7ppm (br); IR (Toluene, cm
-1) ν (Rh-H) and ν (CO) 2051 (s), 2018 (m).Because the ligand L 12 of adding is excessive, can observe L12's
31pNMR (Toluene, 162MHz) δ 145.8ppm.
Gained catalyst room temperature is placed, and tracking stability, places after 3 months, pass through
31pNMR quantitatively follows the tracks of, and finds HRh (L12) (CO)
2corresponding phosphorus spectrum disappears completely, and phosphorus spectrum corresponding to L12 also disappears completely, confirms HRh (L12) (CO)
2decompose completely with L12, the black precipitate that after obvious catalyst decomposes is arranged at bottom, rhodium is separated out.Tracking results is in table 1.
Comparative example 2
Be equipped with in manometric stainless steel autoclave to 200mL in air atmosphere and add [Rh (acac) (CO)
2] (0.7mmol, 181mg) and the L11 bidentate phosphite ester ligand of 1.4mmol, and 70mL dry toluene, connect gas line, after replacing gas reactor three times with synthesis gas (hydrogen: carbon monoxide=1:1), stir with the mechanical agitator of Electromagnetic Drive, be heated to temperature 100 DEG C in still, passing into synthesis gas to stagnation pressure is 2.0MPa, at 100 DEG C, react 1h under the condition of 2.0MPa, obtained rhodium/(bidentate phosphite ester L11) complex catalyst, its structure is: HRh (L11) (CO)
2.
31pNMR (Toluene, 162MHz) δ 172.3ppm,
1j
rhP=233Hz;
1hNMR δ-10.4ppm (dt),
2j
pH=11.2Hz,
1j
rhH=4.0Hz; IR (Toluene, cm
-1) ν (Rh-H) and ν (CO) 2047 (s), 2010 (m).Because the ligand L 11 of adding is excessive, can observe L11's
31pNMR (Toluene, 162MHz) δ 145.2ppm.
Gained catalyst room temperature is placed, and tracking stability, places after 3 months, pass through
31pNMR quantitatively follows the tracks of, and finds HRh (L11) (CO)
2corresponding phosphorus spectrum disappears completely, and phosphorus spectrum corresponding to L11 also disappears completely, confirms HRh (L11) (CO)
2decompose completely with L11, the black precipitate that after obvious catalyst decomposes is arranged at bottom, rhodium is separated out.Tracking results is in table 1.
Embodiment 1
Be equipped with in manometric stainless steel autoclave to 200mL in air atmosphere and add [Rh (acac) (CO)
2] (0.7mmol, 181mg) with the triphenylphosphine L1 monophosphorus ligand of 2.8mmol and the L12 bidentate phosphite ester ligand of 1.4mmol, and 70mL dry toluene, connect gas line, after replacing gas reactor three times with synthesis gas (hydrogen: carbon monoxide=1:1), stir with the mechanical agitator of Electromagnetic Drive, be heated to temperature 100 DEG C in still, passing into synthesis gas to stagnation pressure is 2.0MPa, at 100 DEG C, 1h is reacted under the condition of 2.0MPa, obtained rhodium/(bidentate phosphite ester-monophosphorus ligand) complex catalyst HRh (L12) (L1) (CO).Its molecular structure is as follows:
31p2: δ 175.1ppm of P1: δ 177.9ppm of PNMR (Toluene, 162MHz) L12 and rhodium coordination, L12 and rhodium coordination, the P3:36.2ppm of L1 and rhodium coordination,
1j
rhP1=249Hz,
1j
rhP2=249Hz,
1j
rhP3=141Hz,
2j
p1P2=279Hz,
2j
p1P3=162Hz,
2j
p3P2=152Hz,
1hNMR δ-10.8ppm (m), IR (Toluene, cm
-1) ν (Rh-H) and ν (CO) 2038 (s), 1951 (m).Due to add ligand L 12 and L1 excessive, can observe L12's
31pNMR (Toluene, 162MHz) δ 145.9ppm, L1's
31pNMR (Toluene, 162MHz) δ-5.6ppm.
Gained catalyst room temperature is placed, and tracking stability, places after 3 months, pass through
31pNMR quantitatively follows the tracks of, and finds HRh (L12) (L1) (CO) stable existence, without significant change, and most of L12 still stable existence, small part is decomposed, and ligand L 1 part is oxidized, forms corresponding oxide.Experiment confirms that, under the condition of inert free gas protection, catalyst is long-term storage at room temperature, and HRh (L12) (L1) (CO) and L12 still can stable existences, and the rhodium catalyst sediment without black is separated out.Tracking results is in table 1.
Embodiment 2
Be equipped with in manometric stainless steel autoclave to 200mL in air atmosphere and add [Rh (acac) (CO)
2] (0.7mmol, 181mg) with the triphenylphosphine L1 monophosphorus ligand of 2.8mmol and the L11 bidentate phosphite ester ligand of 1.4mmol, and 70mL dry toluene, connect gas line, after replacing gas reactor three times with synthesis gas (hydrogen: carbon monoxide=1:1), stir with the mechanical agitator of Electromagnetic Drive, be heated to temperature 100 DEG C in still, passing into synthesis gas to stagnation pressure is 2.0MPa, at 100 DEG C, 1h is reacted under the condition of 2.0MPa, obtained rhodium/(bidentate phosphite ester-monophosphorus ligand) complex catalyst HRh (L11) (L1) (CO).Its molecular structure is as follows:
P2: δ 173.8ppm of P1: δ 177.0ppm of L11 and rhodium coordination, L11 and rhodium coordination, the P3:34.3ppm of L1 and rhodium coordination,
1j
rhP1=251Hz;
1j
rhP2=246Hz,
1j
rhP3=141Hz,
2j
p1P2=279Hz,
2j
p1P3=169Hz,
2j
p3P2=145Hz;
1hNMR δ-11.8ppm (ddd)
1j
rhH=7.6Hz,
2j
p2H=21.6Hz,
2j
pH=3.2Hz; IR (Toluene, cm
-1) ν (Rh-H) and ν (CO) 2036 (m), 1948 (m).Due to add ligand L 11 and L1 excessive, can observe L11's
31pNMR (Toluene, 162MHz) δ 143.9ppm, L1's
31pNMR (Toluene, 162MHz) δ-6.6ppm.
Gained catalyst room temperature is placed, and tracking stability, places after 3 months, pass through
31pNMR quantitatively follows the tracks of, and finds HRh (L11) (L1) (CO) stable existence, without significant change, and most of L11 still stable existence, small part is decomposed, and ligand L 1 part is oxidized, forms corresponding oxide.Experiment confirms that, under the condition of inert free gas protection, catalyst is long-term storage at room temperature, and HRh (L11) (L1) (CO) and L11 still can stable existences, and the rhodium catalyst sediment without black is separated out.Tracking results is in table 1.
Embodiment 3
Be equipped with in manometric stainless steel autoclave to 200mL in air atmosphere and add [Rh (acac) (CO)
2] (0.7mmol, 181mg) with the L4 monophosphorus ligand of 2.8mmol and the L12 bidentate phosphite ester ligand of 1.4mmol, and 70mL dry toluene, connect gas line, after replacing gas reactor three times with synthesis gas (hydrogen: carbon monoxide=1:1), stir with the mechanical agitator of Electromagnetic Drive, be heated to temperature 100 DEG C in still, passing into synthesis gas to stagnation pressure is 2.0MPa, at 100 DEG C, 1h is reacted, obtained rhodium/(bidentate phosphite ester-monophosphorus ligand) complex catalyst HRh (L12) (L4) (CO) under the condition of 2.0MPa.Its molecular structure is as follows:
31p2: δ 175.4ppm of P1: δ 177.5ppm of PNMR (Toluene, 162MHz) L12 and rhodium coordination, L12 and rhodium coordination, the P3:34.4ppm of L4 and rhodium coordination,
1j
rhP1=248Hz,
1j
rhP2=249Hz,
1j
rhP3=139Hz,
2j
p1P2=282Hz,
2j
p1P3=157Hz,
2j
p3P2=157Hz;
1hNMR δ-11.2ppm (m); IR (Toluene, cm
-1) ν (Rh-H) and ν (CO) 2039 (m), 1945 (m).Due to add ligand L 12 and L4 excessive, can observe L12's
31pNMR (Toluene, 162MHz) δ 145.9ppm, L4's
31pNMR (Toluene, 162MHz) δ-8.1ppm.
Gained catalyst room temperature is placed, and tracking stability, places after 3 months, pass through
31pNMR quantitatively follows the tracks of, and finds HRh (L12) (L4) (CO) stable existence, without significant change, and most of L12 still stable existence, small part is decomposed, and ligand L 4 part is oxidized, forms corresponding oxide.Experiment confirms that, under the condition of inert free gas protection, catalyst is long-term storage at room temperature, and HRh (L12) (L4) (CO) and L12 still can stable existences, and the rhodium catalyst sediment without black is separated out.Tracking results is in table 1.
Embodiment 4
Be equipped with in manometric stainless steel autoclave to 200mL in air atmosphere and add [Rh (acac) (CO)
2] (0.7mmol, 181mg) with the L2 monophosphorus ligand of 2.8mmol and the L12 bidentate phosphite ester ligand of 1.4mmol, and 70mL dry toluene, connect gas line, after replacing gas reactor three times with synthesis gas (hydrogen: carbon monoxide=1:1), stir with the mechanical agitator of Electromagnetic Drive, be heated to temperature 100 DEG C in still, passing into synthesis gas to stagnation pressure is 2.0MPa, at 100 DEG C, 1h is reacted, obtained rhodium/(bidentate phosphite ester-monophosphorus ligand) complex catalyst HRh (L12) (L2) (CO) under the condition of 2.0MPa.Its molecular structure is as follows:
31p2: δ 175.1ppm of P1: δ 181.0ppm of PNMR (Toluene, 162MHz) L12 and rhodium coordination, L12 and rhodium coordination, the P3:41.5ppm of L2 and rhodium coordination,
1j
rhP1=249Hz,
1j
rhP2=246Hz,
1j
rhP3=172Hz;
2j
p1P2=274Hz,
2j
p1P3=172Hz,
2j
p3P2=141Hz.
1hNMR δ-10.9 (m)
2j
p2H=22.6Hz; IR (Toluene, cm
-1) ν (Rh-H) and ν (CO) 2030 (m), 1945 (m).Due to add ligand L 12 and L2 excessive, can observe L12's
31pNMR (Toluene, 162MHz) δ 145.9ppm, L2's
31pNMR (Toluene, 162MHz) δ-4.2ppm.
Gained catalyst room temperature is placed, and tracking stability, places after 3 months, pass through
31pNMR quantitatively follows the tracks of, and finds HRh (L12) (L2) (CO) stable existence, without significant change, and most of L12 still stable existence, small part is decomposed, and ligand L 2 part is oxidized, forms corresponding oxide.Experiment confirms that, under the condition of inert free gas protection, catalyst is long-term storage at room temperature, and HRh (L12) (L2) (CO) and L12 still can stable existences, and the rhodium catalyst sediment without black is separated out.Tracking results is in table 1.
Embodiment 5
Be equipped with in manometric stainless steel autoclave to 200mL in air atmosphere and add [Rh (acac) (CO)
2] (0.7mmol, 181mg) with the L4 monophosphorus ligand of 2.8mmol and the L11 bidentate phosphite ester ligand of 1.4mmol, and 70mL dry toluene, connect gas line, after replacing gas reactor three times with synthesis gas (hydrogen: carbon monoxide=1:1), stir with the mechanical agitator of Electromagnetic Drive, be heated to temperature 100 DEG C in still, passing into synthesis gas to stagnation pressure is 2.0MPa, at 100 DEG C, 1h is reacted, obtained rhodium/(bidentate phosphite ester-monophosphorus ligand) complex catalyst HRh (L11) (L4) (CO) under the condition of 2.0MPa.Its molecular structure is as follows:
31p1: δ 178.1ppm of PNMR (Toluene, 162MHz) L11 and rhodium coordination, P2: δ 174.8ppm of L11 rhodium coordination, the P3:32.9ppm of L4 rhodium coordination,
1j
rhP1=251Hz,
1j
rhP2=246Hz,
1j
rhP3=142Hz,
2j
p1P2=280Hz,
2j
p1P3=168Hz,
2j
p3P2=148Hz;
1hNMR δ-10.8ppm (m); IR (Toluene, cm
-1) ν (Rh-H) and ν (CO) 2036 (s), 1948 (m).Due to add ligand L 11 and L4 excessive, can observe L11's
31pNMR (Toluene, 162MHz) δ 144.8ppm, L4's
31pNMR (Toluene, 162MHz) δ-8.2ppm.
Gained catalyst room temperature is placed, and tracking stability, places after 3 months, pass through
31pNMR quantitatively follows the tracks of, and finds HRh (L11) (L4) (CO) stable existence, without significant change, and most of L11 still stable existence, small part is decomposed, and ligand L 4 part is oxidized, forms corresponding oxide.Experiment confirms that, under the condition of inert free gas protection, catalyst is long-term storage at room temperature, and HRh (L11) (L4) (CO) and L11 still can stable existences, and the rhodium catalyst sediment without black is separated out.Tracking results is in table 1.
Table 1 complex catalyst room temperature I storage stability comparative result
2, hydroformylation reaction catalyst is complex catalyst II
Ligand L 1-13 has following structure:
Embodiment 6
Be equipped with in manometric stainless steel autoclave to 200mL in air atmosphere and add [Rh (acac) (CO)
2] (0.7mmol, 181mg) with 1 of 1.4mmol, the L12 bidentate phosphite ester ligand of two (diphenylphosphine) propane L3 bidentate phosphine ligands of 3-and 1.4mmol, and 70mL dry toluene, connect gas line, after replacing gas reactor three times with synthesis gas (hydrogen: carbon monoxide=1:1), stir with the mechanical agitator of Electromagnetic Drive, be heated to temperature 100 DEG C in still, passing into synthesis gas to stagnation pressure is 2.0MPa, at 100 DEG C, 1h is reacted under the condition of 2.0MPa, obtained rhodium/(bidentate phosphite ester-biphosphine ligand) complex catalyst HRh (L12) (L3) (CO).Its molecular structure is as follows:
31p2: δ 176.0ppm of P1: δ 180.7ppm of PNMR (Toluene, 162MHz) L12 and rhodium coordination, L12 and rhodium coordination, L3 and rhodium coordination P3:24.0ppm, the P4:-19.6ppm of L3 in complex compound,
1j
rhP1=248Hz,
1j
rhP2=248Hz,
1j
rhP3=139Hz,
2j
p1P2=262Hz,
2j
p1P3=172Hz,
2j
p3P2=152Hz;
1hNMR δ-11.2ppm (m); IR (Toluene, cm
-1) ν (Rh-H) and ν (CO) 2033 (vs), 1948 (s).Due to add ligand L 12 and L3 excessive, can observe free L12's
31pNMR (Toluene, 162MHz) δ 145.4ppm, L3's
31pNMR (Toluene, 162MHz) δ-18.7ppm.
Gained catalyst room temperature is placed, and tracking stability under inert free gas protection, places after 3 months, pass through
31pNMR quantitatively follows the tracks of, and finds HRh (L12) (L3) (CO) stable existence, without significant change, and most of L12 still stable existence, small part is decomposed, and ligand L 3 part is oxidized, forms corresponding oxide.Experiment confirms that, under the condition of inert free gas protection, catalyst is long-term storage at room temperature, and HRh (L12) (L3) (CO) and L12 still can stable existences, and the rhodium catalyst sediment without black is separated out.Tracking results is in table 2.
Embodiment 7
Be equipped with in manometric stainless steel autoclave to 200mL in air atmosphere and add [Rh (acac) (CO)
2] (0.7mmol, 181mg) with BISBI ligand L 1 bidentate phosphine ligands of 1.4mmol and the L12 bidentate phosphite ester ligand of 1.4mmol, and 70mL dry toluene, connect gas line, after replacing gas reactor three times with synthesis gas (hydrogen: carbon monoxide=1:1), stir with the mechanical agitator of Electromagnetic Drive, be heated to temperature 100 DEG C in still, passing into synthesis gas to stagnation pressure is 2.0MPa, at 100 DEG C, 1h is reacted under the condition of 2.0MPa, obtained rhodium/(bidentate phosphite ester-biphosphine ligand) complex catalyst HRh (L12) (L1) (CO).Its molecular structure is as follows:
Due to molecular rigidity after ligand L 12 and BISBI and rhodium complexing, form diastereoisomer,
31the upper appearance of PNMR two groups of peaks, wherein one group of peak is as follows:
31p2: δ 175.9ppm of P1: δ 179.8ppm of PNMR (Toluene, 162MHz) L12 and rhodium coordination, L12 and rhodium coordination, L1 and rhodium coordination P3:30.1ppm, the P4:-11.2ppm of L1 in complex compound,
1j
rhP1=249Hz,
1j
rhP2=248Hz,
1j
rhP3=141Hz,
2j
p1P2=274Hz,
2j
p1P3=170Hz,
2j
p3P2=156Hz; Another group peak is as follows:
31p2: δ 175.4ppm of P1: δ 178.9ppm of PNMR (Toluene, 162MHz) L12 and rhodium coordination, L12 and rhodium coordination, L1 and rhodium coordination P3:28.9ppm, the P4:-11.9ppm of L1 in complex compound,
1j
rhP1=248Hz,
1j
rhP2=248Hz,
1j
rhP3=141Hz,
2j
p1P2=271Hz,
2j
p1P3=168Hz,
2j
p3P2=156Hz;
1hNMR δ-11.1ppm (m); IR (Toluene, cm
-1) ν (Rh-H) and ν (CO) 2034 (vs), 1949 (s).Due to add ligand L 12 and L1 excessive, can observe free L12's
31pNMR (Toluene, 162MHz) δ 145.5ppm, L1's
31pNMR (Toluene, 162MHz) δ-11.6ppm.
Gained catalyst room temperature is placed, and tracking stability under inert free gas protection, places after 3 months, pass through
31pNMR quantitatively follows the tracks of, and finds HRh (L12) (L1) (CO) stable existence, without significant change, and most of L12 still stable existence, small part is decomposed, and ligand L 1 part is oxidized, forms corresponding oxide.Experiment confirms that, under the condition of inert free gas protection, catalyst is long-term storage at room temperature, and HRh (L12) (L1) (CO) and L12 still can stable existences, and the rhodium catalyst sediment without black is separated out.Tracking results is in table 2.
Embodiment 8
Be equipped with in manometric stainless steel autoclave to 200mL in air atmosphere and add [Rh (acac) (CO)
2] (0.7mmol, 181mg) with 1 of 1.4mmol, the L10 bidentate phosphite ester ligand of two (diphenylphosphine) butane L4 bidentate phosphine ligands of 4-and 1.4mmol, and 70mL dry toluene, connect gas line, after replacing gas reactor three times with synthesis gas (hydrogen: carbon monoxide=1:1), stir with the mechanical agitator of Electromagnetic Drive, be heated to temperature 100 DEG C in still, passing into synthesis gas to stagnation pressure is 2.0MPa, at 100 DEG C, 1h is reacted under the condition of 2.0MPa, obtained rhodium/(bidentate phosphite ester-biphosphine ligand) complex catalyst HRh (L10) (L4) (CO).Its molecular structure is as follows:
31p2: δ 176.2ppm of P1: δ 179.8ppm of PNMR (Toluene, 162MHz) L10 and rhodium coordination, L10 and rhodium coordination, L4 and rhodium coordination P3:24.4ppm, the P4:-15.6ppm of L4 in complex compound,
1j
rhP1=249Hz,
1j
rhP2=244Hz,
1j
rhP3=139Hz,
2j
p1P2=269Hz,
2j
p1P3=175Hz,
2j
p3P2=142Hz;
1hNMR δ-11.1 (ddd) J=4Hz,
2j
p2H=22Hz, J=9Hz; IR (Toluene, cm
-1) ν (Rh-H) and ν (CO) 2072 (m), 2033 (s), 1946 (m).Due to add ligand L 10 and L4 excessive, can observe free L10's
31pNMR (Toluene, 162MHz) δ 144.9ppm, L4's
31pNMR (Toluene, 162MHz) δ-16.8ppm.
Gained catalyst room temperature is placed, and tracking stability under inert free gas protection, places after 3 months, pass through
31pNMR quantitatively follows the tracks of, and finds HRh (L10) (L4) (CO) stable existence, without significant change, and most of L10 still stable existence, small part is decomposed, and ligand L 4 part is oxidized, forms corresponding oxide.Experiment confirms that, under the condition of inert free gas protection, catalyst is long-term storage at room temperature, and HRh (L10) (L4) (CO) and L10 still can stable existences, and the rhodium catalyst sediment without black is separated out.Tracking results is in table 2.
Embodiment 9
Be equipped with in manometric stainless steel autoclave to 200mL in air atmosphere and add [Rh (acac) (CO)
2] (0.7mmol, 181mg) with 1 of 1.4mmol, the L10 bidentate phosphite ester ligand of two (diphenylphosphine) propane L3 bidentate phosphine ligands of 3-and 1.4mmol, and 70mL dry toluene, connect gas line, after replacing gas reactor three times with synthesis gas (hydrogen: carbon monoxide=1:1), stir with the mechanical agitator of Electromagnetic Drive, be heated to temperature 100 DEG C in still, passing into synthesis gas to stagnation pressure is 2.0MPa, at 100 DEG C, 1h is reacted under the condition of 2.0MPa, obtained rhodium/(bidentate phosphite ester-biphosphine ligand) complex catalyst HRh (L10) (L3) (CO).Its molecular structure is as follows:
31p2: δ 176.0ppm of P1: δ 180.0ppm of PNMR (Toluene, 162MHz) L10 and rhodium coordination, L10 and rhodium coordination, L3 and rhodium coordination P3:24.2ppm, the P4:-19.1ppm of L3 in complex compound,
1j
rhP1=249Hz,
1j
rhP2=244Hz,
1j
rhP3=139Hz,
2j
p1P2=267Hz,
2j
p1P3=173Hz,
2j
p3P2=139Hz;
1hNMR δ-11.1 (m),
2j
p2H=22Hz; IR (Toluene, cm
-1) ν (Rh-H) and ν (CO) 2072 (s), 2033 (s), 1948 (m).Due to add ligand L 10 and L3 excessive, can observe free L10's
31pNMR (Toluene, 162MHz) δ 144.9ppm, L3's
31pNMR (Toluene, 162MHz) δ-18.1ppm.
Gained catalyst room temperature is placed, and tracking stability under inert free gas protection, places after 3 months, pass through
31pNMR quantitatively follows the tracks of, and finds HRh (L10) (L3) (CO) stable existence, without significant change, and most of L10 still stable existence, small part is decomposed, and ligand L 3 part is oxidized, forms corresponding oxide.Experiment confirms that, under the condition of inert free gas protection, catalyst is long-term storage at room temperature, and HRh (L10) (L3) (CO) and L10 still can stable existences, and the rhodium catalyst sediment without black is separated out.Tracking results is in table 2.
Embodiment 10
Be equipped with in manometric stainless steel autoclave to 200mL in air atmosphere and add [Rh (acac) (CO)
2] (0.7mmol, 181mg) with BISBI ligand L 1 bidentate phosphine ligands of 1.4mmol and the L10 bidentate phosphite ester ligand of 1.4mmol, and 70mL dry toluene, connect gas line, after replacing gas reactor three times with synthesis gas (hydrogen: carbon monoxide=1:1), stir with the mechanical agitator of Electromagnetic Drive, be heated to temperature 100 DEG C in still, passing into synthesis gas to stagnation pressure is 2.0MPa, at 100 DEG C, 1h is reacted under the condition of 2.0MPa, obtained rhodium/(bidentate phosphite ester-biphosphine ligand) complex catalyst HRh (L10) (L1) (CO).Its molecular structure is as follows:
Due to molecular rigidity after ligand L 10 and BISBI and rhodium complexing, form diastereoisomer,
31the upper appearance of PNMR two groups of peaks, wherein one group of peak is as follows:
31p2: δ 175.9ppm of P1: δ 179.1ppm of PNMR (Toluene, 162MHz) L10 and rhodium coordination, L10 and rhodium coordination, L1 and rhodium coordination P3:30.7ppm, the P4:-10.8ppm of L1 in complex compound,
1j
rhP1=249Hz,
1j
rhP2=246Hz,
1j
rhP3=141Hz,
2j
p1P2=271Hz,
2j
p1P3=175Hz,
2j
p3P2=156Hz; Another group peak is as follows:
31p2: δ 175.6ppm of P1: δ 178.3ppm of PNMR (Toluene, 162MHz) L10 and rhodium coordination, L10 and rhodium coordination, L1 and rhodium coordination P3:30.1ppm, the P4:-11.5ppm of L1 in complex compound,
1j
rhP1=249Hz,
1j
rhP2=246Hz,
1j
rhP3=141Hz,
2j
p1P2=269Hz,
2j
p1P3=168Hz,
2j
p3P2=152Hz;
1hNMR δ-11.2ppm (m); IR (Toluene, cm
-1) ν (Rh-H) and ν (CO) 2035 (vs), 1946 (s).Due to add ligand L 10 and L1 excessive, can observe free L10's
31pNMR (Toluene, 162MHz) δ 144.8ppm, L1's
31pNMR (Toluene, 162MHz) δ-11.1ppm.
Gained catalyst room temperature is placed, and tracking stability under inert free gas protection, places after 3 months, pass through
31pNMR quantitatively follows the tracks of, and finds HRh (L10) (L1) (CO) stable existence, without significant change, and most of L12 still stable existence, small part is decomposed, and ligand L 1 part is oxidized, forms corresponding oxide.Experiment confirms that, under the condition of inert free gas protection, catalyst is long-term storage at room temperature, and HRh (L10) (L1) (CO) and L10 still can stable existences, and the rhodium catalyst sediment without black is separated out.Tracking results is in table 2.
Embodiment 11
Be equipped with in manometric stainless steel autoclave to 200mL in air atmosphere and add [Rh (acac) (CO)
2] (0.7mmol, 181mg) with 1 of 1.4mmol, the L12 bidentate phosphite ester ligand of two (diphenylphosphine) butane L4 bidentate phosphine ligands of 3-and 1.4mmol, and 70mL dry toluene, connect gas line, after replacing gas reactor three times with synthesis gas (hydrogen: carbon monoxide=1:1), stir with the mechanical agitator of Electromagnetic Drive, be heated to temperature 100 DEG C in still, passing into synthesis gas to stagnation pressure is 2.0MPa, at 100 DEG C, 1h is reacted under the condition of 2.0MPa, obtained rhodium/(bidentate phosphite ester-biphosphine ligand) complex catalyst HRh (L12) (L4) (CO).Its molecular structure is as follows:
31p2: δ 177.4ppm of P1: δ 180.1ppm of PNMR (Toluene, 162MHz) L12 and rhodium coordination, L12 and rhodium coordination, L4 and rhodium coordination P3:24.8ppm, the P4:-15.7ppm of L4 in complex compound,
1j
rhP1=249Hz,
1j
rhP2=246Hz,
1j
rhP3=139Hz,
2j
p1P2=173Hz,
2j
p1P3=147Hz,
2j
p3P2=139Hz;
1hNMR δ-10.95 (dd,
1j
rhH=8Hz,
2j
pH=20Hz); IR (Toluene, cm
-1) ν (Rh-H) and ν (CO) 2072 (m), 2032 (s), 1946 (m).Due to add ligand L 12 and L4 excessive, can observe free L12's
31pNMR (Toluene, 162MHz) δ 148.5ppm, L4's
31pNMR (Toluene, 162MHz) δ-16.8ppm.
Gained catalyst room temperature is placed, and tracking stability under inert free gas protection, places after 3 months, pass through
31pNMR quantitatively follows the tracks of, and finds HRh (L12) (L4) (CO) stable existence, without significant change, and most of L12 still stable existence, small part is decomposed, and ligand L 4 part is oxidized, forms corresponding oxide.Experiment confirms that, under the condition of inert free gas protection, catalyst is long-term storage at room temperature, and HRh (L12) (L4) (CO) and L12 still can stable existences, and the rhodium catalyst sediment without black is separated out.Tracking results is in table 2.
Table 2 complex catalyst II storage at room temperature stability comparative result
3, hydroformylation reaction catalyst is the mixture of complex catalyst I and complex catalyst II
Embodiment 11
Adopt the catalyst of mixture as hydroformylation reaction of the complex catalyst II of the complex catalyst I of embodiment 1 preparation, embodiment 6 preparation, wherein the mol ratio of complex catalyst I and complex catalyst II is 1:1.Described catalyst room temperature placed, tracking stability under inert free gas protection, places after 3 months, passes through
31pNMR quantitatively follows the tracks of, and finds complex compound I and II stable existence, and without significant change, and most of L12 still stable existence, small part is decomposed, and ligand L 1 and L3 part oxidized, the oxide of formation correspondence.Experiment confirms that, under the condition of inert free gas protection, catalyst is long-term storage at room temperature, and complex catalyst I and complex catalyst II still can stable existences, and the rhodium catalyst sediment without black is separated out.Result is as shown in table 2.
Claims (10)
1. one kind is improved the method for olefin hydroformylation catalyst storage stability; in hydroformylation of olefin; catalyst is at least one in complex catalyst I or complex catalyst II, and described complex catalyst I comprises rhodium, bidentate phosphite ester, monophosphorus ligand, and its general structure is as follows:
Wherein:
(1) X is C
6-C
28replacement or unsubstituted organic divalence bridging arlydene;
(2) Y
1, Y
2, Z
1or Z
2for hydrogen, the tert-butyl group or methoxyl group;
(3) Ar
1-3for the aromatic group of 6-22 carbon atom, and described three Ar groups are identical or not identical; Described complex catalyst II comprises rhodium, bidentate phosphite ester, biphosphine ligand, and its general structure is as follows:
Wherein:
(1) X is C
6-C
28replacement or unsubstituted organic divalence bridging arlydene;
(2) Y
1, Y
2, Z
1or Z
2for hydrogen, the tert-butyl group or methoxyl group;
(3) n is the integer of 1-8, Ar
1-4for the aromatic group of 6-22 carbon atom, and described four Ar groups are identical or not identical.
2. improve the method for olefin hydroformylation catalyst storage stability according to claim 1, it is characterized in that described monophosphorus ligand has following structural formula:
3. improve the method for olefin hydroformylation catalyst storage stability according to claim 1, it is characterized in that described bidentate phosphite ester ligand has following structural formula:
4. improve the method for olefin hydroformylation catalyst storage stability according to claim 1, it is characterized in that the structure of described complex catalyst I is as follows:
5. improve the method for olefin hydroformylation catalyst storage stability according to claim 1, it is characterized in that described bidentate phosphine ligands has following structural formula:
6. improve the method for olefin hydroformylation catalyst storage stability according to claim 1, it is characterized in that the structure of described complex catalyst II is as follows:
7. improve the method for olefin hydroformylation catalyst storage stability according to claim 1, it is characterized in that complex catalyst I adds hot preparation by rhodium dicarbonyl acetylacetonate (I) and bidentate phosphite ester, monophosphorus ligand under synthesis gas atmosphere; The mol ratio of rhodium dicarbonyl acetylacetonate (I) and bidentate phosphite ester, monophosphorus ligand is 1:1-2:1-4; Complex catalyst II adds hot preparation by rhodium dicarbonyl acetylacetonate (I) and bidentate phosphite ester, biphosphine ligand under synthesis gas atmosphere; The mol ratio of rhodium dicarbonyl acetylacetonate (I) and bidentate phosphite ester, biphosphine ligand is 1:1-2:1-2.
8. improve the method for olefin hydroformylation catalyst storage stability according to claim 1, it is characterized in that in described catalyst, complex catalyst I is 0-100:1 with the mol ratio of complex catalyst II.
9. improve the method for hydroformylation catalyst storage stability according to claim 1, it is characterized in that the concentration of rhodium in complex catalyst I is 10 ~ 1500mg/L, in complex catalyst II, the concentration of rhodium is 10 ~ 1500mg/L.
10. improve the method for hydroformylation catalyst storage stability according to claim 9, it is characterized in that the concentration of rhodium in complex catalyst I is 150 ~ 600mg/L, in complex catalyst II, the concentration of rhodium is 150 ~ 600mg/L.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510933178.6A CN105363493A (en) | 2015-12-15 | 2015-12-15 | Method for improving storage stability of hydroformylation catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510933178.6A CN105363493A (en) | 2015-12-15 | 2015-12-15 | Method for improving storage stability of hydroformylation catalyst |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN105363493A true CN105363493A (en) | 2016-03-02 |
Family
ID=55366408
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510933178.6A Pending CN105363493A (en) | 2015-12-15 | 2015-12-15 | Method for improving storage stability of hydroformylation catalyst |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105363493A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106431869A (en) * | 2016-10-09 | 2017-02-22 | 上海华谊（集团）公司 | Method for producing aldehydes through olefin hydroformylation reaction |
| CN111138493A (en) * | 2020-01-13 | 2020-05-12 | 上海华谊（集团）公司 | Method for synthesizing diphosphite |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2002083618A1 (en) * | 2001-04-13 | 2002-10-24 | Dsm Ip Assets B.V. | Continuous hydroformylation process for forming an aldehyde |
| CN101332437A (en) * | 2008-05-29 | 2008-12-31 | 上海焦化有限公司 | Butene hydroformylation catalyst composition and uses thereof |
| CN102266796A (en) * | 2006-12-22 | 2011-12-07 | 中国科学院上海有机化学研究所 | Propylene hydroformylation catalyzing system and method |
| CN102365258A (en) * | 2009-03-31 | 2012-02-29 | 陶氏技术投资有限公司 | Hydroformylation process with a doubly open-ended bisphosphite ligand |
| CN104058944A (en) * | 2014-04-24 | 2014-09-24 | 上海华谊（集团）公司 | Method for preparing aldehyde through alkene hydroformylation reaction |
-
2015
- 2015-12-15 CN CN201510933178.6A patent/CN105363493A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2002083618A1 (en) * | 2001-04-13 | 2002-10-24 | Dsm Ip Assets B.V. | Continuous hydroformylation process for forming an aldehyde |
| CN102266796A (en) * | 2006-12-22 | 2011-12-07 | 中国科学院上海有机化学研究所 | Propylene hydroformylation catalyzing system and method |
| CN101332437A (en) * | 2008-05-29 | 2008-12-31 | 上海焦化有限公司 | Butene hydroformylation catalyst composition and uses thereof |
| CN102365258A (en) * | 2009-03-31 | 2012-02-29 | 陶氏技术投资有限公司 | Hydroformylation process with a doubly open-ended bisphosphite ligand |
| CN104058944A (en) * | 2014-04-24 | 2014-09-24 | 上海华谊（集团）公司 | Method for preparing aldehyde through alkene hydroformylation reaction |
Non-Patent Citations (1)
| Title |
|---|
| 廖本仁等，: "双亚磷酸酯和双膦混合配合体在丁烯氢甲酰化反应中的应用研究", 《分子催化》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106431869A (en) * | 2016-10-09 | 2017-02-22 | 上海华谊（集团）公司 | Method for producing aldehydes through olefin hydroformylation reaction |
| CN106431869B (en) * | 2016-10-09 | 2019-01-18 | 上海华谊（集团）公司 | The method of hydroformylation of olefin production aldehyde |
| CN111138493A (en) * | 2020-01-13 | 2020-05-12 | 上海华谊（集团）公司 | Method for synthesizing diphosphite |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105566081A (en) | Method for preparing aldehyde through olefin hydroformylation | |
| US10766833B2 (en) | Hydroformylation method and catalyst using rhodium-ruthenium dual metal and tetradentate phosphine ligand | |
| King | Alkylaminobis (difluorophosphines): novel bidentate ligands for stabilizing low metal oxidation states and metal-metal bonded systems | |
| Kalck et al. | Use of water-soluble ligands in homogeneous catalysis | |
| CN106431869B (en) | The method of hydroformylation of olefin production aldehyde | |
| CN101331144B (en) | Tetraphosphorus ligands for catalytic hydroformylation and related reactions | |
| Doherty et al. | Iminophosphines: synthesis, formation of 2, 3-dihydro-1H-benzo [1, 3] azaphosphol-3-ium salts and N-(pyridin-2-yl)-2-diphenylphosphinoylaniline, coordination chemistry and applications in platinum group catalyzed Suzuki coupling reactions and hydrosilylations | |
| HU204747B (en) | Process for hydroformylation catalyzed sith transition metal-bis-phosphite complexes | |
| RU2011143929A (en) | METHOD FOR HYDROFORMING USING A DOUBLE OPEN-END BISPHOSPHITE LIGAND | |
| CN106550597A (en) | Carbon monoxide-olefin polymeric comprising the part based on phosphorus and the hydroformylation process using the carbon monoxide-olefin polymeric | |
| Kumar et al. | Hydroformylation of olefins by metals other than rhodium | |
| CN105413747A (en) | Complex catalyst containing monophosphine ligands | |
| CN1909964B (en) | Phsphorus-containing catalyst composition and process for hydroformylation reaction using the same | |
| Pollock et al. | Fluoroarylphosphines as ligands | |
| CN105363493A (en) | Method for improving storage stability of hydroformylation catalyst | |
| CN112010906A (en) | Bisphosphite and preparation method and application thereof | |
| CN111344273B (en) | Aldehyde production method and alcohol production method | |
| CN105498841A (en) | Complex catalyst containing diphosphine ligand | |
| Trzeciak et al. | Perspectives of rhodium organometallic catalysis. Fundamental and applied aspects of hydroformylation | |
| US5103065A (en) | Transition metal complexes as catalysts for hydrogenation hydroformylation and cyclotrimerization | |
| CN117123276A (en) | Phosphine ligand modified nitrogen doped graphene oxide/porous carbon supported metal catalyst and preparation method and application thereof | |
| Keleş et al. | Synthesis and characterization of bis (diphenylphosphinomethyl) amino ligands and their Ni (II), Pd (II) complexes: Application to hydrogenation of styrene | |
| CN101835786A (en) | Method of inhibiting metal precipitation from transition metal complex | |
| CN108794527A (en) | A kind of bidentate phosphine ligands and its application in hydroformylation reaction | |
| JP3945531B2 (en) | Method for preparing rhodium complex solution |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20160302 |