CN105566081A - Method for preparing aldehyde through olefin hydroformylation - Google Patents

Method for preparing aldehyde through olefin hydroformylation Download PDF

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Publication number
CN105566081A
CN105566081A CN201510934929.6A CN201510934929A CN105566081A CN 105566081 A CN105566081 A CN 105566081A CN 201510934929 A CN201510934929 A CN 201510934929A CN 105566081 A CN105566081 A CN 105566081A
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rhodium
complex catalyst
ligand
phosphite ester
catalyst
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赖春波
范曼曼
杨旭石
李媛
高山林
黄晓云
廖本仁
陈建伟
高惠敏
张春雷
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Shanghai Huayi Group Corp
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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
    • 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
    • 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
    • B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
    • B01J2531/0238—Complexes comprising multidentate ligands, i.e. more than 2 ionic or coordinative bonds from the central metal to the ligand, the latter having at least two donor atoms, e.g. N, O, S, P
    • 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

Abstract

The invention relates to a method for preparing aldehyde through olefin hydroformylation, aiming at mainly solving the problems in the prior art that the normal/isomeric ratio of the product is relatively low and the stability of a catalyst is poor. According to the method for preparing the aldehyde through adopting the olefin hydroformylation, in an olefin hydroformylation reaction, the catalyst is at least one of a complex catalyst I and a complex catalyst II. With the adoption of the technical scheme, the problems above are solved very well and the method can be used for the olefin hydroformylation reaction.

Description

The method of preparing aldehyde by alkene hydroformylation
Technical field
The present invention relates to a kind of method of preparing aldehyde by alkene hydroformylation.
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 industrial 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 outstanding advantages such as the reaction conditionss of its high reactivity, outstanding selectivity and gentleness; become the catalyzer of industrial hydroformylation technological 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 activity, the important indicator such as selectivity and work-ing life of catalyzer.
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 catalyzer.In Rh/TPPS catalyst system; water soluble ligand realizes the circulation of catalyzer by being separated; but pure water soluble ligand not easily obtains; easily emulsion is there is on the contrary in reaction process; 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 active 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 phosphorous acid ester larger sting corner effect, effectively can improve selectivity [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 industry member, 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 reactive behavior and selectivity are declined rapidly, 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 metal-salt, but the organic amine added can aggravate the polycondensation of aldehyde compound in follow-up hydroformylation reaction; Patent CN103702758A replaces amine or epoxy compounds by adding and is stored in synthetic gas and/or inert gas blanket gets off to realize the catalyst based storage in the downtime of bidentate phosphite ester and stabilization, but the decomposition of still likely ingress of air aggravation bidentate phosphite ester in actually operating.Two kinds of methods all introduce novel substance in catalytic composition, indirectly promote the stability of part or catalyzer, thus still needing a kind of method finding stability by directly promoting complex catalyst itself, even still can meet the stability of catalyzer 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 catalyst composition 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 catalyzer 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 of just different lower, poor catalyst stability in product in prior art, provides a kind of method of new preparing aldehyde by alkene hydroformylation.The method has the advantage of just different higher, catalyzer Heat stability is good in product.
For solving the problem, the technical solution used in the present invention is as follows: a kind of method of preparing aldehyde by alkene hydroformylation, 1-butylene, carbon monoxide and hydrogen are that 1:0.9 ~ 1.5:0.9 ~ 1.5 enter hydroformylation reaction device with mol ratio, temperature of reaction be 90 ~ 110 DEG C, reaction pressure is 1.5 ~ 2.0Mpa, the reaction times be 1 ~ 1.5h under with catalyst exposure, generate the product comprising aldehyde; Catalyzer 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 arylidene;
(2) Y 1, Y 2, Z 1or Z 2for hydrogen, the tertiary butyl 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 arylidene;
(2) Y 1, Y 2, Z 1or Z 2for hydrogen, the tertiary butyl 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 described hydroformylation reaction device, the mol ratio of 1-butylene and rhodium is 1900 ~ 2050:1, and the mol ratio of phosphite ester ligand, Phosphine ligands, rhodium is 2:2:1 ~ 4:4:1, and described Phosphine ligands is at least one in monophosphorus ligand or biphosphine ligand.
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 synthetic 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 synthetic 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 catalyzer, 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 ~ 1000mg/L, and in complex catalyst II, the concentration of rhodium is 10 ~ 1000mg/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.
Method of the present invention needs regularly the reaction system run or monitors the concentration of above-described Phosphine ligands and described bidentate phosphite ester ligand continuously, if the concentration described in finding is lower than described value, then may cause the loss of described compound due to oxidation or the reason such as degraded, now Phosphine ligands and described bidentate phosphite ester ligand be added in the reaction mixture of use.
The method that hydroformylation of olefin in this patent prepares aldehyde can significantly improve existing Rh (I)/bidentate phosphite ester or the just different of Rh (I)/bidentate phosphine ligands compares selectivity; and can higher catalytic activity be maintained; extend the work-ing life of bisphosphite ligands and catalyzer thereof; be conducive to the economy improving technique; after reducing, the separating energy consumption of system and the consumption of rhodium catalyst, achieve good technique effect.
Below by embodiment, the invention will be further elaborated, but be not limited only to the present embodiment.
Embodiment
The following example contributes to further illustrating the present invention, but does not form any restriction to the present invention.
1, hydroformylation reaction catalyzer 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] (0.07mmol, 18.1mg) and the L12 bidentate phosphite ester ligand of 0.014mmol, and 70mL dry toluene, connect gas tube, after replacing gas reactor three times with synthetic gas (hydrogen: carbon monoxide=1:1), stir with the mechanical stirrer of electromagnetic drive, be heated to temperature 100 DEG C in still, passing into synthetic 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.
Comparative example 2
Be equipped with in manometric stainless steel autoclave to 200mL in air atmosphere and add [Rh (acac) (CO) 2] (0.07mmol, 18.1mg) and the L11 bidentate phosphite ester ligand of 0.14mmol, and 70mL dry toluene, connect gas tube, after replacing gas reactor three times with synthetic gas (hydrogen: carbon monoxide=1:1), stir with the mechanical stirrer of electromagnetic drive, be heated to temperature 100 DEG C in still, passing into synthetic 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.
Embodiment 1
Be equipped with in manometric stainless steel autoclave to 200mL in air atmosphere and add [Rh (acac) (CO) 2] (0.07mmol, 18.1mg) with the triphenylphosphine L1 monophosphorus ligand of 0.28mmol and the L12 bidentate phosphite ester ligand of 0.14mmol, and 70mL dry toluene, connect gas tube, after replacing gas reactor three times with synthetic gas (hydrogen: carbon monoxide=1:1), stir with the mechanical stirrer of electromagnetic drive, be heated to temperature 100 DEG C in still, passing into synthetic 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.
Embodiment 2
Be equipped with in manometric stainless steel autoclave to 200mL in air atmosphere and add [Rh (acac) (CO) 2] (0.07mmol, 18.1mg) with the triphenylphosphine L1 monophosphorus ligand of 0.28mmol and the L11 bidentate phosphite ester ligand of 0.14mmol, and 70mL dry toluene, connect gas tube, after replacing gas reactor three times with synthetic gas (hydrogen: carbon monoxide=1:1), stir with the mechanical stirrer of electromagnetic drive, be heated to temperature 100 DEG C in still, passing into synthetic 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
Embodiment 3
Be equipped with in manometric stainless steel autoclave to 200mL in air atmosphere and add [Rh (acac) (CO) 2] (0.07mmol, 18.1mg) with the L4 monophosphorus ligand of 0.28mmol and the L12 bidentate phosphite ester ligand of 0.14mmol, and 70mL dry toluene, connect gas tube, after replacing gas reactor three times with synthetic gas (hydrogen: carbon monoxide=1:1), stir with the mechanical stirrer of electromagnetic drive, be heated to temperature 100 DEG C in still, passing into synthetic 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.
Embodiment 4
Be equipped with in manometric stainless steel autoclave to 200mL in air atmosphere and add [Rh (acac) (CO) 2] (0.07mmol, 18.1mg) with the L2 monophosphorus ligand of 0.28mmol and the L12 bidentate phosphite ester ligand of 0.14mmol, and 70mL dry toluene, connect gas tube, after replacing gas reactor three times with synthetic gas (hydrogen: carbon monoxide=1:1), stir with the mechanical stirrer of electromagnetic drive, be heated to temperature 100 DEG C in still, passing into synthetic 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.
Embodiment 5
Be equipped with in manometric stainless steel autoclave to 200mL in air atmosphere and add [Rh (acac) (CO) 2] (0.07mmol, 18.1mg) with the L4 monophosphorus ligand of 0.28mmol and the L11 bidentate phosphite ester ligand of 0.14mmol, and 70mL dry toluene, connect gas tube, after replacing gas reactor three times with synthetic gas (hydrogen: carbon monoxide=1:1), stir with the mechanical stirrer of electromagnetic drive, be heated to temperature 100 DEG C in still, passing into synthetic 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.
2, hydroformylation reaction catalyzer 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] (0.07mmol, 18.1mg) with 1 of 0.14mmol, the L12 bidentate phosphite ester ligand of two (diphenylphosphine) propane L3 bidentate phosphine ligands of 3-and 0.14mmol, and 70mL dry toluene, connect gas tube, after replacing gas reactor three times with synthetic gas (hydrogen: carbon monoxide=1:1), stir with the mechanical stirrer of electromagnetic drive, be heated to temperature 100 DEG C in still, passing into synthetic 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.
Embodiment 7
Be equipped with in manometric stainless steel autoclave to 200mL in air atmosphere and add [Rh (acac) (CO) 2] (0.07mmol, 18.1mg) with BISBI ligand L 1 bidentate phosphine ligands of 0.14mmol and the L12 bidentate phosphite ester ligand of 0.14mmol, and 70mL dry toluene, connect gas tube, after replacing gas reactor three times with synthetic gas (hydrogen: carbon monoxide=1:1), stir with the mechanical stirrer of electromagnetic drive, be heated to temperature 100 DEG C in still, passing into synthetic 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 diastereomer, 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.
Embodiment 8
Be equipped with in manometric stainless steel autoclave to 200mL in air atmosphere and add [Rh (acac) (CO) 2] (0.07mmol, 18.1mg) with 1 of 0.14mmol, the L10 bidentate phosphite ester ligand of two (diphenylphosphine) butane L4 bidentate phosphine ligands of 4-and 0.14mmol, and 70mL dry toluene, connect gas tube, after replacing gas reactor three times with synthetic gas (hydrogen: carbon monoxide=1:1), stir with the mechanical stirrer of electromagnetic drive, be heated to temperature 100 DEG C in still, passing into synthetic 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.
Embodiment 9
Be equipped with in manometric stainless steel autoclave to 200mL in air atmosphere and add [Rh (acac) (CO) 2] (0.07mmol, 18.1mg) with 1 of 0.14mmol, the L10 bidentate phosphite ester ligand of two (diphenylphosphine) propane L3 bidentate phosphine ligands of 3-and 0.14mmol, and 70mL dry toluene, connect gas tube, after replacing gas reactor three times with synthetic gas (hydrogen: carbon monoxide=1:1), stir with the mechanical stirrer of electromagnetic drive, be heated to temperature 100 DEG C in still, passing into synthetic 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.
Embodiment 10
Be equipped with in manometric stainless steel autoclave to 200mL in air atmosphere and add [Rh (acac) (CO) 2] (0.07mmol, 18.1mg) with BISBI ligand L 1 bidentate phosphine ligands of 0.14mmol and the L10 bidentate phosphite ester ligand of 0.14mmol, and 70mL dry toluene, connect gas tube, after replacing gas reactor three times with synthetic gas (hydrogen: carbon monoxide=1:1), stir with the mechanical stirrer of electromagnetic drive, be heated to temperature 100 DEG C in still, passing into synthetic 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 diastereomer, 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.
3, hydroformylation reaction catalyzer is the mixture of complex catalyst I and complex catalyst II
Embodiment 11
Adopt the catalyzer 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.
4, the catalyzer of above-described embodiment and comparative example is used for the result of 1-butylene hydroformylation reaction
Be equipped with in manometric stainless steel autoclave to 200mL in air atmosphere and add catalyzer, replace gas reactor three times with synthetic gas, add 1-butylene raw material, be heated to temperature of reaction, the reaction pressure needed for maintenance, straight-through synthetic gas reacts.Reaction process condition and result as shown in table 1.
Table 1
By the above-mentioned reaction solution containing catalyzer under the atmosphere without synthetic gas or nitrogen protection, room temperature places 3 months, again carry out the hydroformylation reaction of 1-butylene: react with the catalyzer of comparative example 1 and 2, the just different ratio of the aldehyde product obtained is less than 2, and the selectivity of n-alkanal is less than 67%; And react with the catalyzer in embodiment, the just different ratio of product remains unchanged substantially, and the selectivity of n-alkanal is greater than 95%.
5, the thermal stability results of the catalyzer of above-described embodiment and comparative example
Be placed in reaction flask by above-mentioned according to fresh obtained rhodium complex catalyst, after falling air with nitrogen replacement, be warming up to 140 DEG C, 120 DEG C thermal treatment 24h.Pass through nuclear-magnetism 31p spectrum observation change of component situation.In table 2.
Table 2

Claims (10)

1. the method for a preparing aldehyde by alkene hydroformylation, 1-butylene, carbon monoxide and hydrogen are that 1:0.9 ~ 1.5:0.9 ~ 1.5 enter hydroformylation reaction device with mol ratio, temperature of reaction be 90 ~ 110 DEG C, reaction pressure is 1.5 ~ 2.0Mpa, the reaction times be 1 ~ 1.5h under with catalyst exposure, generate the product comprising aldehyde; Described catalyzer 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 arylidene;
(2) Y 1, Y 2, Z 1or Z 2for hydrogen, the tertiary butyl 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 arylidene;
(2) Y 1, Y 2, Z 1or Z 2for hydrogen, the tertiary butyl 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 described hydroformylation reaction device, the mol ratio of 1-butylene and rhodium is 1900 ~ 2050:1, and the mol ratio of phosphite ester ligand, Phosphine ligands, rhodium is 2:2:1 ~ 4:4:1, and described Phosphine ligands is at least one in monophosphorus ligand or biphosphine ligand.
2. the method for preparing aldehyde by alkene hydroformylation according to claim 1, is characterized in that described monophosphorus ligand has following structural formula:
3. the method for preparing aldehyde by alkene hydroformylation according to claim 1, is characterized in that described bidentate phosphite ester ligand has following structural formula:
4. the method for preparing aldehyde by alkene hydroformylation according to claim 1, is characterized in that the structure of described complex catalyst I is as follows:
5. the method for preparing aldehyde by alkene hydroformylation according to claim 1, is characterized in that described bidentate phosphine ligands has following structural formula:
6. the method for preparing aldehyde by alkene hydroformylation according to claim 1, is characterized in that the structure of described complex catalyst II is as follows:
7. the method for preparing aldehyde by alkene hydroformylation according to claim 1, is characterized in that complex catalyst I adds hot preparation by rhodium dicarbonyl acetylacetonate (I) and bidentate phosphite ester, monophosphorus ligand under synthetic 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 synthetic gas atmosphere; The mol ratio of rhodium dicarbonyl acetylacetonate (I) and bidentate phosphite ester, biphosphine ligand is 1:1-2:1-2.
8. the method for preparing aldehyde by alkene hydroformylation according to claim 1, is characterized in that in described catalyzer, 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 ~ 1000mg/L, in complex catalyst II, the concentration of rhodium is 10 ~ 1000mg/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.
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EP3438097A1 (en) * 2017-07-31 2019-02-06 Evonik Degussa GmbH Synthesis of 2-(4-(trifluoromethyl)phenyl)-4h-benzo[d][1,3]oxazin-4-one from 1-(4-trifluoromethylbenzoyl)-1h-benzotriazole by adding palladiumchloride (pdcl2) and biphephos (6,6'-[(3,3'-di-tert-butyl-5,5'-dimethoxy-1,1'-biphenyl-2,2'-diyl)bis(oxy)]bis(dibenzo[d,f][1,3,2]dioxaphosphepine)) as well as similar processes
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CN109456154A (en) * 2018-11-14 2019-03-12 成都欣华源科技有限责任公司 A method of fatty aldehyde is prepared by hydroformylation reaction
CN113698280A (en) * 2020-05-21 2021-11-26 中国石油化工股份有限公司 Olefin hydroformylation method
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