Phosphine ligand compounds, catalyst compositions for homogeneous hydroformylation reactions, and methods

Abstract

The present application relates to a kind of phosphine ligand compound, catalyst composition and method for homogeneous hydroformylation reaction.The phosphine ligand compound provided by the present application has the structure as shown in formula (A), wherein M1 is the group as shown in formula (I), M2 is the group as shown in formula (II), M3 is the group as shown in formula (III), and M4 is selected from alkyl group with or without substituent and alkoxy group with or without substituent.The catalyst composition provided by the present application includes rhodium metal compound and the phosphine ligand compound.Using the composition provided by the present application for homogeneous catalytic hydroformylation to prepare aldehyde can significantly improve the reactivity of hydroformylation reaction, and the composition has good recovery effect after the end of hydroformylation reaction, the separated catalyst can be recycled, reduce production cost, and be conducive to industrialized production application.

Description

TECHNICAL FIELD

[0001] The present application relates to a phosphine ligand compound, a catalyst composition and a method for homogeneous hydroformylation reaction. BACKGROUND

[0002] At present, the catalysts used in the industrial hydroformylation production process mainly include cobalt-based catalysts and rhodium-based catalysts. The process using the cobalt-based catalyst has harsh reaction conditions, poor selectivity, many side reactions, high energy consumption, and a complex cobalt recovery process, and the like, and the comprehensive economic and technical indicators are far from those of the process using the rhodium-based catalyst. Therefore, the rhodium-based catalyst gradually becomes the dominant catalyst for industrial hydroformylation reaction. However, the rhodium catalyst is expensive, which increases the production cost of the product to some extent. How to further increase the reaction activity and product selectivity of the rhodium-based catalyst to reduce the use amount of the rhodium catalyst, and to recycle and reuse the catalyst as much as possible is one of the technical problems to be solved in the field at present.

[0003] US8710276 discloses a cyclohexane diphenyl phosphine ligand represented by CHDP. Although the ligand increases the stability of the catalyst, the N / I selectivity is obviously reduced. In addition, CN101293818 discloses a hydroformylation method. By carrying out two-stage reaction on the mixed butene hydroformylation, the difference in reaction of the two kinds of olefins is well solved, and the utilization rate of the olefins is improved. However, the method is only limited to the hydroformylation of low-carbon chain olefins.

[0004] In terms of catalyst recovery, a two-phase catalytic process (especially oil-water two-phase catalysis) has been developed. However, due to the poor solubility of high-carbon olefins with more than 6 carbon atoms in water (some are even completely insoluble), the mass transfer rate is slow, which affects the reaction activity and limits the application of the oil-water two-phase catalytic process in the industrial production of high-carbon olefin hydroformylation. SUMMARY

[0005] In order to solve the above technical problems, the inventors of the present application have found a phosphine ligand compound, a catalyst composition and a method for hydroformylation reaction comprising the compound. The composition provided by the present application has high activity in the hydroformylation reaction and can be efficiently separated and recovered.

[0006] In a first aspect, the present application provides a phosphine ligand compound, which has a structure as shown in formula (A),

[0007]

[0008] In formula (A), M1 is a group represented by formula (I), and M2 is a group represented by formula (II), wherein R1, R2, R3, and R4 are each independently selected from an N-containing heterocycle with or without a substituent, a benzene ring with or without a substituent, and a hydrocarbon group containing a benzene ring, p and q are each independently 0 or 1, and optionally, R1, R2, p, and / or R3, R4, p are linked to additional O to form a ring;

[0009] M3 is a group represented by formula (III), wherein R1' and R2' are independently selected from hydrogen, an alkyl group with or without a substituent, and an alkoxy group with or without a substituent, and m and n are each independently a natural number of 1 to 200;

[0010] M4 is selected from an alkyl group with or without a substituent and an alkoxy group with or without a substituent;

[0011] R 11 -R 16 are each independently selected from hydrogen, an alkyl group with or without a substituent, and an alkoxy group with or without a substituent.

[0012] According to some embodiments of the present application, R1, R2, R3, and R4 are each independently selected from an N-containing five-membered ring, a six-membered ring, or a benzo-heterocycle.

[0013] According to some embodiments of the present application, R1, R2, R3, and R4 are each independently selected from wherein R X and R X’ are each independently selected from hydrogen, a C1-C6 hydrocarbon group, a C1-C6 alkoxy group, a C1-C6 alkanoyl group, a C1-C6 ester group, a halogen, or a cyano group. 10 10 10 10

[0014] According to some embodiments of the present application, R1, R2, R3, and R4 are each independently selected from wherein R X and R X’ are each independently selected from hydrogen, a C1-C6 hydrocarbon group, a C1-C6 alkoxy group, a C1-C6 alkanoyl group, a C1-C6 ester group, a halogen, or a cyano group.

[0015] According to some embodiments of the present application, the halogen is selected from fluorine, chlorine, bromine, and iodine.

[0016] According to some embodiments of the present application, m and n are each independently a natural number of 5 to 200.

[0017] ​​​​According to some embodiments of the application, m, n are each independently 1, 3, 5, 10, 15, 20, 50, 100, 150, 200 and any value therebetween.

[0018] According to some embodiments of the application, R1' and R2' are each independently selected from the group consisting of hydrogen, C1-C6 alkyl with or without substituents and C1-C6 alkoxy with or without substituents. 10 alkyl with or without substituents and C1-C4 alkoxy with or without substituents. 10 alkyl with or without substituents and C1-C4 alkoxy with or without substituents.

[0019] According to some embodiments of the application, R1' and R2' are each independently selected from the group consisting of hydrogen, C1-C6 alkyl with or without substituents and C1-C6 alkoxy with or without substituents.

[0020] According to some embodiments of the application, R1' and R2' are each independently selected from the group consisting of hydrogen, C1-C4 alkyl with or without substituents and C1-C4 alkoxy with or without substituents.

[0021] According to some embodiments of the application, R1' and R2' are each independently selected from the group consisting of C1-C6 alkyl.

[0022] According to some embodiments of the application, R1' and R2' are each independently selected from the group consisting of C1-C4 alkyl.

[0023] In the present application, * in formula (I), formula (II), formula (III) indicates the attachment of the group in formula (A).

[0024] According to some embodiments of the application, M4 is selected from the group consisting of C1-C6 alkyl with or without substituents and C1-C6 alkoxy with or without substituents. 10 alkyl with or without substituents and C1-C4 alkoxy with or without substituents. 10 alkyl with or without substituents and C1-C4 alkoxy with or without substituents.

[0025] According to some embodiments of the application, M4 is selected from the group consisting of C1-C6 alkyl with or without substituents and C1-C6 alkoxy with or without substituents.

[0026] According to some embodiments of the application, M4 is selected from the group consisting of methyl, ethyl, n-propyl, i-propyl, n-butyl, t-butyl, i-butyl, n-pentyl, i-pentyl, n-hexyl, n-heptyl, methoxy, ethoxy, n-propoxy, i-propoxy, n-butoxy, t-butoxy, i-butoxy, n-pentoxy, i-pentoxy, n-hexoxy and n-heptoxy.

[0027] According to some embodiments of the application, R 11 -R 16 are each independently selected from the group consisting of hydrogen, C1-C6 alkyl with or without substituents and C1-C6 alkoxy with or without substituents. 10 alkyl with or without substituents and C1-C4 alkoxy with or without substituents. 10 alkyl with or without substituents and C1-C4 alkoxy with or without substituents.

[0028] According to some embodiments of the present application, R 11 -R 16 each independently selected from the group consisting of hydrogen, C1-C6 alkyl with or without substituents, and C1-C6 alkoxy with or without substituents.

[0029] According to some embodiments of the present application, R 11 -R 16 each independently selected from the group consisting of hydrogen, methyl, ethyl, n-propyl, i-propyl, n-butyl, t-butyl, i-butyl, n-pentyl, i-pentyl, n-hexyl, n-heptyl, methoxy, ethoxy, n-propoxy, i-propoxy, n-butoxy, t-butoxy, i-butoxy, n-pentoxy, i-pentoxy, n-hexoxy, and n-heptoxy.

[0030] According to some embodiments of the present application, R 11 -R 16 each independently selected from the group consisting of hydrogen, C1-C4 alkyl with or without substituents, and C1-C4 alkoxy with or without substituents.

[0031] According to some embodiments of the present application, the substituents are selected from the group consisting of halogen, C1-C6 alkyl, and C1-C6 alkoxy. 10 alkyl, and C1-C 10 alkoxy.

[0032] According to some embodiments of the present application, the substituents are selected from the group consisting of halogen, C1-C6 alkyl, and C1-C6 alkoxy.

[0033] According to preferred embodiments of the present application, the substituents are selected from the group consisting of halogen, C1-C4 alkyl, and C1-C4 alkoxy.

[0034] According to some embodiments of the present application, in the substituents, the halogen is selected from the group consisting of fluorine, chlorine, bromine, and iodine.

[0035] According to some embodiments of the present application, in the substituents, the C1-C 10 alkyl is selected from the group consisting of methyl, ethyl, n-propyl, i-propyl, n-butyl, t-butyl, i-butyl, n-pentyl, i-pentyl, n-hexyl, and n-heptyl.

[0036] According to some embodiments of the present application, in the substituents, the C1-C 10 alkoxy is selected from the group consisting of methoxy, ethoxy, n-propoxy, i-propoxy, n-butoxy, t-butoxy, i-butoxy, n-pentoxy, i-pentoxy, n-hexoxy, and n-heptoxy.

[0037] According to the present application, in formula (I), when there is no additional O, R1, R2, P are not in a ring, i.e., when there is an additional O, R1, R2, P are in a ring with O, i.e.

[0038] According to the present application, in formula (II), R1, R2, P do not form a ring when there is no additional O, and R3, R4, P form a ring with O when there is an additional O.

[0039] According to some embodiments of the present application, M1, M2 are each independently selected from

[0040] According to some embodiments of the present application, the phosphine ligand compound has a structure as shown in formula (B),

[0041]

[0042] In formula (B), R1, R2, R3, and R4 are each independently selected from a N-containing heterocycle with or without a substituent, a benzene ring with or without a substituent, and a benzene ring-containing hydrocarbon group;

[0043] R1' and R2' are independently selected from hydrogen, an alkyl group with or without a substituent, and an alkoxy group with or without a substituent, and m, n are each independently a natural number of 1-200;

[0044] R5 is selected from an alkyl group with or without a substituent, and an alkoxy group with or without a substituent;

[0045] R 11 -R 16 are each independently selected from hydrogen, an alkyl group with or without a substituent, and an alkoxy group with or without a substituent.

[0046] According to some embodiments of the present application, in formula (B), R1, R2, R3, and R4 are each independently selected from a five-membered ring, a six-membered ring, or a benzoheterocycle.

[0047] According to some embodiments of the present application, in formula (B), R1, R2, R3, and R4 are each independently selected from wherein R X and R X’ are each independently selected from hydrogen, a C1-C 10 hydrocarbon group, a C1-C 10 alkoxy group, a C1-C 10 alkanoyl group, a C1-C 10 ester group, a halogen, or a cyano group.

[0048] According to some embodiments of the present application, in formula (B), R1, R2, R3, and R4 are each independently selected from wherein R X and R X’each independently selected from hydrogen, C1-C6 alkyl, C1-C6 alkoxy, C1-C6 alkanoyl, C1-C6 ester, halogen or cyano.

[0049] According to some embodiments of the present application, in formula (B), the halogen is selected from fluorine, chlorine, bromine and iodine.

[0050] According to some embodiments of the present application, in formula (B), m, n are each independently a natural number from 5 to 200.

[0051] According to some specific embodiments of the present application, in formula (B), m, n are each independently 1, 3, 5, 10, 15, 20, 50, 100, 150, 200 and any value therebetween.

[0052] According to some embodiments of the present application, in formula (B), R1' and R2' are each independently selected from hydrogen, C1-C6 alkyl with or without substituent and C1-C6 alkoxy with or without substituent. 10 alkyl with or without substituent and C1-C4 alkoxy with or without substituent. 10 alkyl with or without substituent and C1-C4 alkoxy with or without substituent.

[0053] According to some embodiments of the present application, in formula (B), R1' and R2' are each independently selected from hydrogen, C1-C6 alkyl with or without substituent and C1-C6 alkoxy with or without substituent.

[0054] According to some embodiments of the present application, in formula (B), R1' and R2' are each independently selected from hydrogen, C1-C4 alkyl with or without substituent and C1-C4 alkoxy with or without substituent.

[0055] According to some embodiments of the present application, in formula (B), R1' and R2' are each independently selected from C1-C6 alkyl.

[0056] According to some embodiments of the present application, in formula (B), R1' and R2' are each independently selected from C1-C4 alkyl.

[0057] According to some embodiments of the present application, in formula (B), R5 is selected from C1-C6 alkyl with or without substituent and C1-C6 alkoxy with or without substituent. 10 alkyl with or without substituent and C1-C4 alkoxy with or without substituent. 10 alkyl with or without substituent and C1-C4 alkoxy with or without substituent.

[0058] According to some embodiments of the present application, in formula (B), R5 is selected from C1-C6 alkyl with or without substituent and C1-C6 alkoxy with or without substituent.

[0059] According to some embodiments of the application, in formula (B), R5is selected from the group consisting of methyl, ethyl, n-propyl, i-propyl, n-butyl, t-butyl, i-butyl, n-pentyl, i-pentyl, n-hexyl, n-heptyl, methoxy, ethoxy, n-propoxy, i-propoxy, n-butoxy, t-butoxy, i-butoxy, n-pentoxy, i-pentoxy, n-hexoxy and n-heptoxy.

[0060] According to some embodiments of the application, in formula (B), R 11 -R 16 each independently is selected from the group consisting of hydrogen, C1-C6alkyl with or without substituents and C1-C6alkoxy with or without substituents. 10 alkyl and C1-C4alkoxy with or without substituents. 10 alkoxy.

[0061] According to some embodiments of the application, in formula (B), R 11 -R 16 each independently is selected from the group consisting of hydrogen, C1-C6alkyl with or without substituents and C1-C6alkoxy with or without substituents.

[0062] According to some embodiments of the application, in formula (B), R 11 -R 16 each independently is selected from the group consisting of hydrogen, methyl, ethyl, n-propyl, i-propyl, n-butyl, t-butyl, i-butyl, n-pentyl, i-pentyl, n-hexyl, n-heptyl, methoxy, ethoxy, n-propoxy, i-propoxy, n-butoxy, t-butoxy, i-butoxy, n-pentoxy, i-pentoxy, n-hexoxy and n-heptoxy.

[0063] According to some embodiments of the application, in formula (B), R 11 -R 16 each independently is selected from the group consisting of hydrogen, C1-C4alkyl with or without substituents and C1-C4alkoxy with or without substituents.

[0064] According to some embodiments of the application, in formula (B), the substituents are selected from the group consisting of halogen, C1-C6alkyl and C1-C6alkoxy, preferably from the group consisting of halogen, C1-C4alkyl and C1-C4alkoxy. 10 alkyl and C1-C4alkoxy. 10 alkoxy.

[0065] According to some embodiments of the application, in the substituents, the halogen is selected from the group consisting of fluorine, chlorine, bromine and iodine; the C1-C6alkyl is selected from the group consisting of methyl, ethyl, n-propyl, i-propyl, n-butyl, t-butyl, i-butyl, n-pentyl, i-pentyl, n-hexyl and n-heptyl; and the C1-C6alkoxy is selected from the group consisting of methoxy, ethoxy, n-propoxy, i-propoxy, n-butoxy, t-butoxy, i-butoxy, n-pentoxy, i-pentoxy, n-hexoxy and n-heptoxy. 10 alkyl and C1-C4alkoxy. 10The alkoxy group is selected from the group consisting of methoxy, ethoxy, n-propoxy, iso-propoxy, n-butoxy, t-butoxy, iso-butoxy, n-pentoxy, iso-pentoxy, n-hexoxy and n-heptoxy.

[0066] In the second aspect, the present application provides a catalyst composition for preparing aldehydes by hydroformylation, comprising the phosphine ligand compound of the first aspect and a rhodium metal compound.

[0067] According to some embodiments of the present application, the structure of the rhodium metal compound is shown in formula (B):

[0068] Rh (L 1 ) x (L 2 ) y (L 3 ) z (B)

[0069] wherein L 1 , L 2 and L 3 are each independently selected from the group consisting of hydrogen, CO, halogen, triphenylphosphine and acetylacetone; x, y and z are each independently selected from an integer from 0 to 5, and at least one of x, y and z is not 0.

[0070] According to some embodiments of the present application, the halogen is selected from the group consisting of fluorine, chlorine, bromine and iodine, and preferably is chlorine.

[0071] According to some embodiments of the present application, the molar ratio of the phosphine ligand to the rhodium metal compound is 0.5:1-200:1, for example, can be 0.5:1, 1:1, 5:1, 10:1, 20:1, 50:1, 100:1, 120:1, 150:1, 180:1, 200:1 and any value therebetween, in terms of metal rhodium.

[0072] According to some embodiments of the present application, the molar ratio of the phosphine ligand to the rhodium metal compound is 1:1-100:1, in terms of metal rhodium.

[0073] According to preferred embodiments of the present application, the molar ratio of the phosphine ligand to the rhodium metal compound is 2:1-50:1, in terms of metal rhodium.

[0074] The composition provided by the present application, introducing the bis-phosphine ligand with polyethylene glycol amino unit, in combination with the rhodium metal compound, can improve the reactivity of the hydroformylation reaction, and the composition has good recovery effect after the hydroformylation reaction, and the separated catalyst can be recycled.

[0075] The composition provided by the present application can significantly improve the reactivity when used in the preparation of aldehydes by homogeneous catalytic hydroformylation, and can also be efficiently separated and recovered. Therefore, in a third aspect, the present application provides a method for preparing aldehydes by homogeneous hydroformylation, which comprises contacting an olefin raw material and the catalyst composition according to the second aspect with carbon monoxide and hydrogen in the presence of an organic solvent to generate aldehydes.

[0076] According to some embodiments of the present application, the olefin is a C2-C 12 olefin.

[0077] According to preferred embodiments of the present application, the olefin is a C5-C 12 olefin.

[0078] According to further preferred embodiments of the present application, the olefin is a C6-C 10 olefin.

[0079] According to some embodiments of the present application, the hydroformylation reaction is carried out in an organic solvent, and the organic solvent comprises at least one of aliphatic hydrocarbon compounds and aromatic hydrocarbon compounds.

[0080] According to some embodiments of the present application, the aliphatic hydrocarbon compounds comprise at least one of aldehydes with 4-10 carbon atoms, ketones with 4-10 carbon atoms, and alkanes with 4-10 carbon atoms. 10 10 10

[0081] According to some embodiments of the present application, the aromatic hydrocarbon compounds comprise at least one of acetylbenzene, toluene, xylene, and chlorobenzene.

[0082] According to some embodiments of the present application, the amount of the rhodium metal compound added is 0.1-10 mmol / L in terms of metal rhodium, for example, can be 0.1 mmol / L, 0.25 mmol / L, 0.5 mmol / L, 1 mmol / L, 1.5 mmol / L, 2 mmol / L, 3 mmol / L, 4 mmol / L, 5 mmol / L, 6 mmol / L, 7 mmol / L, 8 mmol / L, 9 mmol / L, 10 mmol / L, and any value therebetween.

[0083] According to some embodiments of the present application, the amount of the rhodium metal compound added is 0.2-5 mmol / L in terms of metal rhodium.

[0084] ​​​According to some embodiments of the present application, the molar ratio of the olefin to the rhodium in the catalyst composition is (500-100000): 1, for example, it can be 500: 1, 1000: 1, 2000: 1, 5000: 1, 8000: 1, 10000: 1, 20000: 1, 50000: 1, 80000: 1, 100000: 1, and any value therebetween.

[0085] According to preferred embodiments of the present application, the molar ratio of the olefin to the rhodium in the catalyst composition is (1000-10000): 1.

[0086] According to further preferred embodiments of the present application, the molar ratio of the olefin to the rhodium in the catalyst composition is (2000-8000): 1.

[0087] According to some embodiments of the present application, the temperature of the contacting is 50°C-120°C, for example, it can be 50°C, 55°C, 60°C, 65°C, 70°C, 75°C, 80°C, 85°C, 90°C, 100°C, 110°C, 120°C, and any value therebetween.

[0088] According to preferred embodiments of the present application, the temperature of the contacting is 80°C-100°C.

[0089] According to some embodiments of the present application, the pressure of the contacting is 0.1 MPa-10 MPa, for example, it can be 0.1 MPa, 0.5 MPa, 1.0 MPa, 1.5 MPa, 2.0 MPa, 2.5 MPa, 3.0 MPa, 3.5 MPa, 4.0 MPa, 4.5 MPa, 5.0 MPa, 6.0 MPa, 7.0 MPa, 8.0 MPa, 9.0 MPa, 10 MPa, and any value therebetween.

[0090] According to preferred embodiments of the present application, the pressure of the contacting is 0.1 MPa-4 MPa.

[0091] According to some embodiments of the present application, the time of the contacting is 1 hour-8 hours.

[0092] According to preferred embodiments of the present application, the time of the contacting is 2 hours-5 hours.

[0093] According to some embodiments of the present application, the method further comprises: prior to the contacting, pre-mixing the olefin with the catalyst composition.

[0094] According to some embodiments of the present application, the pre-mixing time is less than 10 min.

[0095] According to a preferred embodiment of the present application, the premixing time is less than 5 min.

[0096] According to a further preferred embodiment of the present application, the premixing time is 1-3 min.

[0097] The present application improves the reaction activity of the hydroformylation reaction by introducing a phosphine ligand containing polyethylene glycol amino in combination with a rhodium metal compound, and the composition has good recovery effect after the hydroformylation reaction, the separated catalyst can be recycled, the production cost is reduced, and it is beneficial to industrialized production and application. DETAILED DESCRIPTION

[0098] The following examples are only used to illustrate the present application in detail, but it should be understood that the scope of the present application is not limited to these examples.

[0099] Preparation Example 1

[0100] The synthetic route of the phosphine ligand containing polyethylene glycol amino used in Example 1 is as follows:

[0101]

[0102] Preparation of Compound I:

[0103] Dissolve methyl-pentaethylene glycol-bromide (48 mmol) in ammonia-methanol solution (3 mol / L), and after complete dissolution, warm to 40°C, and react for 12 hours. After the reaction is completed, remove the solvent, dissolve the residue in dichloromethane, filter, wash the filter cake with dichloromethane, combine the filtrates, adjust the pH of the filtrate to about 4.0, stand to separate the layers, separate the aqueous phase, and wash the aqueous phase with dichloromethane. Then slowly add saturated sodium carbonate solution to the aqueous phase to adjust the pH of the solution to about 9.0, extract with dichloromethane three times, combine the organic phases, dry with anhydrous magnesium sulfate, filter, and concentrate under reduced pressure to obtain Compound I.

[0104] Preparation of Compound II:

[0105] Under nitrogen protection, add 9,9-dimethylxanthene (5.7 mmol), tert-butyl chloride (5 mmol), dichloromethane (100 mL), and ferric chloride (0.6 mmol) to a 250 ml three-necked flask, and stir at room temperature for 15 hours. After the reaction is completed, add water to the reaction solution to terminate the reaction, pour the mixture into a separatory funnel, stand to separate the layers, collect the organic phase, dry the organic phase with anhydrous magnesium sulfate, and remove the organic solvent to obtain Compound II.

[0106] Preparation of Compound III:

[0107] To a solution of compound II (4 mmol) in acetic anhydride was added Br2(5 mmol) in glacial acetic acid at 0 °C. After the addition was complete, the solution was allowed to warm to room temperature and stirred for 2 h. The solution was then poured into excess ice water and the precipitate was collected by filtration. The white solid was washed with sodium bisulfate (10% aqueous solution) and water and dried under vacuum to give compound III.

[0108] Preparation of compound IV:

[0109] Compound I (3 mmol) and compound III (2 mmol) were added to a round bottom flask containing dimethyl sulfoxide under nitrogen protection. After stirring to homogeneity, tetrabutylammonium bromide and potassium tert-butoxide were added and the temperature was raised to 130 °C. The reaction was monitored by TLC and upon completion, the temperature was lowered and the solution was diluted with water. The solution was allowed to stand and separate into layers. The organic layer was collected and the aqueous layer was extracted with ethyl acetate. The organic layers were combined and washed with saturated brine, dried over anhydrous magnesium sulfate, filtered and concentrated under vacuum. Compound IV was isolated by silica gel column chromatography (eluent: ethyl acetate: hexane = 7:1).

[0110] Preparation of compound V:

[0111] Compound IV (4.3 mmol) was dissolved in glacial acetic acid and Br2(15.6 mmol) was added dropwise over a period of time. The mixture was stirred at 50 °C for 20 h, cooled to room temperature and water was added to the reaction flask. K2CO3solution was added at a low rate. The mixture was extracted with CH2Cl2and the organic layer was dried over anhydrous magnesium sulfate. The crude material was filtered and recrystallized from tetrahydrofuran and ethanol to give compound V.

[0112] Preparation of phosphine ligand containing polyethylene glycol amino group:

[0113] An amount of intermediate V (13.3 mmol) was placed in a reaction vessel with dry THF under nitrogen protection at -50 °C and 2.5 M n-butyllithium in hexane was added dropwise. After the addition was complete, the mixture was stirred at -50 °C for 2 h and a precipitate was formed. The temperature was lowered to -70 °C and a solution of compound VI (30 mmol) in toluene was added. The mixture was stirred for 1 h and the temperature was raised to room temperature. The mixture was then evaporated under reduced pressure and the residue was dissolved in dichloromethane and hexane was added with stirring. The resulting solid was recrystallized from hot methanol to give the target product. 1 H NMR (400 MHz, CDC13): δ = 7.36 (s, 1H), 7.28 (m, 8H), 7.25 (d, J = 2.4 Hz, 1H), 6.82 (s, 1H), 6.71 (s, 1H), 6.27 (m, 8H), 4.18 (t, 3J = 6.2 Hz, 4H), 3.54 - 3.73 (m, 36H), 3.30 (s, 6H), 1.72 (s, 6H), 1.35 (s, 9H).

[0114] Preparation Example 2

[0115] The synthetic route of the phosphine ligand used in Comparative Example 1 is as follows:

[0116]

[0117] A certain amount of 4,5-dibromo-2,7-di-tert-butyl-9,9-dimethyloxyxanthene and dry THF were put into a reaction kettle at -50°C under nitrogen protection, 2.5M n-butyllithium hexane solution was added dropwise, after the dropwise addition was completed, stirring was continued at -50°C for 2h, and a precipitate was formed. The temperature was lowered to -70°C, a toluene solution of compound IV was added, stirred for 1h, the temperature was raised to room temperature, then evaporated under reduced pressure, the evaporation residue was dissolved in dichloromethane, hexane was added again under stirring. The generated solid was recrystallized from hot methanol to obtain the target product. 1 H NMR (400 MHz, CDC13): δ = 7.36 (s, 2H), 7.28 (m, 8H), 7.25 (s, 2H), 6.27 (m, 8H), 1.72 (s, 6H), 1.35 (s, 18H).

[0118] Example 1

[0119] The acetylacetone dicarbonyl rhodium was used as the main catalyst, the phosphine ligand containing polyethylene glycol amino prepared in Preparation Example 1 (wherein m = n = 5) was used as the ligand, the molar ratio of the main catalyst (calculated by rhodium) to the ligand was 1:5, the molar ratio of 1-octene:Rh was 10000:1, and the concentration of Rh was 1.6 mmol / L. The hydrogen formylation reaction device used a 50 mL high-pressure kettle reaction device. After the closed reaction system was purged with N2, it was replaced several times with synthesis gas (CO:H2=1:1) and the temperature control system of the system was opened to maintain the temperature of the whole system at 80°C, the vent valve was opened, then the toluene solution of the catalyst was quickly added into the reaction kettle, then 1-octene was added into the reaction kettle. The vent valve was closed, pre-mixed and stirred for 2 min, the pressure was set to 2 MPa, synthesis gas (CO:H2=1:1) was introduced thereinto for reaction, the reaction was carried out for 2h, after cooling to below 20°C, the pressure was released, the reaction liquid was discharged into a separator through the bottom valve of the high-pressure kettle, the lower layer was the catalyst layer, and the upper layer was the organic product layer. The organic product layer was analyzed by gas chromatography, the conversion rate of 1-octene was 94.7%, the aldehyde selectivity was 94.9%, and the normal / iso ratio (linear aldehyde / branched aldehyde) was 213. ICP analysis showed that the content of metallic rhodium in the organic product layer was 2.36 ppm.

[0120] Example 2

[0121] The experimental method is the same as Example 1, except that the phosphine ligand structure is changed (compound of structure (A) where m = n = 3, and the rest of the structure remains unchanged), and the rest of the experimental conditions remain unchanged. The conversion of 1-octene is 92.0%, the selectivity of aldehyde is 93.4%, the normal / iso ratio (linear aldehyde / branched aldehyde) is 149, and the content of metal rhodium in the organic product layer is 44.3 ppm by ICP analysis.

[0122] Example 3

[0123] The experimental method is the same as Example 1, except that the phosphine ligand structure containing polyethylene glycol amino is changed (compound of structure (A) where m = n = 1, and the rest of the structure remains unchanged), and the rest of the experimental conditions remain unchanged. The conversion of 1-octene is 90.7%, the selectivity of aldehyde is 91.4%, the normal / iso ratio (linear aldehyde / branched aldehyde) is 111, and the reaction solution does not have obvious stratification in the separator.

[0124] Example 4

[0125] The experimental method of Example 4 is the same as Example 1, except that the molar ratio of the main catalyst (calculated as rhodium) to the ligand in the solution is changed to 1:2, and the rest of the experimental conditions remain unchanged. The conversion of 1-octene is 82.3%, the selectivity of aldehyde is 70.5%, the normal / iso ratio (linear aldehyde / branched aldehyde) is 91, and the content of metal rhodium in the organic product layer is 3.11 ppm by ICP analysis.

[0126] Example 5

[0127] The experimental method of Example 5 is the same as Example 1, except that the molar ratio of the main catalyst (calculated as rhodium) to the ligand in the solution is changed to 1:30, and the rest of the experimental conditions remain unchanged. The conversion of 1-octene is 95.01%, the selectivity of aldehyde is 96.0%, the normal / iso ratio (linear aldehyde / branched aldehyde) is 228, and the content of metal rhodium in the organic product layer is 2.31 ppm by ICP analysis.

[0128] Example 6

[0129] The experimental method of Example 6 is the same as Example 1, except that the concentration of rhodium in the solution is changed to 0.25 mmol / L, and the rest of the experimental conditions remain unchanged. The conversion of 1-octene is 68.3%, the selectivity of aldehyde is 86.7%, the normal / iso ratio (linear aldehyde / branched aldehyde) is 170, and the content of metal rhodium in the organic product layer is 2.07 ppm by ICP analysis.

[0130] Example 7

[0131] The experimental method of Example 7 is the same as that of Example 1, except that the concentration of rhodium in the solution is changed to 2.5 mmol / L, and the other experimental conditions remain unchanged. The conversion of 1-octene is 95.8%, the selectivity of aldehyde is 96.4%, the normal / iso ratio (straight-chain aldehyde / branched-chain aldehyde) is 212, and the content of metallic rhodium in the organic product layer is 2.15 ppm by ICP analysis.

[0132] Comparative Example 1

[0133] The experimental method is the same as that of Example 1, except that the phosphine ligand added is the compound prepared in Preparation Example 2 without the polyethylene glycol amino side chain group, and the other experimental conditions remain unchanged. The test results are as follows: the conversion of 1-octene is 99.0%, the selectivity of aldehyde is 95.2%, the normal / iso ratio (straight-chain aldehyde / branched-chain aldehyde) is 88, and the reaction solution does not separate into layers in the separator.

[0134] As can be seen from the comparative example, the phosphine ligand without a side chain cannot be separated by cooling after the reaction is completed.

[0135] It should be noted that the above-described examples are used to explain the present application and do not constitute any limitation on the present application. The present application is described by referring to the above-described typical examples, but it should be understood that all the words therein are descriptive and explanatory words, rather than limiting words. Modifications can be made to the present application within the scope of the claims of the present application, and the present application can be revised without departing from the scope and spirit of the present application. Although the present application described therein relates to specific methods, materials and examples, it does not mean that the present application is limited to the specific examples disclosed therein, on the contrary, the present application can be extended to all other methods and applications with the same function.

Claims

1. A catalyst composition for use in a homogeneous hydroformylation reaction, characterized in that, The phosphine ligand compound has a structure as shown in formula (A), and the rhodium metal compound has a structure as shown in formula (B), Formula (A) Formula (I) Formula (II) Formula (III) In formula (A), M1is a group of formula (I) and M2is a group of formula (II), wherein R1, R2, R3and R4are each independently selected from , wherein R X and R X’ are each independently selected from hydrogen, C1-C 10 alkyl, C1-C 10 alkoxy; M3 is a group as shown in formula (III), wherein R1' and R2' are independently selected from hydrogen, an alkyl group with or without substituent, and an alkoxy group with or without substituent, and m and n are each independently a natural number of 3-20; M4 is selected from an alkyl group with or without substituent, and an alkoxy group with or without substituent; R 11 -R 16 each independently is selected from the group consisting of hydrogen, alkyl with or without substituents, and alkoxy with or without substituents; said substituents are selected from the group consisting of halogen, Ci-C 10 alkyl and Ci-C 10 alkoxy; The rhodium metal compound has a structure as shown in formula (B): Rh(L 1 ) x (L 2 ) y (L 3 ) z (B) wherein L 1 , L 2 and L 3 are each independently selected from the group consisting of hydrogen, CO, halogen, triphenylphosphine and acetylacetone; x, y and z are each independently selected from an integer from 0 to 5, at least one of x, y and z being different from 0. The molar ratio of the phosphine ligand to the rhodium metal compound is 5:1-100:1, calculated based on the metal rhodium; The starting olefin for the homogeneous hydroformylation reaction is a C6-C 10 olefin.

2. The catalyst composition of claim 1, wherein, R1and R2are each independently selected from the group consisting of hydrogen, C1-C20alkyl with or without substituents, 10 C1-C20alkyl with or without substituents, 10 C1-C20alkyl with or without substituents, m, n are each independently a natural number of 5-20; and / or M4 is selected from C1-C1 cells with or without substituents. 10 Alkyl groups and C1-C groups with or without substituents 10 alkoxy; and / or R 11 -R 16 each independently is selected from the group consisting of hydrogen, C1-C4alkyl with or without substituents, and C1-C4alkoxy with or without substituents. 10 each independently is selected from the group consisting of hydrogen, C1-C4alkyl with or without substituents, and C1-C4alkoxy with or without substituents. 10 each independently is selected from the group consisting of hydrogen, C1-C4alkyl with or without substituents, and C1-C4alkoxy with or without 3. The catalyst composition of claim 1, wherein, said halogen is selected from chlorine, bromine and iodine; said C1-C 10 alkyl is selected from methyl, ethyl, n-propyl, i-propyl, n-butyl, t-butyl, i-butyl, n-pentyl, i-pentyl, n-hexyl and n-heptyl; said C1-C 10 alkoxy is selected from methoxy, ethoxy, n-propoxy, i-propoxy, n-butoxy, t-butoxy, i-butoxy, n-pentoxy, i-pentoxy, n-hexoxy and n-heptoxy.

4. The catalyst composition of any one of claims 1-3, wherein, M1, M2are each independently .

5. A process for a homogeneous hydroformylation reaction comprising contacting a C6-Ci8 olefinic feedstock and a catalyst composition according to any one of claims 1-4 with carbon monoxide and hydrogen in the presence of an organic solvent to produce an aldehyde. 10 5. A process for a homogeneous hydroformylation reaction comprising contacting a C6-Ci8 olefinic feedstock and a catalyst composition according to any one of claims 1-4 with carbon monoxide and hydrogen in the presence of an organic solvent to produce an aldehyde.

6. The method of claim 5, wherein, The organic solvent comprises at least one of an aliphatic hydrocarbon compound and an aromatic hydrocarbon compound; and / or The addition amount of the rhodium metal compound is 0.1-10 mmol / L, calculated based on the metal rhodium; and / or The C6-C 10 The molar ratio of rhodium in the olefin and the catalyst composition is (500-100000):1; and / or The temperature of the contacting is 50-120°C; and / or The pressure of the contacting is 0.1-10 MPa; and / or The time of the contacting is 1-8 hours.

7. The method of claim 6, wherein, said aliphatic hydrocarbon compounds comprise at least one of C4-C 10 aldehydes, C4-C 10 ketones and C4-C 10 alkanes, and / or said aromatic hydrocarbon compounds comprise at least one of acetophenone, toluene, xylene and chlorobenzene; and / or, The addition amount of the rhodium metal compound is 0.2-5 mmol / L, calculated based on the metal rhodium; and / or The C6-C 10 The molar ratio of rhodium in the olefin and the catalyst composition is (1000-10000):1; and / or The temperature of the contacting is 80-100°C; and / or The pressure of the contacting is 0.1-4 MPa; and / or The time of the contacting is 2-5 hours.

8. The method of claim 7, wherein, said C6-Ci8-aryl is unsubstituted or substituted by one or more halogen, Ci-C4-alkyl, Ci-C4-haloalkyl, Ci-C4-alkoxy, Ci-C4-haloalkoxy, nitro or cyano; 10 the molar ratio of olefin to rhodium in the catalyst composition is (2000-8000):

9. The method according to any one of claims 5-8, characterized in that, The method also includes, prior to the contacting, the C6-C 10 The olefins are pre-mixed with the catalyst composition.

10. The method of claim 9, wherein, The premixing time is less than 10 min.

11. The method of claim 10, wherein, The premixing time is less than 5 min.

12. The method of claim 11, wherein, The premixing time is 1-3 min.

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