Symmetrical phosphine ligand containing polyethylene glycol amino group and its application

Abstract

The present application relates to a kind of containing polyethylene glycol amino symmetrical phosphine ligand and its application in homogeneous catalytic hydroformylation preparation aldehyde. Including rhodium metal compound and the catalyst composition described in the present application containing polyethylene glycol amino symmetrical phosphine ligand is introduced containing polyethylene glycol amino symmetrical phosphine ligand, by its combination with rhodium metal compound in composition, can improve the reactivity of hydroformylation reaction. At the same time, the catalyst composition has good recovery effect after the end of hydroformylation reaction, the separated catalyst composition can be recycled, reduce production cost, be conducive to industrialized production application.

Description

Technical Field

[0001] The invention belongs to the technical field of hydroformylation, and particularly relates to a symmetrical phosphine ligand containing polyethylene glycol amino groups and application thereof in preparing aldehydes by homogeneous catalytic hydroformylation. Background Art

[0002] In recent years, with the rapid development of plastics processing, automobile industry, cable industry and construction industry worldwide, the global demand for plasticizers has been increasing, which in turn has increased the demand for plasticizer alcohols, especially the demand for high-carbon alcohols above C6 has grown rapidly.

[0003] At present, the catalyst adopted by the industrial hydroformylation production process mainly contains cobalt-based catalysts and rhodium-based catalysts. Among them, the process using cobalt-based catalysts requires harsh reaction conditions, poor selectivity, many side reactions, and factors such as high energy consumption and complex cobalt recovery process. Its comprehensive economic and technical indicators are far less than the process using rhodium-based catalysts. Therefore, rhodium-based catalysts have gradually become the leading catalysts for industrial hydroformylation reactions. However, rhodium catalysts are expensive, which has increased the production cost of products to a certain extent. How to further increase the reactivity and product selectivity of rhodium-based catalysts to achieve the purpose of reducing the rhodium catalyst usage while recycling the catalyst as much as possible is one of the technical problems that are urgently needed to be solved in this field.

[0004] The activity of Rh-based catalysts in the hydroformylation process and the N / I selectivity (ratio of normal aldehyde to isomeric aldehyde) produced depend on the combination of catalyst precursor and ligand as well as the operating conditions.

[0005] U.S. Patent No. 8,710,276 discloses a cyclohexanediphenylphosphine ligand represented by the ligand CHDP. Although this ligand increases catalyst stability, the N / I selectivity is significantly reduced. U.S. Patent No. 8,507,731 discloses a catalyst combination of Rh(CO)2(acac) and a calixarene bidentate phosphine ligand in Examples 8 to 14. This catalyst combination exhibits high N / I selectivity, but has low reactivity. Furthermore, the ligand is relatively complex, the synthesis steps are cumbersome, and the cost of use is high. Furthermore, Chinese Patent No. CN101293818 discloses a hydroformylation method that effectively solves the problem of reaction differences between two olefins by performing a two-stage reaction on the hydroformylation of mixed butenes, thereby improving olefin utilization. However, this method is limited to the hydroformylation of low-carbon chain olefins.

[0006] In terms of catalyst recovery, two-phase catalytic processes (especially oil-water two-phase catalysis) have been developed. However, due to the poor solubility of higher carbon olefins above C6 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 higher carbon olefin hydroformylation. Summary of the Invention

[0007] The present invention addresses the deficiencies of the prior art and provides a symmetrical phosphine ligand containing polyethylene glycol amino groups, a catalyst composition comprising the symmetrical phosphine ligand containing polyethylene glycol amino groups for homogeneous catalytic hydroformylation to produce aldehydes, and a method for homogeneous hydroformylation to produce aldehydes using the composition. The composition incorporates the symmetrical phosphine ligand containing polyethylene glycol amino groups. When used in combination with a rhodium metal compound, the reactivity of the hydroformylation reaction can be enhanced. Furthermore, the catalyst composition exhibits excellent recovery after the hydroformylation reaction, and the recovered catalyst composition can be recycled.

[0008] To this end, the first aspect of the present invention provides a symmetrical phosphine ligand containing a polyethylene glycol amino group, the structure of which is shown in formula (I):

[0009]

[0010] Wherein, R1 and R2 are each independently selected from any one of a heterocyclic ring containing N and a substituted or unsubstituted benzene ring; preferably selected from Any one of the following, where R X and R X’ Each independently selected from hydrogen, C1-C 10 Hydrocarbon groups, C1~C 10 Alkoxy, C1~C 10 Alkanoyl, C1~C 10 Any one of an ester group, a halogen group and a nitrile group;

[0011] R3, R4, R5 and R6 are each independently selected from hydrogen, C1-C5 hydrocarbon group, C1-C5 alkoxy group, halogen and -NH-(CH2CH2O) m Any of CH3, and at least one of them is -NH-(CH2CH2O) m CH3, wherein m is selected from natural numbers of 4 to 200, preferably 5 to 50.

[0012] The second aspect of the present invention provides a catalyst composition for preparing aldehydes by homogeneous catalytic hydroformylation, which comprises a rhodium metal compound and the symmetrical phosphine ligand containing polyethylene glycol amino groups as described in the first aspect of the present invention.

[0013] In some embodiments of the present invention, the molar ratio of the rhodium metal compound to the symmetrical phosphine ligand containing polyethylene glycol amino groups is 1:(0.5-200), preferably 1:(2-50), calculated as rhodium metal.

[0014] In other embodiments of the present invention, the rhodium metal compound is as shown in formula (II):

[0015] Rh(L 1 ) x (L 2 ) y (L 3 ) z Formula (II)

[0016] Among them, L 1 , L 2 and L 3 Each is independently selected from any one of hydrogen, CO, halogen, triphenylphosphine and acetylacetone; wherein x, y and z are each independently selected from a natural number of 0 to 5, and at least one of x, y and z is not 0.

[0017] The third aspect of the present invention provides a method for preparing aldehydes by homogeneous catalytic hydroformylation, which comprises reacting an olefin feedstock with carbon monoxide and hydrogen in the presence of a solution consisting of the catalyst composition according to the second aspect of the present invention and a solvent to produce the aldehyde.

[0018] In some embodiments of the present invention, the olefin is C2 to C 12 Olefins, preferably C5 to C 12 Olefins, more preferably C6 to C 10 Olefins.

[0019] In other embodiments of the present invention, the molar ratio of the olefin to the rhodium metal compound is (500-100000):1, preferably (1000-100000):1, and more preferably (2000-8000):1, calculated as metallic rhodium.

[0020] In some embodiments of the present invention, in the solution, the concentration of rhodium, calculated as metallic rhodium, is 0.1 mmol / L to 3 mmol / L, preferably 0.25 mmol / L to 2.5 mmol / L, and more preferably 1.5 mmol / L to 2.5 mmol / L.

[0021] In other embodiments of the present invention, the solvent is an organic solvent. Preferably, the solvent is selected from C4 to C 10 Aldehydes, C4~C 10 Ketone, C4~C 10 One or more of alkanes, acetophenone, toluene, xylene and chlorobenzene.

[0022] In some embodiments of the present invention, the reaction temperature is 50°C to 120°C, preferably 80°C to 100°C.

[0023] In other embodiments of the present invention, the reaction pressure is 0.1 MPa to 10 MPa, preferably 0.1 MPa to 4 MPa.

[0024] In some embodiments of the present invention, the reaction time is 1 to 8 hours, preferably 2 to 5 hours.

[0025] In other embodiments of the present invention, the olefin feedstock is premixed with the solution before contacting with carbon monoxide and hydrogen; preferably, the premixing time is less than 10 minutes, preferably less than 5 minutes, and more preferably 1 to 3 minutes.

[0026] The present invention has the beneficial effects of introducing a symmetrical phosphine ligand containing a polyethylene glycol amino group into the composition. This ligand, when used in combination with the rhodium metal compound in the composition, can enhance the reactivity of the hydroformylation reaction. Furthermore, the catalyst composition exhibits excellent recovery after the hydroformylation reaction. The separated catalyst composition can be recycled, reducing production costs and facilitating industrial production applications. DETAILED DESCRIPTION

[0027] As mentioned above, existing catalysts for hydroformylation to produce aldehydes have disadvantages such as low reaction activity, low N / I (ratio of normal aldehyde to isomeric aldehyde) selectivity, applicability only to the hydroformylation of low-carbon chain olefins, and difficulty in recovery.

[0028] The inventors of the present application have discovered through research that when a phosphine ligand containing a polyethylene glycol amino group is used in combination with a rhodium metal compound to catalyze a hydroformylation reaction, the reaction activity and N / I selectivity of the hydroformylation reaction can be improved. At the same time, after the hydroformylation reaction is completed, the catalyst composition can be well recovered by cooling, and the separated catalyst composition can be recycled.

[0029] Therefore, the first aspect of the present invention relates to a symmetrical phosphine ligand containing a polyethylene glycol amino group, the structure of which is shown in formula (I):

[0030]

[0031] Wherein, R1 and R2 are each independently selected from any one of a heterocyclic ring containing N and a substituted or unsubstituted benzene ring; preferably selected from Any one of the following, where R X and R X’ Each independently selected from hydrogen, C1-C 10 Hydrocarbon groups, C1~C 10 Alkoxy, C1~C 10 Alkanoyl, C1~C 10 Any one of an ester group, a halogen group and a nitrile group;

[0032] R3, R4, R5 and R6 are each independently selected from hydrogen, C1-C5 hydrocarbon group, C1-C5 alkoxy group, halogen and -NH-(CH2CH2 O) m Any of CH3, and at least one of them is -NH-(CH2CH2O) m CH3, wherein m is selected from natural numbers of 4 to 200, preferably 5 to 50.

[0033] In some preferred embodiments of the present invention, the R X and R X’ Each independently selected from hydrogen and C1-C 10 R3, R4, R5 and R6 are each independently selected from hydrogen and C1 to C5 alkyl.

[0034] The second aspect of the present invention relates to a catalyst composition for preparing aldehydes by homogeneous catalytic hydroformylation, which comprises a rhodium metal compound and the symmetrical phosphine ligand containing polyethylene glycol amino groups as described in the first aspect of the present invention.

[0035] In some embodiments of the present invention, the molar ratio of the rhodium metal compound to the symmetrical phosphine ligand containing polyethylene glycol amino groups is 1:(0.5-200) calculated as rhodium metal. In some specific embodiments of the present invention, the molar ratio of the rhodium metal compound to the phosphine ligand containing polyethylene glycol amino groups can be 1:0.5, 1:2, 1:5, 1:10, 1:20, 1:30, 1:50, 1:80, 1:100, 1:150, 1:200, etc. calculated as rhodium metal. In some preferred embodiments of the present invention, the molar ratio of the rhodium metal compound to the phosphine ligand containing polyethylene glycol amino groups is 1:(2-50) calculated as rhodium metal.

[0036] In other embodiments of the present invention, the rhodium metal compound is as shown in formula (II):

[0037] Rh(L 1 ) x (L 2 ) y (L 3 ) z Formula (II)

[0038] Among them, L 1 , L 2 and L 3 Each is independently selected from any one of hydrogen, CO, halogen, triphenylphosphine and acetylacetone; x, y and z are each independently selected from natural numbers of 0 to 5, and at least one of x, y and z is not 0.

[0039] In some specific embodiments of the present invention, the halogen may be chlorine, bromine or iodine, etc., preferably chlorine.

[0040] The catalyst composition provided by the present invention introduces a symmetrical bisphosphine ligand having a polyethylene glycol amino unit and is used in combination with a rhodium metal compound to improve the reaction activity of the hydroformylation reaction. In addition, the catalyst composition has a good recovery effect after the hydroformylation reaction is completed, and the separated catalyst composition can be recycled.

[0041] The third aspect of the present invention relates to a method for preparing aldehydes by homogeneous catalytic hydroformylation, which comprises reacting an olefin feedstock with a mixture of carbon monoxide and hydrogen in the presence of a solution consisting of the catalyst composition described in the second aspect of the present invention and a solvent to produce the aldehyde.

[0042] In the present invention, carbon monoxide and hydrogen (synthesis gas) participating in the reaction are added in a mixed form and react with the olefin raw material in the form of a mixed gas.

[0043] In some embodiments of the present invention, the olefin is C2 to C 12 Olefins, preferably C5 to C 12 Olefins, more preferably C6 to C 10 In some specific embodiments of the present invention, the olefin raw material used is octene.

[0044] In other embodiments of the present invention, the molar ratio of the olefin to the rhodium metal compound is (500-100,000):1, calculated as rhodium metal. In some specific embodiments of the present invention, the molar ratio of the olefin to the rhodium metal compound can be 500:1, 1000:1, 2000:1, 5000:1, 8000:1, 10,000:1, 50,000:1, or 100,000:1, etc., calculated as rhodium metal. In some preferred embodiments of the present invention, the molar ratio of the olefin to the rhodium metal compound is (1000-100,000):1, calculated as rhodium metal. In some more preferred embodiments of the present invention, the molar ratio of the olefin to the rhodium metal compound is (2000-8000):1, calculated as rhodium metal.

[0045] In some embodiments of the present invention, in the solution, the concentration of rhodium is 0.1 mmol / L to 3 mmol / L, calculated as metallic rhodium. In some specific embodiments of the present invention, in the solution, the concentration of rhodium can be 0.1 mmol / L, 0.25 mmol / L, 0.5 mmol / L, 1.0 mmol / L, 1.2 mmol / L, 1.4 mmol / L, 1.6 mmol / L, 1.8 mmol / L, 2.0 mmol / L, 2.5 mmol / L or 3.0 mmol / L, etc., calculated as metallic rhodium. In some preferred embodiments of the present invention, in the solution, the concentration of rhodium is 0.25 mmol / L to 2.5 mmol / L, calculated as metallic rhodium. In some more preferred embodiments of the present invention, in the solution, the concentration of rhodium is 1.5 mmol / L to 2.5 mmol / L, calculated as metallic rhodium.

[0046] In other embodiments of the present invention, the solvent is an organic solvent. Preferably, the solvent is selected from C4 to C 10 Aldehydes, C4~C 10 Ketone, C4~C 10 One or more of alkanes, acetophenone, toluene, xylene and chlorobenzene.

[0047] In some embodiments of the present invention, the reaction temperature is 50°C to 120°C, preferably 80°C to 100°C.

[0048] In other embodiments of the present invention, the reaction pressure is 0.1 MPa to 10 MPa, preferably 0.1 MPa to 4 MPa.

[0049] In some embodiments of the present invention, the reaction time is 1 to 8 hours, preferably 2 to 5 hours.

[0050] In other embodiments of the present invention, the olefin feedstock is premixed with the solution before contacting with carbon monoxide and hydrogen; preferably, the premixing time is less than 10 minutes, preferably less than 5 minutes, and more preferably 1 to 3 minutes.

[0051] Example

[0052] To make the present invention easier to understand, the present invention will be further described in detail below with reference to the following examples. These examples are merely illustrative and are not intended to limit the scope of application of the present invention. The raw materials or components used in the present invention can be obtained by commercial routes or conventional methods unless otherwise specified.

[0053] The calculation formulas for olefin conversion and aldehyde selectivity in the following examples are as follows:

[0054]

[0055]

[0056] Preparation Example 1

[0057] The synthetic route of the symmetrical phosphine ligand containing polyethylene glycol amino used in Example 1 is as follows:

[0058]

[0059] Preparation of Compound A: Refer to the literature Chemical Communications (2019), 55(91), 13721-13724.

[0060] Preparation of Compound B: 500 mL three-necked flask was added 180 mL acetic acid, the three-necked flask was placed in an ice water bath, 30 mL nitric acid (69%) was added dropwise under stirring within 1 h, 3 mL sulfuric acid (95%) was added dropwise in the mixed acid. Then 3.2 mmol of compound A was added, and stirred at 0°C for 2 h. After the reaction was completed, the reaction solution was slowly poured into a sodium hydroxide solution (10%), and stirred in an ice water bath for 1 h. The solid precipitate was collected by filtration and dried under vacuum. The dried solid precipitate was dissolved in tetrahydrofuran. The solvent was removed by evaporation to obtain compound B.

[0061] Preparation of Compound C: A round-bottom flask was added with 3 mmol of compound B and 75 mL of ethanol, and then 192 mL of hydrochloric acid was added dropwise after being mixed uniformly within 1 h. The reaction was carried out by refluxing for 15 h after adding 45 mL of SnCl2·2H2O (176 mM) in ethanol dropwise in the mixed solution. After the reaction was completed, concentration and filtration were carried out, and the filtrate was neutralized with an aqueous sodium hydroxide solution. After dichloromethane extraction, the solvent was removed, and the obtained solid material was dissolved in hot ethanol, and then n-hexane was added after cooling to obtain compound C.

[0062] Preparation of Compound D: 80 mL autoclave was added with compound C (3.6 mmol) and 3 mL of anhydrous ethanol. The system was purged with nitrogen, and heated to 100°C. Then 43.2 mmol of ethylene oxide (EO) was added, and the pressure was maintained at 0.4 MPa for 6 h. After ethoxylation, the solvent was removed in vacuum to obtain the solid compound D. 1 HNMR (CDCI3): δ = 7.78 (d, 2H), 7.43 (s, 2H), 7.38 (t, 2H), 7.24 (d, 2H), 7.13-7.11 (m, 2H), 6.71-6.45 (m, 8H), 6.12-6.04 (m, 8H), 3.46 (m, 4H), 3.54-3.73 (m, 44H), 3.30 (s, 6H) ppm.

[0063] Example 1

[0064] Rhodium acetylacetonate dicarbonyl was used as the main catalyst, and a symmetrical phosphine ligand containing a polyethylene glycol amino group (where m=6) was used as the ligand. The molar ratio of the main catalyst (calculated as rhodium metal) to the ligand was 1:5, and the molar ratio of 1-octene to Rh (calculated as rhodium metal) was 10,000:1. The hydroformylation reaction was carried out in a 50 mL autoclave. After the closed reaction system was purged with N2, the atmosphere was replaced several times with synthesis gas (CO:H2=1:1). The temperature control system was activated to maintain the entire system temperature at 80°C. The vent valve was opened, and a toluene solution of the main catalyst (Rh concentration in the solution was 1.6 mmol / L) was quickly added to the reactor, followed by the addition of 1-octene. The vent valve was closed, and the mixture was premixed and stirred for 2 minutes. The pressure was set to 2 MPa, and synthesis gas (CO:H2 = 1:1) was introduced into the reaction mixture for 2 hours. The temperature was then reduced to below 20°C and the pressure was released. The reaction liquid was separated into a separator through the bottom valve of the autoclave. The lower layer was the catalyst layer, and the upper layer was the organic product layer. Gas chromatography analysis of the organic product layer showed a 1-octene conversion of 92.3%, an aldehyde selectivity of 96.1%, and a normal-isobaric ratio (linear aldehyde / branched-chain aldehyde) of 217. ICP analysis of the rhodium content in the organic product layer revealed 3.43 ppm.

[0065] Example 2

[0066] The experimental method was the same as that of Example 1, except that the structure of the symmetrical phosphine ligand containing polyethylene glycol amino group was changed (compound of formula (I), wherein m=4, and the rest of the structure remained unchanged), and the other experimental conditions remained unchanged. The conversion of 1-octene was 92.7%, the selectivity for aldehyde was 94.2%, the normal-iso ratio (straight-chain aldehyde / branched-chain aldehyde) was 164, and the content of metal rhodium in the organic product layer by ICP analysis was 43.3 ppm.

[0067] Example 3

[0068] The experimental method was the same as that of Example 1, except that the structure of the symmetrical phosphine ligand containing polyethylene glycol amino group was changed (compound of formula (I), wherein m=14, and the rest of the structure remained unchanged), and the other experimental conditions remained unchanged. The 1-octene conversion was 55.6%, the aldehyde selectivity was 95.4%, the normal-iso ratio (straight-chain aldehyde / branched-chain aldehyde) was 188, and the ICP analysis showed that the content of metal rhodium in the organic product layer was less than 2 ppm.

[0069] Example 4

[0070] The experimental method was the same as that in Example 1, except that the molar ratio of the main catalyst (in terms of rhodium) to the ligand in the solution was changed to 1:2, and the other experimental conditions remained unchanged. The 1-octene conversion was 80.5%, the aldehyde selectivity was 70.1%, the normal-iso ratio (straight-chain aldehyde / branched-chain aldehyde) was 92, and the ICP analysis showed that the content of metallic rhodium in the organic product layer was 2.63 ppm.

[0071] Example 5

[0072] The experimental method was the same as that in Example 1, except that the molar ratio of the main catalyst (in terms of rhodium) to the ligand in the solution was changed to 1:30, and the other experimental conditions remained unchanged. The conversion of 1-octene was 90.1%, the aldehyde selectivity was 96.5%, the normal-iso ratio (straight-chain aldehyde / branched-chain aldehyde) was 226, and the content of metallic rhodium in the organic product layer by ICP analysis was 3.09 ppm.

[0073] Example 6

[0074] The experimental method was the same as that in Example 1, except that the molar ratio of the main catalyst (in terms of rhodium) to the ligand in the solution was changed to 1:50, and the other experimental conditions remained unchanged. The conversion of 1-octene was 89.5%, the aldehyde selectivity was 96.7%, the normal-iso ratio (straight-chain aldehyde / branched-chain aldehyde) was 224, and the content of metallic rhodium in the organic product layer by ICP analysis was 2.43 ppm.

[0075] Example 7

[0076] The experimental method was the same as that in Example 1, except that the Rh concentration in the solution was changed to 0.25 mmol / L and the other experimental conditions remained unchanged. The 1-octene conversion was 66.8%, the aldehyde selectivity was 89.0%, the normal-iso ratio (straight-chain aldehyde / branched-chain aldehyde) was 179, and the ICP analysis showed that the content of metallic rhodium in the organic product layer was 3.34 pm.

[0077] Example 8

[0078] The experimental method was the same as that in Example 1, except that the Rh concentration in the solution was changed to 2.5 mmol / L and the other experimental conditions remained unchanged. The 1-octene conversion was 92.0%, the aldehyde selectivity was 96.0%, the normal-iso ratio (straight-chain aldehyde / branched-chain aldehyde) was 207, and the ICP analysis showed that the content of metallic rhodium in the organic product layer was 4.07 ppm.

[0079] Example 9

[0080] The experimental method was the same as in Example 1, wherein the molar ratio of 1-octene:Rh was 2000:1, and the remaining experimental conditions remained unchanged. The 1-octene conversion was 95.4%, the aldehyde selectivity was 94.8%, the normal-iso ratio (straight-chain aldehyde / branched-chain aldehyde) was 218, and the content of metallic rhodium in the organic product layer by ICP analysis was 3.47 ppm.

[0081] Example 10

[0082] The experimental method was the same as in Example 1, wherein the molar ratio of 1-octene:Rh was 8000:1, and the remaining experimental conditions remained unchanged. The 1-octene conversion was 93.8%, the aldehyde selectivity was 95.3%, the normal-iso ratio (straight-chain aldehyde / branched-chain aldehyde) was 220, and the content of metallic rhodium in the organic product layer by ICP analysis was 3.42 ppm.

[0083] Comparative Example 1

[0084] The experimental method is the same as that of Example 1, wherein the added phosphine ligand does not contain -NH-(CH2CH2O) m CH3, and the other experimental conditions remained unchanged. The test results were as follows: 1-octene conversion rate was 87.3%, aldehyde selectivity was 93.1%, normal-iso ratio (straight-chain aldehyde / branched-chain aldehyde) was 193, and the reaction liquid had no obvious stratification in the separator.

[0085] Comparative Example 2

[0086] The experimental method was the same as that of Example 1, except that the structure of the symmetrical phosphine ligand containing polyethylene glycol amino group was changed (compound of formula (I), wherein m=1, and the rest of the structure remained unchanged). The other experimental conditions remained unchanged. The 1-octene conversion was 93.5%, the aldehyde selectivity was 93.9%, the iso-ratio (straight-chain aldehyde / branched-chain aldehyde) was 96, and the reaction solution showed no obvious stratification in the separator.

[0087] As can be seen from the comparative examples, when the phosphine ligand does not contain -NH-(CH2CH2O) m CH3 or although the phosphine ligand contains -NH-(CH2CH2O) m CH3, but when the m value is too low, the reaction activity of the co-catalyst in the catalyst composition is slightly reduced. More importantly, cooling after the reaction is completed cannot separate the catalyst composition.

[0088] It should be noted that the embodiments described above are only used to explain the present invention and do not constitute any limitation of the present invention. The present invention has been described with reference to typical embodiments, but it should be understood that the words used therein are descriptive and explanatory words, rather than restrictive words. The present invention may be modified as specified within the scope of the claims of the present invention, and the present invention may be revised without departing from the scope and spirit of the present invention. Although the present invention described therein relates to specific methods, materials and embodiments, it does not mean that the present invention is limited to the specific examples disclosed therein. On the contrary, the present invention can be extended to all other methods and applications with the same function.

Claims

1. A symmetrical phosphine ligand containing polyethylene glycol amino groups for homogeneous catalytic hydroformylation to prepare aldehydes, wherein the structure is shown in formula (I): Formula (I) in, R1 and R2 are each independently selected from 、 Any one of R X and R X’ Each independently selected from hydrogen, C1~C 10 Any one of the alkoxy groups; R3, R4, R5 and R6 are each independently selected from hydrogen, C1 to C5 alkoxy and Any of the following, and at least one of them is , where m is a natural number selected from 4 to 6.

2. A catalyst composition for preparing aldehydes by homogeneous catalytic hydroformylation, comprising a rhodium metal compound and the symmetrical phosphine ligand containing polyethylene glycol amino groups as claimed in claim 1.

3. The composition according to claim 2, characterized in that Calculated on the basis of metallic rhodium, the molar ratio of the rhodium metal compound to the symmetrical phosphine ligand containing polyethylene glycol amino groups is 1:(0.5-200).

4. The composition according to claim 3, characterized in that Calculated on the basis of metallic rhodium, the molar ratio of the rhodium metal compound to the symmetrical phosphine ligand containing polyethylene glycol amino groups is 1:(2-50).

5. The catalyst composition according to claim 4, characterized in that Calculated on the basis of metallic rhodium, the molar ratio of the rhodium metal compound to the symmetrical phosphine ligand containing polyethylene glycol amino groups is 1:(5-50).

6. The composition according to any one of claims 2 to 5, characterized in that The rhodium metal compound is shown in formula (II): Rh(L 1 ) x (L 2 ) y (L 3 ) z Formula (II) Among them, L 1 , L 2 and L 3 Each is independently selected from any one of hydrogen, CO, halogen, triphenylphosphine and acetylacetone; wherein x, y and z are each independently selected from a natural number of 0 to 5, and at least one of x, y and z is not 0.

7. A method for preparing aldehydes by homogeneous catalytic hydroformylation, comprising reacting an olefin feedstock with carbon monoxide and hydrogen in the presence of a solution consisting of the catalyst composition according to any one of claims 2 to 6 and a solvent to produce the aldehyde.

8. The method according to claim 7, characterized in that The olefin is C2~C 12 Olefin; and / or, in terms of metallic rhodium, the molar ratio of the olefin to the rhodium metal compound is (500~100000):

1.

9. The method according to claim 8, characterized in that The olefin is C5~C 12 Olefin; and / or, in terms of metallic rhodium, the molar ratio of the olefin to the rhodium metal compound is (1000~100000):

1.

10. The method according to claim 9, characterized in that The olefin is C6~C 10 Olefin; and / or, in terms of metallic rhodium, the molar ratio of the olefin to the rhodium metal compound is (2000~8000):

1.

11. The method according to claim 7, characterized in that In the solution, the concentration of rhodium is 0.1 mmol / L to 3 mmol / L, calculated as metallic rhodium.

12. The method according to claim 11, characterized in that In the solution, the concentration of rhodium is 0.25 mmol / L to 2.5 mmol / L, calculated as metallic rhodium.

13. The method according to claim 12, characterized in that In the solution, the concentration of rhodium is 1.5 mmol / L to 2.5 mmol / L, calculated as metallic rhodium.

14. The method according to any one of claims 7 to 13, characterized in that The solvent is an organic solvent.

15. The method according to claim 14, characterized in that The solvent is selected from C4~C 10 Aldehydes, C4~C 10 Ketone, C4~C 10 One or more of alkanes, acetophenone, toluene, xylene and chlorobenzene.

16. The method according to any one of claims 7 to 13, characterized in that: The reaction temperature is 50° C. to 120° C.; and / or the reaction pressure is 0.1 MPa to 10 MPa; and / or the reaction time is 1 hour to 8 hours.

17. The method according to claim 16, wherein The reaction temperature is 80° C. to 100° C.; and / or the reaction pressure is 0.1 MPa to 4 MPa; and / or the reaction time is 2 hours to 5 hours.

18. The method according to any one of claims 7 to 13, characterized in that: The olefin feedstock is premixed with the solution before contacting with carbon monoxide and hydrogen.

19. The method according to claim 18, characterized in that The premixing time is less than 10 minutes.

20. The method according to claim 19, characterized in that The premixing time is less than 5 minutes.

21. The method according to claim 20, characterized in that The premixing time is 1 to 3 minutes.

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