Supported catalyst and application thereof in synthesis of isononanal through hydroformylation reaction

Abstract

The invention discloses a supported catalyst and application thereof in synthesis of isononanal through hydroformylation reaction, and relates to the technical field of catalyst synthesis. A supported catalyst comprises an intermediate B and a rhodium or cobalt-containing compound supported on the intermediate B. The loading amount of the rhodium or cobalt-containing compound supported on the intermediate B is 0.5-2%. The structure of the intermediate B is as follows: # imgabs0 #, wherein R1 and R2 are the same or different aryl, alkyl, substituted aryl and alkyl; m and n are polymerization degrees, and m and n are integers between 100 and 1000. The supported catalyst prepared by the invention is high and stable in activity, can be recycled, and is beneficial to reducing the cost of preparing aldehyde by hydroformylation. In addition, the supported catalyst is used for catalyzing olefin hydroformylation to prepare isononanal, and the conversion rate and selectivity of olefin can be improved.

Description

Technical Field

[0001] The invention relates to the technical field of catalyst synthesis, and in particular to a supported catalyst and application thereof in the synthesis of isononanal by hydroformylation reaction. Background Art

[0002] As an important organic chemical raw material and organic synthesis intermediate, isononanal is widely used in plasticizers, surfactants, fragrances, detergents and organic synthesis. Starting from isononanal, it can be processed into fine chemical products with higher application value through one or more steps. For example, isononanal can be converted into isononyl esters through hydrogenation and esterification, which are used as plasticizers; isononanoic acid can be obtained through oxidation, which can be used in lubricants, printing inks, industrial detergents and other industries.

[0003] The preparation of aldehydes by hydroformylation of olefins and synthesis gas is an important method for the industrial preparation of aldehydes. Since the discovery of hydroformylation catalysts in the 1830s, there have been a large number of reports on the application of catalysts in hydroformylation, mainly cobalt and rhodium catalysts. At present, most industrial catalytic olefin hydroformylation uses a homogeneous reaction system, which leads to a series of problems such as catalyst separation and recycling. Especially in the hydroformylation of high-carbon olefins, the resulting aldehyde has a high boiling point, which leads to a high separation temperature from the catalyst. Rhodium catalysts are easily decomposed and deactivated at high temperatures, and the separation process of cobalt catalysts is more complicated, which will undoubtedly increase product costs.

[0004] Since it is difficult to separate the catalyst from the product in homogeneous hydroformylation reaction, catalyst immobilization has become a hot topic in research. 2 The supported rhodium complex catalyst was prepared by reflux impregnation as a carrier, and catalyzed the hydroformylation of isobutylene in a high-pressure reactor. The reaction pressure was 3.0 MPa, the synthesis gas ratio CO:H2=1:1, the reaction temperature was 105°C, and the space-time yield was 526.8h -1 , selectivity 100% (CN1781602A).

[0005] Jiang Weili et al. used a bridging ligand to bond the rhodium complex to the superparamagnetic Fe 3 O 4 The surface of nanoparticles is used to obtain a hydroformylation catalyst of a rhodium complex immobilized on ferromagnetic nanoparticles. The reaction pressure is 3.0 MPa, the reaction temperature is 90°C, the olefin conversion rate can reach more than 92%, and the aldehyde selectivity can reach more than 95% (CN104475161A). In addition, there are also supported catalysts such as molecular sieves, alumina, and polyglycerol, but there are still some problems in this field, such as low catalyst activity, unsuitability for high-carbon olefins, and short catalyst life.

[0006] Based on the above background, it is very necessary to develop a new type of supported catalyst to make the separation of product and catalyst simple, the catalyst resistant to high temperature, the product selectivity high, and the hydroformylation process simplified. In addition, the catalyst should also have higher activity and stability. Therefore, the development of a suitable supported catalyst for simplifying the hydroformylation process of high carbon olefins to prepare aldehydes is an objective requirement of this type of reaction at present, and it will have a good application prospect in industrialization. Summary of the invention

[0007] The purpose of the present invention is to overcome the shortcomings of the prior art and provide a supported catalyst and its application in the hydroformylation reaction to synthesize isononanal. The supported catalyst prepared by the present invention has high activity and stability, can be recycled, and is conducive to reducing the cost of preparing aldehydes by hydroformylation. In addition, the supported catalyst is used to catalyze the hydroformylation of olefins to prepare isononanal, which can improve the conversion rate and selectivity of olefins.

[0008] To achieve the above object, the technical solution adopted by the present invention is:

[0009] In a first aspect, the present invention provides a supported catalyst, comprising an intermediate B and a rhodium or cobalt-containing compound supported on the intermediate B, wherein the loading amount of the rhodium or cobalt-containing compound supported on the intermediate B is 0.5-2%;

[0010] The structure of the intermediate B is shown below:

[0011] Where R 1 , R 2 are the same or different aryl, alkyl, substituted aryl, alkyl; m and n are the degree of polymerization, and m and n are integers between 100 and 1000.

[0012] The present invention adopts intermediate B as a carrier and a rhodium- or cobalt-containing compound as an active substance, loads the rhodium- or cobalt-containing compound on the intermediate B, and controls the loading amount of the rhodium- or cobalt-containing compound loaded on the intermediate B, thereby facilitating the improvement of the activity stability of the supported catalyst, and the activity will not be significantly reduced after multiple cycles.

[0013] Preferably, the supported catalyst is obtained by immersing the intermediate B in a solution containing a rhodium or cobalt compound, and the concentration of the solution containing a rhodium or cobalt compound is 0.1-2 mol / L, preferably 0.1-1 mol / L.

[0014] Preferably, the immersion temperature is 25-120° C., and the immersion time is 1-8 h.

[0015] More preferably, the immersion temperature is 50-80°C, and the immersion time is 2-4h.

[0016] The present invention can increase the dispersion and loading amount of the active substance by controlling the impregnation temperature and time, thereby improving the activity of the catalyst.

[0017] Preferably, the rhodium or cobalt-containing compound comprises rhodium trichloride (RhCl 3 ), rhodium acetate (Rh(OAc) 3 ), rhodium sulfate (Rh 2 (SO 4 ) 3 ), dimer (1,5-cyclooctadiene) rhodium chloride (Rh 2 (COD) 2 Cl 2 ), dimerized rhodium acetate (Rh 2 (OAc) 4 ), rhodium nitrate (Rh(NO 3 ) 3 ), carbonyl rhodium (Rh 6 (CO) 16 , Rh 4 (CO) 12 ), dicarbonyl acetylacetonate rhodium (Rh(acac)(CO) 2 ), acetylacetonato(1,5-cyclooctadiene)rhodium (Rh(acac)(COD)), dicarbonylchlororhodium dimer (Rh 2 (CO) 4 Cl 2 ), tris(m-triphenylphosphine trisulfonic acid sodium salt) chlorocarbonyl rhodium (RhCl(CO)(TPPTS) 3 ), tris(m-triphenylphosphine trisulfonic acid sodium salt) hydride carbonyl rhodium (HRh(CO)(TPPTS) 3 )、Cobalt Carbonyl (Co(CO) 4 or Co 2 (CO) 8 ), bis(triphenylphosphine)cobalt dibromide (Co(PPh 3 ) 2 Br 2 ) at least one of.

[0018] Preferably, the R 1 , R 2 The terminal groups are connected to each other, which can not only enrich the structure of the phosphine ligand, but also increase the structural rigidity and steric hindrance of the phosphine ligand.

[0019] Preferably, the preparation method of the intermediate B comprises the following steps:

[0020] (1) adding poly(styrene-4-chloromethylstyrene) into an alkaline solution for hydrolysis to obtain an intermediate A, wherein the molar ratio of the poly(styrene-4-chloromethylstyrene) to the alkaline solution is 1:(2-10);

[0021] (2) reacting intermediate A with sodium iodide and disubstituted chlorophosphine to obtain intermediate B; the molar ratio of intermediate A, sodium iodide and disubstituted chlorophosphine is 1:(2-10):(2-8).

[0022] The structures of the poly(styrene-4-chloromethylstyrene), disubstituted chlorophosphine, and intermediate A are shown below:

[0023]

[0024] Preferably, in step (1), the molar ratio of poly(styrene-4-chloromethylstyrene) to the alkaline solution is 1:(4-8).

[0025] The invention controls the molar ratio of poly(styrene-4-chloromethylstyrene) to the alkaline solution so that the activity of the supported catalyst is not easily affected.

[0026] Preferably, the reaction temperature during the hydrolysis in step (1) is 50-120° C., and the reaction time is 6-18 h.

[0027] More preferably, the reaction temperature during the hydrolysis in step (1) is 80-110° C., and the reaction time is 8-16 h.

[0028] Preferably, the alkaline solution in step (1) is at least one of potassium hydroxide, sodium hydroxide, sodium carbonate and potassium carbonate.

[0029] Preferably, in step (2), the reaction temperature is 25-100° C. and the reaction time is 2-16 h.

[0030] More preferably, in step (2), the reaction temperature is 40-80° C. and the reaction time is 5-12 h.

[0031] Preferably, in the step (2), the molar ratio of the intermediate A, sodium iodide and disubstituted chlorophosphine is 1:(4-8):(4-7).

[0032] The present invention can control the byproducts generated in the reaction process of converting the intermediate A into the intermediate B by controlling the molar ratio of the intermediate A, sodium iodide and disubstituted chlorophosphine, thereby ensuring the purity of the phosphine ligand and improving the activity of the supported catalyst.

[0033] In a second aspect, the present invention further provides an application of the above-mentioned supported catalyst in the hydroformylation reaction to synthesize isononanal, comprising the following steps:

[0034] Olefins and supported catalysts are added to the reactor, nitrogen is replaced and synthesis gas is introduced, the temperature is increased to carry out hydroformylation reaction, and after the reaction is completed, isononanal is obtained by filtering.

[0035] Preferably, the reaction temperature is 25-150° C., the reaction time is 2-18 h, and the reaction pressure is 0.5-30 MPa.

[0036] More preferably, the reaction temperature is 50-120° C., the reaction time is 5-12 h, and the reaction pressure is 1-20 MPa.

[0037] Preferably, the olefin comprises at least one of diisobutylene, butene, butene-2, butadiene, isobutylene, 1-pentene, cyclopentene, cyclopentadiene, 1-hexene, cyclohexene, 1-heptene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, cyclooctene, 1-nonene, tripropylene, and tetrapropylene.

[0038] Compared with the prior art, the present invention has the following beneficial effects:

[0039] The supported catalyst prepared by the present invention has high activity and stability, can be recycled, and is conducive to reducing the cost of preparing aldehydes by hydroformylation. In addition, the supported catalyst is used to catalyze the hydroformylation of olefins to prepare isononanal, which can improve the conversion rate and selectivity of olefins. DETAILED DESCRIPTION

[0040] In order to better illustrate the purpose, technical solutions and advantages of the present invention, the present invention will be further described below in conjunction with specific embodiments, but the protection scope and implementation methods of the present invention are not limited thereto.

[0041] Unless otherwise specified, the materials and reagents used in the following examples are commercially available.

[0042] Poly(styrene-4-chloromethylstyrene), manufacturer: Sigma-Aldrich, product number: 659177;

[0043] Diphenylphosphine chloride, manufacturer: Aladdin, CAS number: 1079-66-9;

[0044] Sodium iodide, manufacturer: Aladdin, CAS number: 7681-82-5.

[0045] Example 1

[0046] A method for preparing a supported catalyst comprises the following steps:

[0047] (1) adding poly(styrene-4-chloromethylstyrene) to a potassium carbonate solution, the reaction temperature is 100° C., the reaction time is 10 h, filtering, washing with deionized water, and drying at 120° C. for 24 h to obtain an intermediate A, wherein the molar ratio of poly(styrene-4-chloromethylstyrene) to the alkaline solution is 1:2;

[0048] (2) Add intermediate A to a round-bottom flask, then add sodium iodide, diphenylphosphine chloride, and solvent acetonitrile, the reaction temperature is 80°C, the reaction time is 12 hours, filter at room temperature, wash the product with n-hexane, and then dry at 120°C for 24 hours to obtain intermediate B, the molar ratio of intermediate A, sodium iodide, and disubstituted phosphine chloride is 1:6:6;

[0049] (3) The intermediate B was immersed in a toluene solution of dicarbonyl rhodium chloride dimer with a concentration of 2 mol / L, the immersion temperature was 60° C., the immersion time was 4 h, and after the immersion was completed, it was washed with methanol and dried at 70° C. for 72 h to obtain a supported catalyst. The loading amount of the intermediate B was 1%.

[0050] The invention discloses an application of a supported catalyst in a hydroformylation reaction to synthesize isononanal, comprising the following steps:

[0051] 500 mmol of diisobutylene and 10 mmol of supported catalyst were added to a 300 mL autoclave to replace N 2 The mixture was evacuated, connected to carbon monoxide and hydrogen cylinders, and rapidly heated to 120°C. At the same time, the system pressure was adjusted to 15.0 MPa, the stirring rate was 800 rpm, and maintained for 8 hours. After the reaction was completed, the isononanal product was obtained by filtration.

[0052] After the reaction was completed, the supported catalyst was separated by filtration under nitrogen protection, and the catalyst was continuously recycled according to the above hydroformylation process conditions for five consecutive times. The results are as follows:

[0053]

[0054] Example 2

[0055] A method for preparing a supported catalyst comprises the following steps:

[0056] (1) adding poly(styrene-4-chloromethylstyrene) to a potassium carbonate solution, the reaction temperature is 100° C., the reaction time is 10 h, filtering, washing with deionized water, and drying at 120° C. for 24 h to obtain an intermediate A, wherein the molar ratio of poly(styrene-4-chloromethylstyrene) to the alkaline solution is 1:10;

[0057] (2) Add intermediate A to a round-bottom flask, then add sodium iodide, di-p-tolylphosphine chloride, and solvent acetonitrile, the reaction temperature is 80°C, the reaction time is 12 hours, filter at room temperature, wash the product with n-hexane, and then dry at 120°C for 24 hours to obtain intermediate B, the molar ratio of intermediate A, sodium iodide, and disubstituted phosphine chloride is 1:6:6;

[0058] (3) The intermediate B was immersed in a toluene solution of dicarbonyl rhodium chloride dimer with a concentration of 2 mol / L, the immersion temperature was 50° C., the immersion time was 2 h, and after the immersion was completed, it was washed with methanol and dried at 70° C. for 72 h to obtain a supported catalyst. The loading amount of the intermediate B was 0.5%.

[0059] The invention discloses an application of a supported catalyst in a hydroformylation reaction to synthesize isononanal, comprising the following steps:

[0060] 500 mmol of diisobutylene and 10 mmol of supported catalyst were added to a 300 mL autoclave to replace N 2 The mixture was evacuated, connected to carbon monoxide and hydrogen cylinders, and rapidly heated to 120°C. At the same time, the system pressure was adjusted to 15.0 MPa, the stirring rate was 800 rpm, and maintained for 8 hours. After the reaction was completed, the isononanal product was obtained by filtration.

[0061] After the reaction was completed, the supported catalyst was separated by filtration under nitrogen protection, and the catalyst was continuously recycled according to the above hydroformylation process conditions for five consecutive times. The results are as follows:

[0062]

[0063] Example 3

[0064] A method for preparing a supported catalyst comprises the following steps:

[0065] (1) adding poly(styrene-4-chloromethylstyrene) to a potassium carbonate solution, the reaction temperature is 100° C., the reaction time is 10 h, filtering, washing with deionized water, and drying at 120° C. for 24 h to obtain an intermediate A, wherein the molar ratio of poly(styrene-4-chloromethylstyrene) to the alkaline solution is 1:2;

[0066] (2) Add intermediate A to a round-bottom flask, then add sodium iodide, bis(2,4,6-trimethylphenyl)phosphine chloride, and solvent acetonitrile, the reaction temperature is 80°C, the reaction time is 12 hours, filter at room temperature, wash the product with n-hexane, and then dry at 120°C for 24 hours to obtain intermediate B, the molar ratio of intermediate A, sodium iodide, and disubstituted phosphine chloride is 1:6:6;

[0067] (3) The intermediate B was immersed in a toluene solution of dicarbonyl rhodium chloride dimer with a concentration of 2 mol / L, the immersion temperature was 80° C., the immersion time was 4 h, and after the immersion was completed, it was washed with methanol and dried at 70° C. for 72 h to obtain a supported catalyst. The loading amount of the intermediate B was 2%.

[0068] The invention discloses an application of a supported catalyst in a hydroformylation reaction to synthesize isononanal, comprising the following steps:

[0069] 500 mmol of diisobutylene and 10 mmol of supported catalyst were added to a 300 mL autoclave to replace N 2 The mixture was evacuated, connected to carbon monoxide and hydrogen cylinders, and rapidly heated to 120°C. At the same time, the system pressure was adjusted to 15.0 MPa, the stirring rate was 800 rpm, and maintained for 8 hours. After the reaction was completed, the isononanal product was obtained by filtration.

[0070] After the reaction was completed, the supported catalyst was separated by filtration under nitrogen protection, and the catalyst was continuously recycled according to the above hydroformylation process conditions for five consecutive times. The results are as follows:

[0071]

[0072] Example 4

[0073] A method for preparing a supported catalyst comprises the following steps:

[0074] (1) adding poly(styrene-4-chloromethylstyrene) to a potassium carbonate solution, the reaction temperature is 100° C., the reaction time is 10 h, filtering, washing with deionized water, and drying at 120° C. for 24 h to obtain an intermediate A, wherein the molar ratio of poly(styrene-4-chloromethylstyrene) to the alkaline solution is 1:2;

[0075] (2) Add intermediate A to a round-bottom flask, then add sodium iodide, bis(3,5-dimethyl-4-methoxyphenyl)phosphine chloride, and solvent acetonitrile, the reaction temperature is 80°C, the reaction time is 12 hours, filter at room temperature, wash the product with n-hexane, and then dry at 120°C for 24 hours to obtain intermediate B, the molar ratio of intermediate A, sodium iodide, and disubstituted phosphine chloride is 1:6:6;

[0076] (3) The intermediate B was immersed in a toluene solution of dicarbonyl rhodium chloride dimer with a concentration of 2 mol / L, the immersion temperature was 60° C., the immersion time was 4 h, and after the immersion was completed, it was washed with methanol and dried at 70° C. for 72 h to obtain a supported catalyst. The loading amount of the intermediate B was 1%.

[0077] The invention discloses an application of a supported catalyst in a hydroformylation reaction to synthesize isononanal, comprising the following steps:

[0078] 500 mmol of diisobutylene and 10 mmol of supported catalyst were added to a 300 mL autoclave to replace N 2 The mixture was evacuated, connected to carbon monoxide and hydrogen cylinders, and rapidly heated to 120°C. At the same time, the system pressure was adjusted to 15.0 MPa, the stirring rate was 800 rpm, and maintained for 8 hours. After the reaction was completed, the isononanal product was obtained by filtration.

[0079] After the reaction was completed, the supported catalyst was separated by filtration under nitrogen protection, and the catalyst was continuously recycled according to the above hydroformylation process conditions for five consecutive times. The results are as follows:

[0080]

[0081] Example 5

[0082] A method for preparing a supported catalyst comprises the following steps:

[0083] (1) adding poly(styrene-4-chloromethylstyrene) to a potassium carbonate solution, the reaction temperature is 100° C., the reaction time is 10 h, filtering, washing with deionized water, and drying at 120° C. for 24 h to obtain an intermediate A, wherein the molar ratio of poly(styrene-4-chloromethylstyrene) to the alkaline solution is 1:2;

[0084] (2) Add intermediate A to a round-bottom flask, then add sodium iodide, diphenylphosphine chloride, and solvent acetonitrile, the reaction temperature is 80°C, the reaction time is 12 hours, filter at room temperature, wash the product with n-hexane, and then dry at 120°C for 24 hours to obtain intermediate B, the molar ratio of intermediate A, sodium iodide, and disubstituted phosphine chloride is 1:6:6;

[0085] (3) The intermediate B was immersed in a toluene solution of carbonyl cobalt with a concentration of 2 mol / L at a temperature of 60° C. for 4 h. After the immersion, it was washed with methanol and dried at 70° C. for 72 h to obtain a supported catalyst. The supported amount of the intermediate B was 1%.

[0086] The invention discloses an application of a supported catalyst in a hydroformylation reaction to synthesize isononanal, comprising the following steps:

[0087] 500 mmol of diisobutylene and 10 mmol of supported catalyst were added to a 300 mL autoclave to replace N 2 The mixture was evacuated, connected to carbon monoxide and hydrogen cylinders, and rapidly heated to 120°C. At the same time, the system pressure was adjusted to 15.0 MPa, the stirring rate was 800 rpm, and maintained for 8 hours. After the reaction was completed, the isononanal product was obtained by filtration.

[0088] After the reaction was completed, the catalyst was filtered and separated under nitrogen protection, and the catalyst was continuously recycled according to the above hydroformylation process conditions for five consecutive times. The results are as follows:

[0089]

[0090] Comparative Example 1

[0091] The difference from Example 1 is that in the preparation of the supported catalyst, an equimolar amount of diisopropylphosphine chloride is used in step (2) to replace diphenylphosphine chloride, and the other steps are the same as in Example 1.

[0092] After the reaction was completed, the catalyst was filtered and separated under nitrogen protection, and the catalyst was continuously recycled according to the above hydroformylation process conditions for five consecutive times. The results are as follows:

[0093]

[0094] Comparative Example 2

[0095] The difference from Example 1 is that in the preparation of the supported catalyst, an equal molar amount of chloro(tert-butyl)phenylphosphine is used in step (2) to replace diphenylphosphine chloride, and the other steps are the same as Example 1.

[0096] After the reaction was completed, the catalyst was filtered and separated under nitrogen protection, and the catalyst was continuously recycled according to the above hydroformylation process conditions for five consecutive times. The results are as follows:

[0097]

[0098] According to the results of Comparative Examples 1-2, it can be seen that not any phosphine ligand can make the supported catalyst have a higher activity. Only by using one of diphenylphosphine chloride, di-p-tolylphosphine chloride, bis(2,4,6-trimethylphenyl)phosphine chloride, and bis(3,5-dimethyl-4-methoxyphenyl)phosphine chloride as the phosphine ligand can the activity stability of the supported catalyst be improved, and its activity will not decrease significantly after multiple cycles.

[0099] Comparative Example 3

[0100] The difference from Example 1 is that in the preparation of the supported catalyst, the impregnation temperature in step (3) is 150° C., and the other steps are the same as in Example 1.

[0101] After the reaction was completed, the catalyst was filtered and separated under nitrogen protection, and the catalyst was continuously recycled according to the above hydroformylation process conditions for five consecutive times. The results are as follows:

[0102]

[0103] Comparative Example 4

[0104] The difference from Example 1 is that in the preparation of the supported catalyst, the impregnation time in step (3) is 10 h, and the other steps are the same as in Example 1.

[0105] After the reaction was completed, the catalyst was filtered and separated under nitrogen protection, and the catalyst was continuously recycled according to the above hydroformylation process conditions for five consecutive times. The results are as follows:

[0106]

[0107] According to the results of Comparative Examples 3-4, both the impregnation time and temperature will affect the distribution and stability of the active substance, thereby affecting the performance of the catalyst. Therefore, by controlling the impregnation temperature and time within the range defined by the present invention, it is beneficial to increase the activity of the supported catalyst.

[0108] Comparative Example 5

[0109] The difference from Example 1 is that in the preparation of the supported catalyst, the loading amount of the intermediate B is 0.2%, and the other steps are the same as those in Example 1.

[0110] After the reaction was completed, the catalyst was filtered and separated under nitrogen protection, and the catalyst was continuously recycled according to the above hydroformylation process conditions for five consecutive times. The results are as follows:

[0111]

[0112] Comparative Example 6

[0113] The difference from Example 1 is that in the preparation of the supported catalyst, the loading amount of the intermediate B is 5%, and the other steps are the same as those in Example 1.

[0114] After the reaction was completed, the catalyst was filtered and separated under nitrogen protection, and the catalyst was continuously recycled according to the above hydroformylation process conditions for five consecutive times. The results are as follows:

[0115]

[0116] Finally, it should be noted that the above embodiments are only used to illustrate the technical solution of the present invention rather than to limit the scope of protection of the present invention. Although the present invention has been described in detail with reference to the preferred embodiments, those skilled in the art should understand that the technical solution of the present invention can be modified or replaced by equivalents without departing from the essence and scope of the technical solution of the present invention.

Claims

1. A supported catalyst, characterized in that It comprises an intermediate B and a rhodium or cobalt-containing compound loaded on the intermediate B, wherein the loading amount of the rhodium or cobalt-containing compound loaded on the intermediate B is 0.5-2%; The structure of the intermediate B is shown below: Where R 1 , R 2 are the same or different aryl, alkyl, substituted aryl, alkyl; m and n are the degree of polymerization, and m and n are integers between 100 and 1000.

2. The supported catalyst according to claim 1, characterized in that The supported catalyst is obtained by immersing the intermediate B in a solution containing a rhodium or cobalt compound, wherein the concentration of the solution containing the rhodium or cobalt compound is 0.1-2 mol / L.

3. The supported catalyst according to claim 1, wherein The immersion temperature is 25-120° C., and the immersion time is 1-8 hours.

4. The supported catalyst according to claim 1, characterized in that The rhodium or cobalt-containing compound includes at least one of rhodium trichloride, rhodium acetate, rhodium sulfate, dimer (1,5-cyclooctadiene) rhodium chloride, dimer rhodium acetate, rhodium nitrate, carbonyl rhodium, dicarbonyl acetylacetonate rhodium, acetylacetonate (1,5-cyclooctadiene) rhodium, dicarbonyl rhodium chloride dimer, tris (sodium salt of m-triphenylphosphine trisulfonate) carbonyl rhodium chloride, tris (sodium salt of m-triphenylphosphine trisulfonate) hydrogenated carbonyl rhodium, carbonyl cobalt, and bis (triphenylphosphine) cobalt dibromide.

5. The supported catalyst according to claim 1, characterized in that The preparation method of the intermediate B comprises the following steps: (1) adding poly(styrene-4-chloromethylstyrene) into an alkaline solution for hydrolysis to obtain an intermediate A, wherein the molar ratio of the poly(styrene-4-chloromethylstyrene) to the alkaline solution is 1:(2-10); (2) reacting intermediate A with sodium iodide and disubstituted chlorophosphine to obtain intermediate B; the molar ratio of intermediate A, sodium iodide and disubstituted chlorophosphine is 1:(2-10):(2-8).

6. The supported catalyst as claimed in claim 5, characterized in that The alkaline solution in step (1) is at least one of potassium hydroxide, sodium hydroxide, sodium carbonate and potassium carbonate.

7. The supported catalyst according to claim 5, characterized in that The reaction temperature during the hydrolysis in step (1) is 50-120° C., and the reaction time is 6-18 hours.

8. The supported catalyst as claimed in claim 5, characterized in that The disubstituted phosphine chloride in step (2) is one of diphenylphosphine chloride, di-p-tolylphosphine chloride, bis(2,4,6-trimethylphenyl)phosphine chloride and bis(3,5-dimethyl-4-methoxyphenyl)phosphine chloride.

9. The supported catalyst according to claim 5, characterized in that In the step (2), the reaction temperature is 25-100° C. and the reaction time is 2-16 h.

10. Use of the supported catalyst according to any one of claims 1 to 9 in the hydroformylation reaction to synthesize isononanal, characterized in that: The following steps are involved: Olefins and supported catalysts are added to the reactor, nitrogen is replaced and synthesis gas is introduced, the temperature is increased to carry out hydroformylation reaction, and after the reaction is completed, isononanal is obtained by filtering.

11. Use of the supported catalyst according to claim 10 in the hydroformylation reaction to synthesize isononanal, characterized in that: The reaction temperature is 25-150° C., the reaction time is 2-18 hours, and the reaction pressure is 0.5-30 MPa.

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