A supported catalyst and its application in the hydroformylation reaction to synthesize isononanal.

Abstract

This invention discloses a supported catalyst and its application in the hydroformylation reaction to synthesize isononanal, relating to the technical field of catalyst synthesis. A supported catalyst includes an intermediate B and a rhodium- or cobalt-containing compound supported on the intermediate B, wherein the loading of the rhodium- or cobalt-containing compound on the intermediate B is 0.5-2%; the structure of the intermediate B is shown below: wherein R… 1 R 2 The groups m and n are the same or different aryl, alkyl, substituted aryl, and alkyl groups; m and n are the degrees of polymerization, and are integers between 100 and 1000. The supported catalyst prepared by this invention has high activity and stability, can be recycled, and is beneficial to reducing the cost of hydroformylation to aldehydes. Furthermore, using the supported catalyst to catalyze the hydroformylation of olefins to isononanal can improve the conversion rate and selectivity of olefins.

Description

Technical Field

[0001] This invention relates to the technical field of catalyst synthesis, and more particularly to a supported catalyst and its application in the hydroformylation reaction to synthesize isononanal. Background Technology

[0002] Isonononaldehyde, as an important organic chemical raw material and organic synthesis intermediate, is widely used in plasticizers, surfactants, fragrances, detergents, and organic synthesis. Starting from isonononaldehyde, it can be processed in one or more steps into fine chemical products with higher application value. For example, isonononaldehyde can be converted into isononyl ester through hydrogenation and esterification, which can be used as a plasticizer; oxidation yields isonononic acid, which can be used in lubricants, printing inks, and industrial detergents.

[0003] The hydroformylation of olefins and syngas to produce aldehydes is an important industrial method for aldehyde production. Since the discovery of hydroformylation catalysts in the 1830s, numerous reports have documented their application, primarily using cobalt and rhodium catalysts. Currently, most industrial catalytic hydroformylation of olefins employs homogeneous reaction systems, leading to a series of issues related to catalyst separation and recycling. Particularly in the hydroformylation of high-carbon olefins, the resulting aldehydes have high boiling points, resulting in high separation temperatures from the catalyst. Rhodium catalysts are prone to decomposition and deactivation at high temperatures, while the separation process for cobalt catalysts is even more complex, undoubtedly increasing product costs.

[0004] Due to the difficulty in separating the catalyst from the product in homogeneous hydroformylation reactions, catalyst immobilization has become a research hotspot. Chu Wei et al. used phosphotungstic acid-modified SiO2 as a support and prepared a supported rhodium-based complex catalyst by reflux impregnation. This catalyst catalyzed the hydroformylation of isobutylene in a high-pressure reactor at a pressure of 3.0 MPa, a syngas ratio of CO:H2 = 1:1, a reaction temperature of 105 °C, and a space-time yield of 526.8 h⁻¹. -1 100% selectivity (CN1781602A).

[0005] Jiang Weili et al. used bridging ligands to bond rhodium complexes to the surface of superparamagnetic Fe3O4 nanoparticles, obtaining a hydroformylation catalyst with rhodium complexes supported on ferromagnetic nanoparticles. At a reaction pressure of 3.0 MPa and a reaction temperature of 90 °C, the olefin conversion rate reached over 92%, and the aldehyde selectivity reached over 95% (CN104475161A). Besides this, other supported catalysts such as molecular sieves, alumina, and polyglycerol have been used. However, some problems still exist in this field, such as low catalyst activity, inapplicability to high-carbon olefins, and short catalyst lifetime.

[0006] Against this backdrop, it is essential to develop a novel supported catalyst that simplifies product-catalyst separation, provides high-temperature resistance, exhibits high product selectivity, and simplifies the hydroformylation process. Furthermore, the catalyst should possess higher activity and stability. Therefore, developing suitable supported catalysts to simplify the hydroformylation process of high-carbon olefins to prepare aldehydes is an objective requirement for this type of reaction and will undoubtedly have excellent application prospects in industrialization. Summary of the Invention

[0007] The purpose of this invention is to overcome the shortcomings of existing technologies and provide a supported catalyst and its application in the hydroformylation reaction to synthesize isonononal. The supported catalyst prepared by this invention has high activity and stability, can be recycled, and is beneficial to reducing the cost of hydroformylation to aldehydes. Furthermore, using the supported catalyst to catalyze the hydroformylation of olefins to prepare isonononal can improve the conversion rate and selectivity of olefins.

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

[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 of the rhodium- or cobalt-containing compound on the intermediate B is 0.5-2%.

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

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

[0012] This invention uses intermediate B as a support and a rhodium or cobalt-containing compound as an active material. By loading the rhodium or cobalt-containing compound onto intermediate B and controlling the loading amount of the rhodium or cobalt-containing compound onto intermediate B, the activity stability of the supported catalyst can be improved, and its activity will not decrease significantly after multiple cycles.

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

[0014] Preferably, the impregnation temperature is 25-120℃ and the impregnation time is 1-8h.

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

[0016] This invention can increase the dispersion and loading of active materials by controlling the impregnation temperature and time, thereby improving the activity of the catalyst.

[0017] Preferably, the rhodium or cobalt-containing compounds include rhodium trichloride (RhCl3), rhodium acetate (Rh(OAc)3), rhodium sulfate (Rh2(SO4)3), dimeric (1,5-cyclooctadiene)rhodium chloride (Rh2(COD)2Cl2), dimeric rhodium acetate (Rh2(OAc)4), rhodium nitrate (Rh(NO3)3), and rhodium carbonyl (Rh6(CO)3). 16 Rh4(CO) 12 At least one of the following: dicarbonyl acetylacetonate rhodium (Rh(acac)(CO)2), acetylacetonate (1,5-cyclooctadiene) rhodium (Rh(acac)(COD)), dicarbonyl chloride rhodium dimer (Rh2(CO)4Cl2), tri(m-triphenylphosphine trisulfonate sodium salt) chlorocarbonyl rhodium (RhCl(CO)(TPPTS)3), tri(m-triphenylphosphine trisulfonate sodium salt) chlorohydrocarbonyl rhodium (HRh(CO)(TPPTS)3), carbonyl cobalt (Co(CO)4 or Co2(CO)8), and bis(triphenylphosphine) cobalt dibromide (Co(PPh3)2Br2).

[0018] Preferably, the R 1 R 2 The interconnection of the end groups not only enriches the structure of phosphine ligands but also increases their structural rigidity and steric hindrance.

[0019] Preferably, the method for preparing intermediate B includes the following steps:

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

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

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

[0023]

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

[0025] This invention controls the molar ratio of poly(styrene-4-chloromethylstyrene) to alkaline solution, making the activity of the supported catalyst less susceptible to influence.

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

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

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

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

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

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

[0032] This invention controls the byproducts generated during the reaction of intermediate A to intermediate B by controlling the molar ratio of intermediate A, sodium iodide, and disubstituted phosphine chloride, thereby ensuring the purity of the phosphine ligand and improving the activity of the supported catalyst.

[0033] Secondly, the present invention also provides an application of the above-mentioned supported catalyst in the hydroformylation reaction to synthesize isononanal, comprising the following steps:

[0034] An olefin and a supported catalyst were added to the reactor, nitrogen was used to replace the catalyst and syngas was introduced. The reactor was heated to carry out a hydroformylation reaction. After the reaction was completed, the mixture was filtered to obtain isononal.

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

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

[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, tripolypropylene, and tetrapolypropylene.

[0038] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0039] The supported catalyst prepared by this invention exhibits high activity and stability, and can be recycled, which helps reduce the cost of hydroformylation to aldehydes. Furthermore, using the supported catalyst to catalyze the hydroformylation of olefins to isononanal can improve the conversion rate and selectivity of olefins. Detailed Implementation

[0040] To better illustrate the purpose, technical solution, and advantages of the present invention, the present invention will be further described below in conjunction with specific embodiments, but the scope of protection and implementation 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 No.: 659177;

[0043] Diphenylphosphine chloride, Manufacturer: Aladdin, CAS No.: 1079-66-9;

[0044] Sodium iodide, manufacturer: Aladdin, CAS No.: 7681-82-5.

[0045] Example 1

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

[0047] (1) Poly(styrene-4-chloromethylstyrene) was added to potassium carbonate solution, the reaction temperature was 100℃, the reaction time was 10h, filtered, washed with deionized water, and dried at 120℃ for 24h to obtain intermediate A. The molar ratio of poly(styrene-4-chloromethylstyrene) to alkaline solution was 1:2.

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

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

[0050] The application of a supported catalyst in the hydroformylation reaction to synthesize isononanal includes the following steps:

[0051] Add 500 mmol of diisobutylene and 10 mmol of supported catalyst to a 300 mL high-pressure reactor, replace with N2 and evacuate, connect carbon monoxide and hydrogen cylinders, rapidly heat to 120 °C, adjust the system pressure to 15.0 MPa, stir at 800 rpm, maintain for 8 h, and filter after the reaction to obtain isononanal product.

[0052] After the reaction was completed, the supported catalyst was separated by filtration under nitrogen protection. The catalyst was then recycled five times under the same hydroformylation process conditions. The results are as follows:

[0053]

[0054] Example 2

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

[0056] (1) Poly(styrene-4-chloromethylstyrene) was added to potassium carbonate solution, the reaction temperature was 100℃, the reaction time was 10h, filtered, washed with deionized water, and dried at 120℃ for 24h to obtain intermediate A. The molar ratio of poly(styrene-4-chloromethylstyrene) to alkaline solution was 1:10.

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

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

[0059] The application of a supported catalyst in the hydroformylation reaction to synthesize isononanal includes the following steps:

[0060] Add 500 mmol of diisobutylene and 10 mmol of supported catalyst to a 300 mL high-pressure reactor, replace with N2 and evacuate, connect carbon monoxide and hydrogen cylinders, rapidly heat to 120 °C, adjust the system pressure to 15.0 MPa, stir at 800 rpm, maintain for 8 h, and filter after the reaction to obtain isononanal product.

[0061] After the reaction was completed, the supported catalyst was separated by filtration under nitrogen protection. The catalyst was then recycled five times under the same hydroformylation process conditions. The results are as follows:

[0062]

[0063] Example 3

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

[0065] (1) Poly(styrene-4-chloromethylstyrene) was added to potassium carbonate solution, the reaction temperature was 100℃, the reaction time was 10h, filtered, washed with deionized water, and dried at 120℃ for 24h to obtain intermediate A. The molar ratio of poly(styrene-4-chloromethylstyrene) to alkaline solution was 1:2.

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

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

[0068] The application of a supported catalyst in the hydroformylation reaction to synthesize isononanal includes the following steps:

[0069] Add 500 mmol of diisobutylene and 10 mmol of supported catalyst to a 300 mL high-pressure reactor, replace with N2 and evacuate, connect carbon monoxide and hydrogen cylinders, rapidly heat to 120 °C, adjust the system pressure to 15.0 MPa, stir at 800 rpm, maintain for 8 h, and filter after the reaction to obtain isononanal product.

[0070] After the reaction was completed, the supported catalyst was separated by filtration under nitrogen protection. The catalyst was then recycled five times under the same hydroformylation process conditions. The results are as follows:

[0071]

[0072] Example 4

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

[0074] (1) Poly(styrene-4-chloromethylstyrene) was added to potassium carbonate solution, the reaction temperature was 100℃, the reaction time was 10h, filtered, washed with deionized water, and dried at 120℃ for 24h to obtain intermediate A. The molar ratio of poly(styrene-4-chloromethylstyrene) to alkaline solution was 1:2.

[0075] (2) Add intermediate A to a round-bottom flask, then add sodium iodide, bis(3,5-dimethyl4-methoxyphenyl)phosphine chloride, and acetonitrile as solvent. The reaction temperature is 80℃ and the reaction time is 12h. Filter at room temperature, wash the product with n-hexane, and then dry at 120℃ for 24h to obtain intermediate B. The molar ratio of intermediate A, sodium iodide, and disubstituted phosphine chloride is 1:6:6.

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

[0077] The application of a supported catalyst in the hydroformylation reaction to synthesize isononanal includes the following steps:

[0078] Add 500 mmol of diisobutylene and 10 mmol of supported catalyst to a 300 mL high-pressure reactor, replace with N2 and evacuate, connect carbon monoxide and hydrogen cylinders, rapidly heat to 120 °C, adjust the system pressure to 15.0 MPa, stir at 800 rpm, maintain for 8 h, and filter after the reaction to obtain isononanal product.

[0079] After the reaction was completed, the supported catalyst was separated by filtration under nitrogen protection. The catalyst was then recycled five times under the same hydroformylation process conditions. The results are as follows:

[0080]

[0081] Example 5

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

[0083] (1) Poly(styrene-4-chloromethylstyrene) was added to potassium carbonate solution, the reaction temperature was 100℃, the reaction time was 10h, filtered, washed with deionized water, and dried at 120℃ for 24h to obtain intermediate A. The molar ratio of poly(styrene-4-chloromethylstyrene) to alkaline solution was 1:2.

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

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

[0086] The application of a supported catalyst in the hydroformylation reaction to synthesize isononanal includes the following steps:

[0087] Add 500 mmol of diisobutylene and 10 mmol of supported catalyst to a 300 mL high-pressure reactor, replace with N2 and evacuate, connect carbon monoxide and hydrogen cylinders, rapidly heat to 120 °C, adjust the system pressure to 15.0 MPa, stir at 800 rpm, maintain for 8 h, and filter after the reaction to obtain isononanal product.

[0088] After the reaction was completed, the catalyst was separated by filtration under nitrogen protection. The catalyst was then recycled five times under the same hydroformylation process conditions. 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, step (2) uses an equimolar amount of diisopropylphosphine chloride instead of diphenylphosphine chloride, while the other steps are the same as in Example 1.

[0092] After the reaction was completed, the catalyst was separated by filtration under nitrogen protection. The catalyst was then recycled five times under the same hydroformylation process conditions. 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, step (2) uses an equimolar amount of chloro(tert-butyl)phenylphosphine instead of diphenylphosphine chloride, while the other steps are the same as in Example 1.

[0096] After the reaction was completed, the catalyst was separated by filtration under nitrogen protection. The catalyst was then recycled five times under the same hydroformylation process conditions. The results are as follows:

[0097]

[0098] The results of Comparative Examples 1-2 show that not any phosphine ligand can result in high activity of the supported catalyst. Only by using one of the following phosphine ligands—diphenylphosphine chloride, di-p-tolylphosphine chloride, bis(2,4,6-trimethylphenyl)phosphine chloride, or bis(3,5-dimethyl-4-methoxyphenyl)phosphine chloride—can the activity stability of the supported catalyst be improved, and its activity will not decrease significantly even 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 separated by filtration under nitrogen protection. The catalyst was then recycled five times under the same hydroformylation process conditions. 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 separated by filtration under nitrogen protection. The catalyst was then recycled five times under the same hydroformylation process conditions. The results are as follows:

[0106]

[0107] As shown in Comparative Examples 3-4, both impregnation time and temperature affect the distribution and stability of the active material, thus influencing the catalyst performance. Therefore, controlling the impregnation temperature and time within the range defined in this invention is beneficial for improving 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 of intermediate B is 0.2%, and the other steps are the same as in Example 1.

[0110] After the reaction was completed, the catalyst was separated by filtration under nitrogen protection. The catalyst was then recycled five times under the same hydroformylation process conditions. 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 of intermediate B is 5%, while the other steps are the same as in Example 1.

[0114] After the reaction was completed, the catalyst was separated by filtration under nitrogen protection. The catalyst was then recycled five times under the same hydroformylation process conditions. The results are as follows:

[0115]

[0116] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention and are not intended to limit the scope of protection of the present invention. Although the present invention has been described in detail with reference to preferred embodiments, those skilled in the art should understand that modifications or equivalent substitutions can be made to the technical solutions of the present invention without departing from the essence and scope of the technical solutions of the present invention.

Claims

1. A supported catalyst, characterized in that, It includes intermediate B and a rhodium- or cobalt-containing compound supported on intermediate B, wherein the loading of the rhodium- or cobalt-containing compound on intermediate B is 0.5-2%; The structure of intermediate B is shown below: ;where R 1 R 2 The same phenyl, p-tolyl, 2,4,6-trimethylphenyl or 3,5-dimethyl-4-methoxyphenyl; m and n are the degree of polymerization, and m and n are integers between 100 and 1000.

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

3. The supported catalyst as described in claim 2, characterized in that, The immersion temperature is 25-120℃, and the immersion time is 1-8 hours.

4. The supported catalyst as described in claim 1, characterized in that, The rhodium or cobalt-containing compounds include at least one of rhodium trichloride, rhodium acetate, rhodium sulfate, dimeric (1,5-cyclooctadiene) rhodium chloride, dimeric rhodium acetate, rhodium nitrate, carbonyl rhodium, dicarbonyl acetylacetone rhodium, acetylacetone (1,5-cyclooctadiene) rhodium, dicarbonyl rhodium chloride dimer, tris(m-triphenylphosphine trisulfonate sodium salt) chlorocarbonyl rhodium, tris(m-triphenylphosphine trisulfonate sodium salt) hydroxyl rhodium carbonyl, carbonyl cobalt, and bis(triphenylphosphine) cobalt dibromide.

5. The supported catalyst as described in claim 1, characterized in that, The preparation method of the intermediate B includes the following steps: (1) Poly(styrene-4-chloromethylstyrene) is added to an alkaline solution for hydrolysis to obtain intermediate A, wherein the molar ratio of poly(styrene-4-chloromethylstyrene) to alkaline solution is 1:(2-10). (2) Intermediate A is reacted with sodium iodide and disubstituted phosphine chloride to obtain intermediate B; the molar ratio of intermediate A, sodium iodide and disubstituted phosphine chloride is 1:(2-10):(2-8).

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

7. The supported catalyst as described in claim 5, characterized in that, The reaction temperature during hydrolysis in step (1) is 50-120℃, and the reaction time is 6-18h.

8. The supported catalyst as described in claim 5, characterized in that, In step (2), the disubstituted phosphine chloride is one of diphenylphosphine chloride, di-p-tolylphosphine chloride, bis(2,4,6-trimethylphenyl)phosphine chloride, and bis(3,5-dimethyl4-methoxyphenyl)phosphine chloride.

9. The supported catalyst as described in claim 5, characterized in that, The reaction temperature in step (2) is 25-100℃ and the reaction time is 2-16h.

10. The application of the supported catalyst according to any one of claims 1-9 in the hydroformylation reaction to synthesize isononanal, characterized in that, Includes the following steps: An olefin and a supported catalyst were added to the reactor, nitrogen was used to replace the catalyst and syngas was introduced. The reactor was heated to carry out a hydroformylation reaction. After the reaction was completed, the mixture was filtered to obtain isononal.

11. The application of the supported catalyst as described in claim 10 in the hydroformylation reaction to synthesize isononanal, characterized in that, The reaction temperature is 25-150℃, the reaction time is 2-18 h, and the reaction pressure is 0.5-30 MPa.

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