A process for the hydroformylation of propylene or derivatives thereof

Abstract

The application discloses a solid-phase catalyst for propylene and its derivatives hydroformylation reaction and a preparation method and application thereof. The solid-phase catalyst takes phosphine-containing organic polymer as a carrier and takes metal Rh, Co, Ir, Pd or Pt as an active component. The phosphine-containing organic polymer carrier is formed by self-polymerization of an olefin-based functionalized organic phosphine ligand or mixed polymerization of the olefin-based functionalized organic phosphine ligand and a monodentate organic phosphine ligand. The polymer with high ligand concentration is obtained by adopting a bulk polymerization, solution polymerization, suspension polymerization or emulsion polymerization method. The obtained phosphine-containing organic polymer carrier is added into a solution containing the active component Rh, Co, Ir, Pd or Pt precursor, and is fully stirred and vacuum-extracted to remove the solvent, so that the high-efficiency solid-phase catalyst suitable for propylene and its derivatives hydroformylation can be obtained. The catalyst is suitable for propylene and its derivatives (propenoic acid and ester, propenol, propenyl ether and the like) hydroformylation reaction, and has the characteristics of strong substrate applicability, good catalyst stability, high activity and selectivity.

Description

Technical Field

[0001] This invention belongs to the field of heterogeneous catalysis, specifically relating to a solid-phase catalyst for the hydroformylation reaction of propylene and its derivatives, its preparation method, and its application. Background Technology

[0002] Aldehydes are very useful chemical intermediates, and their subsequent conversion products, such as alcohols, acids, esters, and fatty amines, are all very important fine chemical products, widely used as organic solvents, plasticizers, and surfactants.

[0003] Propylene and its derivatives are important C3 platform compounds, and their hydroformylation into higher value-added aldehydes, alcohols, and diols is of great significance. Currently, the world produces approximately 10 million tons of aldehydes annually through hydroformylation, of which about 50% is butyraldehyde, produced from the hydroformylation of propylene. The recovery and reuse of catalysts in industrially applied technologies are difficult, resulting in significant loss of metals and ligands, and high production costs.

[0004] To facilitate the recycling of catalysts, a great deal of work has been done in the field of heterogeneous catalysis of hydroformylation catalysts. However, traditional heterogeneous catalysis methods have revealed a series of problems that need to be solved and overcome, especially the problem of insufficient catalyst stability after heterogeneity (J.Mol.Catal.A-Chem.,2002,182:107-123; Eur.J.Org.Chem.,2012,2012:6309-6320).

[0005] The aldehydes produced by the hydroformylation of propylene and its derivatives (acrylic acid and esters, allyl alcohol, allyl ether, etc.) are a mixture of normal and isoaldehydes. The plasticizers, surfactants, and glycols subsequently prepared from normal aldehydes exhibit superior properties. From this perspective, normal aldehydes are the desired product. Therefore, improving the ratio of normal to isoaldehydes in the product is a crucial issue. Summary of the Invention

[0006] To address the aforementioned problems, the present invention aims to provide a solid-phase catalyst for the hydroformylation reaction of propylene and its derivatives, its preparation method, and its application.

[0007] The technical solution of this invention is as follows:

[0008] A solid-phase catalyst for the hydroformylation reaction of propylene and its derivatives, wherein the solid-phase catalyst uses a phosphine-containing organic polymer as a support and one or two of metals Rh, Co, Ir, Pd or Pt as active components.

[0009] The phosphine-containing organic polymer carrier is obtained by self-polymerization of olefin-functionalized polydentate organophosphine ligands through bulk polymerization, solution polymerization, suspension polymerization or emulsion polymerization, or by blending with olefin-functionalized monodentate organophosphine ligands.

[0010] The obtained phosphine-containing organic polymer support is added to a solution containing active components Rh, Co, Ir, Pd or Pt precursors, and the mixture is stirred thoroughly to coordinate, thus obtaining a highly efficient solid-phase catalyst suitable for the hydroformylation of propylene and its derivatives.

[0011] The catalyst has a metal loading range of 0.01–10 wt%, and the olefinic functional group in the phosphine ligand used for polymerization is a vinyl functional group.

[0012] Preferably, the olefin-functionalized monodentate organophosphorus ligand is a vinyl-containing triphenylphosphorus ligand, and the olefin-functionalized polydentate organophosphorus ligand is a vinyl-containing bidentate organophosphorus ligand.

[0013] The olefin-containing multidentate organophosphorus ligands (one or more of AJ) and the synthetic routes are as follows:

[0014]

[0015]

[0016] The olefin-containing monodentate organophosphorus ligand is selected from one or more of the following:

[0017]

[0018]

[0019]

[0020]

[0021] The organic polymer carrier has a hierarchical porous structure and a specific surface area of ​​10–3000 m². 2 / g, preferably in the range of 100–1000m 2 / g, pore volume 0.1~10.0cm³ 3 / g, preferably 0.5~2.0cm 3 / g, with a pore size distribution of 0.01–100.0 nm, preferably 0.5–5.0 nm;

[0022] The metal loading of the active component in the catalyst ranges from 0.01 to 10 wt%, with a preferred range of 0.1 to 2 wt%.

[0023] The preparation method of the phosphine-containing organic polymer support is as follows: after fully dissolving and mixing the multidentate organophosphine ligand and / or monodentate organophosphine ligand, the olefin group in the organophosphine ligand is polymerized by solvothermal polymerization using a free radical initiator to generate a phosphine-containing organic polymer support with a hierarchical porous structure.

[0024] The solid-phase catalyst is prepared by stirring the precursor of the active metal component and the phosphorus-containing organic polymer support in a solvent. The active metal component and the exposed P in the phosphorus-containing organic polymer support form a strong coordination bond. After evaporating the solvent, a solid-phase catalyst suitable for the hydroformylation reaction of propylene and its derivatives is obtained.

[0025] The specific preparation steps of the solid-phase catalyst are as follows:

[0026] a) Under an inert gas atmosphere of 273–473 K, add monodentate organophosphorus ligands and / or polydentate organophosphorus ligands, with or without crosslinking agents, and then add free radical initiators to the solvent, and stir the mixture for 0.1–100 hours to obtain a prepolymer solution, with the preferred stirring time range being 0.1–20 hours;

[0027] b) Transfer the prepolymer mixture obtained in step a) to a high-pressure reactor for polymerization. Under an inert gas atmosphere of 273–473 K, allow it to stand or stir for 1–100 hours to obtain a phosphine-containing organic polymer.

[0028] c) The phosphine-containing organic polymer obtained in step b) is subjected to vacuum removal of solvent at room temperature to obtain an organic polymer containing exposed P with a hierarchical porous structure, which is the support for the solid-phase catalyst.

[0029] d) Under an inert gas atmosphere of 273–473 K, in a solvent containing an active metal precursor (the concentration of the active metal in the precursor solution ranges from 0.001 to 1 mol L). -1 Add the organic polymer support obtained in step c), stir for 0.1 to 100 hours, preferably 0.1 to 20 hours, and then remove the solvent under vacuum at room temperature to obtain a solid-phase catalyst for the hydroformylation reaction of propylene and its derivatives.

[0030] The solvent mentioned in steps a) and d) is one or more of water, methanol, ethanol, dichloromethane, chloroform, benzene, toluene, xylene or tetrahydrofuran;

[0031] The crosslinking agent mentioned in step a) is one or more of styrene, divinylbenzene, tristyrene, ethylene, propylene, or butadiene; the free radical initiator is one or more of tert-butyl hydroperoxide, azobisisobutyronitrile, azobisisoheptanenitrile, cyclohexanone peroxide, or benzoyl peroxide.

[0032] The molar ratio of monodentate organophosphorus ligands to multidentate organophosphorus ligands in step a) is 0.01:1 to 100:1, preferably 1:1 to 100:1. When a crosslinking agent is added, the molar ratio of monodentate organophosphorus ligands to crosslinking agents is 0.01:1 to 10:1, preferably 0.1:1 to 1:1. The molar ratio of monodentate organophosphorus ligands to free radical initiators is 300:1 to 10:1, preferably 100:1 to 10:1. Before polymerization into an organic polymer, the concentration of monodentate organophosphorus ligands in the solvent ranges from 0.01 to 1000 g / L, preferably 0.1 to 10 g / L. The inert gas mentioned in steps a), b), and d) is selected from one or more of Ar, He, N2, and CO2.

[0033] The active component is one or more of Rh, Co, Ir, Pd, or Pt, wherein the precursor of Rh is one or more of RhH(CO)(PPh3)3, Rh(CO)2(acac), RhCl3, and Rh(CH3COO)2; the precursor of Co is one or more of Co(CH3COO)2, Co(CO)2(acac), Co(acac)2, and CoCl2; and the precursor of Ir is Ir(CO)3(acac), Ir(C The catalyst contains one or more of the following: H3COO)3, Ir(acac)3, and IrCl4; the precursor of Pd is one or more of the following: Pd(CH3COO)2, Pd(acac)2, PdCl2, Pd(PPh3)4, and PdCl2(CH3CN)2; the precursor of Pt is one or more of the following: Pt(acac)2, PtCl4, and PtCl2(NH3)2; the metal loading in the catalyst ranges from 0.01 to 10 wt%, preferably from 0.1 to 2 wt%.

[0034] A solid-phase catalyst for the hydroformylation of propylene and its derivatives is loaded into a reactor. A reaction mixture and raw materials propylene or propylene derivatives (acrylic acid and esters, propylene alcohol, propylene ethers, etc.) are introduced. The main components of the mixture are H2 and CO, with the volume content of H2+CO being 20-90%, the H2 / CO volume ratio being 0.5-5.0, and the gas space velocity being 100-20000 h⁻¹. -1 (The preferred range is 1000~20000h) -1 The raw material propylene or propylene derivative has a purity of 0.1% to 100% and a liquid hourly space velocity of 0.01 to 10.0 h⁻¹. -1 The hydroformylation reaction is carried out at a reaction temperature of 323–573 K and a reaction pressure of 0.1–10.0 MPa. The reactor can be a fixed-bed reactor, a fluidized-bed reactor, or a slurry-bed reactor.

[0035] This invention provides a solid-phase catalyst for the hydroformylation of propylene and its derivatives, characterized by good stability, high activity, and high selectivity. Furthermore, the performance of the prepared catalyst can be controlled by adjusting various parameters during catalyst preparation to make it suitable for different reaction substrates and hydroformylation processes.

[0036] The reaction principle of this invention:

[0037] The vinyl-functionalized polydentate phosphine ligands designed in this invention exhibit strong steric hindrance. Simultaneously, the electron-withdrawing groups attached to the phosphorus (P) endow the polydentate ligands with suitable electronic and steric effects. The organic polymer backbone formed by the self-polymerization of the vinyl polydentate phosphine ligands or copolymerization with vinyl monodentate phosphine ligands contains a large number of exposed phosphorus atoms with lone pairs of electrons, which can form multiple P-metal coordination bonds with the empty orbitals of transition active metal ions, thereby forming catalytically active sites. These multiple coordination bonds prevent the loss of the metal active component, endowing the catalyst with high stability and significantly extending its lifetime. The active metal component is highly dispersed in the phosphine-containing organic polymer support in a single-atom form, greatly improving the metal utilization efficiency and significantly enhancing the catalyst activity. The significant steric effects of the polydentate and monodentate phosphine ligands in the backbone allow the prepared catalyst to significantly improve the regioselectivity of the hydroformylation product aldehyde, resulting in a higher proportion of n-aldehydes in the product.

[0038] The beneficial effects of this invention are as follows:

[0039] This invention provides a solid-phase catalyst for the hydroformylation of propylene and its derivatives, suitable for bubble bed, slurry bed, fixed bed, and trickle bed reaction processes. In the hydroformylation of propylene and its derivatives, it significantly improves conversion rate and selectivity for n-aldehydes, solving long-standing problems such as poor stability and selectivity, and severe metal component loss, in the heterogeneous process of olefin hydroformylation catalysts. Based on this new reaction process using a solid-phase catalyst, the product aldehyde exhibits a high n-to-iso ratio, good catalyst stability, and simple and efficient separation of reactants and products from the catalyst, greatly reducing the cost of industrial production of olefin hydroformylation and providing a new industrial technology for the hydroformylation of propylene and its derivatives.

[0040] Furthermore, another beneficial effect of this invention is that the upper half of the olefin functionalization of the 10 vinyl polydentate phosphine ligands designed in the claims is the same for AE, and we have already established the industrial preparation steps. The upper half of FJ is also the same, and we can already produce them in the factory. Therefore, compared with the patents previously filed by our research group, the 10 key vinyl polydentate ligands involved in this patent have significant cost advantages, and the synthetic routes are relatively simple, with significantly higher yields than previous schemes. Attached Figure Description

[0041] Figure 1 Synthetic routes for the 10 vinyl polydentate phosphine ligands involved in the claims.

[0042] Figure 2 yes Figure 1 Schematic diagram of the self-polymerization technology route of F-multidentate phosphine ligands.

[0043] Figure 3 This is a schematic diagram of a typical crosslinking agent used in polymerization.

[0044] Figure 4 The N2 physical adsorption curve is the solid-phase catalyst obtained in Example 1.

[0045] Figure 5 This is a pore size distribution diagram of the solid catalyst obtained in Example 1. Detailed Implementation

[0046] The following embodiments provide a better illustration of the present invention, but do not limit the scope of protection of the present invention.

[0047] Example 1

[0048] The preparation method of the organophosphine ligand polymer support is as follows: Under a protective atmosphere of Ar gas at 298 K, 1.0 g of vinyldiphosphine ligand (product F in the attached figure) and 50 g of monodentate ligand tris(4-vinylphenyl)phosphine were dissolved in 500.0 ml of tetrahydrofuran solvent. 0.01 g of free radical initiator azobisisobutyronitrile was added to the above solution, and the mixture was stirred for 2 hours to obtain a prepolymer. The prepolymer was transferred to an autoclave and polymerized at 373 K under a protective atmosphere of Ar gas using a solvothermal polymerization method for 24 h. After the polymerization reactor cooled to room temperature, the solvent was removed under vacuum at room temperature to obtain a phosphine-containing organic polymer support copolymerized from the diphosphine ligand and the tris(4-vinylphenyl)phosphine organic monomer.

[0049] Solid-phase catalyst for the hydroformylation of propylene and its derivatives: 3.13 mg of rhodium acetylacetone carbonyl (Rh(CO)2(acac)) was dissolved in 10.0 ml of tetrahydrofuran solvent, and 1.0 g of the phosphine-containing organic polymer prepared above was added. The mixture was stirred at 298 K and under an inert Ar atmosphere for 15 hours. The solvent was removed under vacuum at room temperature to obtain a solid-phase catalyst suitable for the hydroformylation of propylene and its derivatives. This catalyst is a multi-coordinated solid-phase catalyst.

[0050] Example 2

[0051] In Example 2, the polymer support preparation steps were identical to those in Example 1, except that 50.0 g of vinyldiphosphine ligand (product F in the attached figure) was weighed out and the comonomer tris(4-vinylphenyl)phosphine was not added. Figure 2 This is a schematic diagram of the self-polymerization route of diphosphine ligand F.

[0052] Example 3

[0053] In Example 3, except that 0.005 g of the free radical initiator azobisisobutyronitrile was weighed out to replace 0.01 g of the free radical initiator azobisisobutyronitrile, the rest of the catalyst preparation process was the same as in Example 1.

[0054] Example 4

[0055] In Example 4, the catalyst preparation process was the same as in Example 1, except that 50.0 ml of tetrahydrofuran solvent was used instead of 500.0 ml of tetrahydrofuran solvent.

[0056] Example 5

[0057] In Example 5, the catalyst preparation process was the same as in Example 1, except that 500.0 ml of dichloromethane solvent was used instead of 500.0 ml of tetrahydrofuran solvent.

[0058] Example 6

[0059] In Example 6, the catalyst preparation process was the same as in Example 1, except that the polymerization temperature was replaced with 353K instead of 373K.

[0060] Example 7

[0061] In Example 7, the catalyst preparation process was the same as in Example 1, except that a 6-hour polymerization time was used instead of a 24-hour polymerization time.

[0062] Example 8

[0063] In Example 8, except for the addition of 10.0 g of styrene as a crosslinking agent, the rest of the catalyst preparation process was the same as in Example 1.

[0064] Example 9

[0065] In Example 9, the catalyst synthesis process was the same as in Example 1, except that the same number of moles of cobalt dicarbonyl acetylacetone were used to replace rhodium carbonyl acetylacetone in 10.0 ml of tetrahydrofuran solvent.

[0066] Example 10

[0067] In Example 10, the catalyst synthesis process was the same as in Example 1, except that the same number of moles of acetylacetone tricarbonyl iridium were weighed to replace acetylacetone carbonyl rhodium and dissolved in 10.0 ml of tetrahydrofuran solvent.

[0068] Example 11

[0069] In Example 11, the catalyst synthesis process was the same as in Example 1, except that the same number of moles of palladium dichloride were used to replace rhodium carbonyl acetylacetone in 10.0 ml of tetrahydrofuran solvent.

[0070] Example 12

[0071] In Example 12, 1.0g of the attached... Figure 1 In this example, A replaces the diphosphine ligand in Example 1, and the rest of the catalyst synthesis process is the same as in Example 1.

[0072] Example 13

[0073] In Example 13, 1.0g of the attached material was weighed. Figure 1 In this example, B replaces the diphosphine ligand in Example 1, and the rest of the catalyst synthesis process is the same as in Example 1.

[0074] Example 14

[0075] In Example 14, 1.0g of the attached... Figure 1 The C in this example replaces the diphosphine ligand in Example 1, and the rest of the catalyst synthesis process is the same as in Example 1.

[0076] Example 15

[0077] In Example 15, 1.0g of the attached material was weighed. Figure 1 The D in this example replaces the diphosphine ligand in Example 1, and the rest of the catalyst synthesis process is the same as in Example 1.

[0078] Example 16

[0079] In Example 16, 1.0g of the attached material was weighed. Figure 1 In this example, E replaces the diphosphine ligand in Example 1, and the rest of the catalyst synthesis process is the same as in Example 1.

[0080] Example 17

[0081] In Example 17, 1.0g of the attached material was weighed. Figure 1 In this example, G replaces the diphosphine ligand in Example 1, and the rest of the catalyst synthesis process is the same as in Example 1.

[0082] Example 18

[0083] In Example 18, 1.0g of the attached... Figure 1The H in the catalyst is used to replace the diphosphine ligand in Example 1, and the rest of the catalyst synthesis process is the same as in Example 1.

[0084] Example 19

[0085] In Example 19, 1.0g of the attached... Figure 1 The I in Example 1 replaces the diphosphine ligand, and the rest of the catalyst synthesis process is the same as in Example 1.

[0086] Example 20

[0087] In Example 20, 1.0g of the attached... Figure 1 J replaces the diphosphine ligand in Example 1, and the rest of the catalyst synthesis process is the same as in Example 1.

[0088] Example 21

[0089] In Example 21, we prepared a conventional Rh / SiO2 supported catalyst. The specific preparation steps were as follows: 3.13 mg of rhodium acetylacetone carbonyl (Rh(CO)2(acac)) was weighed and dissolved in 10.0 ml of tetrahydrofuran solvent. 1.0 g of 100-mesh SiO2 (purchased from Qingdao Ocean Chemical Plant) was added. This mixture was stirred at 298 K under an inert gas atmosphere for 24 hours. The solvent was then removed under vacuum at room temperature to obtain the conventional Rh / SiO2 supported catalyst.

[0090] Example 22

[0091] 0.2 g of the catalyst synthesized in Examples 1-21 was placed in a fixed-bed reactor, and the space velocity of the reactants (C3H6:CO:H2 = 1:1:1) was controlled at 1000 h⁻¹. -1 The reaction was conducted at 110℃ and 1 MPa. The product was collected in an ice-bath cooled collection tank (maintained at 263K). The obtained liquid product was analyzed by HP-7890N gas chromatography equipped with an HP-5 capillary column and an FID detector, using n-propanol as an internal standard. The tail gas from the collection tank was analyzed online by HP-7890N gas chromatography equipped with a Porapak-QS column and a TCD detector. The reaction results are listed in Table 1.

[0092] Table 1. Specific surface area of ​​catalysts synthesized in Examples 1-21 and results of propylene hydroformylation reaction

[0093]

[0094]

[0095] Table 1 shows that for this type of solid-phase catalyst, the active component Rh exhibits the best hydroformylation performance for propylene. Under the same reaction conditions, the hydroformylation activity of the traditional supported Rh / SiO2 catalyst is only about one-sixth that of the self-supported metal catalyst containing phosphine organic polymers, and the positive-to-sero-to-negative ratio of the aldehyde is also lower.

[0096] Example 23

[0097] The catalyst synthesized in Example 1 was placed in a trickle bed continuous reactor with a catalyst loading of 0.2 g and the synthesis gas (CO:H2 = 1:1) space velocity controlled at 2000 h⁻¹. -1 The liquid flow rate of propylene derivatives was controlled at 0.6 h / min. -1 The reaction temperature was controlled at 100℃ and the reaction pressure at 1MPa. The reaction results are listed in Table 2.

[0098] Table 2. Results of hydroformylation of propylene derivatives

[0099]

[0100]

Claims

1. A method for the hydroformylation reaction of propylene derivatives, characterized in that... In the presence of a solid-phase catalyst, propylene derivatives undergo selective hydrogenation; the propylene derivatives are selected from one or more of acrylic acid, acrylates, allyl alcohol, and allyl ethers, wherein the acrylates are selected from methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, and n-butyl acrylate, and the allyl ethers are selected from methacrylic ether, ethylacrylic ether, n-propylacrylic ether, isopropylacrylic ether, and allyl phenyl ether. The solid-phase catalyst uses a phosphine-containing organic polymer as a support and one or two of the metals Rh, Co, Ir, Pd or Pt as active components. The phosphine-containing organic polymer carrier is obtained by copolymerization of olefin-functionalized polydentate organophosphine ligands with olefin-functionalized monodentate organophosphine ligands through solution polymerization, suspension polymerization, or emulsion polymerization. The obtained phosphine-containing organic polymer support is added to a solution containing a precursor with active components, and the mixture is stirred for coordination to obtain a solid-phase catalyst suitable for the hydroformylation of propylene and its derivatives. The metal loading in the catalyst ranges from 0.01 to 10 wt%. The olefin-functionalized multidentate organophosphorus ligand used in the polymerization has a vinyl functional group in the olefin group; the olefin-functionalized multidentate organophosphorus ligand is a dipentate organophosphorus ligand containing a vinyl group. The olefin-containing monodentate organophosphorus ligand is: , The synthetic route for the olefin-containing polydentate organophosphorus ligand F is as follows: , The molar ratio of the monodentate organophosphorus ligand to the polydentate organophosphorus ligand is 0.01:1 to 100:

1.

2. The method according to claim 1, characterized in that: The molar ratio of the monodentate organophosphorus ligand to the polydentate organophosphorus ligand is 1:1 to 100:1; The metal loading in the catalyst ranges from 0.1 to 2 wt%.

3. The method according to claim 1, characterized in that: The organic polymer carrier has a hierarchical porous structure and a specific surface area of ​​10~3000 m². 2 / g, pore volume 0.1~10.0cm³ 3 / g, pore size distribution is 0.01~100.0nm; The metal loading of the active component in the catalyst ranges from 0.01 to 10 wt%.

4. The method according to claim 1, characterized in that: The organic polymer carrier has a hierarchical porous structure and a specific surface area of ​​100~1000 m². 2 / g, pore volume 0.5~2.0cm 3 / g, pore size distribution is 0.5~5.0nm; The metal loading of the active component in the catalyst ranges from 0.1 to 2 wt%.

5. The method according to claim 1, characterized in that: The specific preparation steps of the solid-phase catalyst are as follows: a) Under an inert atmosphere of 273~473K, add multidentate organophosphorus ligands and monodentate organophosphorus ligands to a solvent, with or without adding a crosslinking agent and a free radical initiator, and stir the mixture for 0.1~100 hours to obtain a prepolymer solution, with the preferred stirring time range being 0.1~20 hours; b) Transfer the prepolymer mixed solution obtained in step a) to a high-pressure reactor for polymerization. Under an inert atmosphere of 273~473K, allow it to stand or stir for 1~100 hours to carry out the polymerization reaction and obtain the phosphine-containing organic polymer. c) Remove the solvent from the phosphine-containing organic polymer obtained in step b), and you will get an organic polymer containing bare P with a hierarchical porous structure, which is the support for the solid-phase catalyst. d) Under an inert gas atmosphere of 273–473 K, the organic polymer support obtained in step c) is added to a solvent containing an active metal component precursor, and the mixture is stirred for 0.1–100 hours. Afterward, the solvent is removed to obtain a solid-phase catalyst for the hydroformylation of propylene and its derivatives, wherein the concentration of the active metal in the precursor solution ranges from 0.001 to 1 mol L. -1 .

6. The method according to claim 5, characterized in that: The stirring time in step d) is 0.1 to 20 hours.

7. The method according to claim 5, characterized in that: The solvent mentioned in steps a) and d) is one or more of water, methanol, ethanol, dichloromethane, chloroform, benzene, toluene, xylene or tetrahydrofuran; The crosslinking agent mentioned in step a) is one or more of styrene, divinylbenzene, pyrostristyrene, ethylene, propylene, or butadiene; the free radical initiator is one or more of tert-butyl hydroperoxide, azobisisobutyronitrile, azobisisoheptanenitrile, cyclohexanone peroxide, or benzoyl peroxide. The molar ratio of monodentate organophosphorus ligands to polydentate organophosphorus ligands in step a) is 0.01:1 to 100:

1. With the addition of a crosslinking agent, the molar ratio of monodentate organophosphorus ligand to crosslinking agent is 0.01:1 to 10:

1. The molar ratio of the multidentate organophosphorus ligand to the free radical initiator is 300:1 to 10:

1. Before polymerization into organic polymers, the concentration of the multidentate organophosphorus ligand in the solvent ranges from 0.01 to 1000 g / L. The inert atmosphere gas described in steps a), b), and d) is selected from one or more of Ar, He, N2, and CO2.

8. The method according to claim 7, characterized in that: The molar ratio of monodentate organophosphorus ligands to polydentate organophosphorus ligands in step a) is 1:1 to 100:1; When a crosslinking agent is added, the molar ratio of monodentate organophosphorus ligand to crosslinking agent is 0.1:1 to 1:1; The molar ratio of the multidentate organophosphorus ligand to the free radical initiator is 100:1 to 10:1; Before polymerization into organic polymers, the concentration of multidentate organophosphorus ligands in the solvent ranges from 0.1 to 10 g / L.

9. The preparation method according to claim 5, characterized in that: The active component is one or more of Rh, Co, Ir, Pd, or Pt, wherein the precursor of Rh is one or more of RhH(CO)(PPh3)3, Rh(CO)2(acac), RhCl3, and Rh(CH3COO)2; and the precursor of Co is Co(CH3COO)2, Co(CO)2(acac), or Co... One or more of (acac)2 and CoCl2; the precursor of Ir is one or more of Ir(CO)3(acac), Ir(CH3COO)3, Ir(acac)3, and IrCl4; the precursor of Pd is one or more of Pd(CH3COO)2, Pd(acac)2, PdCl2, Pd(PPh3)4, and PdCl2(CH3CN)2; the precursor of Pt is one or more of Pt(acac)2, PtCl4, and PtCl2(NH3)2; the metal loading in the catalyst ranges from 0.01 to 10 wt%.

10. The preparation method according to claim 9, characterized in that: The metal loading in the catalyst ranges from 0.1 to 2 wt%.

11. The method according to any one of claims 1-10, characterized in that: A solid catalyst is loaded into a reactor, and a reaction mixture and a propylene derivative are introduced. The main components of the mixture are H2 and CO, with the volume content of H2+CO being 20-100%, the H2 / CO volume ratio being 0.5-5.0, and the gas space velocity being 100-20000 h⁻¹. -1 The time space velocity of the feed liquid is 0.01~10.0 h⁻¹. -1 The hydroformylation reaction was carried out at a reaction temperature of 323~573K and a reaction pressure of 0.1~10.0MPa.

12. The method according to claim 11, characterized in that: Gas space velocity is 1000~20000h -1 .

13. The method according to claim 12, characterized in that: The gas mixture may or may not contain an inert atmosphere gas, selected from one or more of Ar, He, N2 and CO2; The reactor is a fixed-bed reactor, a fluidized-bed reactor, or a slurry-bed reactor.

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