Preparation and application of multi-substituent porous organic polymer catalyst

Abstract

The invention relates to preparation and application of a multi-substituent porous organic polymer catalyst. More specifically, the heterogeneous catalyst is composed of a metal active component and an organic polymer wherein the metal active component is one of metals Rh, Ru, Ir, Pd, Co or Cu; the multi-substituent porous organic polymer is a porous polymer generated by carrying out solvothermal copolymerization on a multi-substituent triaryl phosphine monomer. Substituent groups can influence dispersion force and electron transfer conditions in ligand molecules, and have remote regulation and control effects on metal site electron characteristics and steric hindrance, so that the catalytic performance of the catalyst is improved; the metal component and rich P atoms on the surface of the polymer carrier are coordinated to stably exist on the carrier, so that the heterogeneous catalyst shows excellent catalytic reaction activity and stability in the reaction, and the catalyst is easy to separate from reactants and products, and has great industrial application prospects.

Description

Technical Field

[0001] This invention relates to the preparation and application of a multi-substituted porous organic polymer catalyst, belonging to the fields of heterogeneous catalysis and fine chemical technology. Background Technology

[0002] In recent years, porous organic polymers have been widely used as a novel material in gas storage, energy storage, catalysis, and other fields. Porous organic polymers possess advantages such as high specific surface area, hierarchical pore structure, excellent thermal stability, and high density of exposed coordination atoms within the polymer backbone, making them a promising candidate for heterogeneous catalysis.

[0003] Triphenylphosphine is a commonly used ligand in organic synthesis and industrial production. The preparation of porous organic polymers by vinylation of triphenylphosphine followed by solvothermal polymerization, and then loading them with active metal precursors to prepare catalysts, has become an emerging research area in recent years. However, traditional triphenylphosphine polymers have poor π-electron acceptor ability and limited steric hindrance effects, meaning their catalytic performance can only be controlled by changing the loading amount or doping agents, which severely limits their widespread application. Summary of the Invention

[0004] To address the aforementioned problems, the present invention aims to provide a method for preparing and applying a multi-substituted porous organic polymer catalyst.

[0005] The solid catalyst is characterized by comprising a metallic active component and a multi-substituted porous organic polymer, wherein the metallic active component is one of the metals Rh, Ru, Ir, Pd, Cu, or Co; and the multi-substituted porous organic polymer is a porous polymer generated by solvothermal copolymerization of multi-substituted triarylphosphine monomers. The substituents can affect the intramolecular dispersion forces and electron transfer of the ligand molecules, and have a long-range regulatory effect on the electronic properties and steric hindrance of the metal sites, thereby improving the catalytic activity of the catalyst.

[0006] In one embodiment, the metal active component accounts for 0.01%-20% of the total weight of the solid catalyst;

[0007] In one embodiment, the multi-substituted triarylphosphine monomer is selected from one or more of the following L1-L114 phosphine-containing ligands:

[0008]

[0009]

[0010]

[0011] In one embodiment, the porous organic polymer has a specific surface area of ​​200-2000 m². 2 / g, pore volume 0.1-5.0cm 3 / g, with a pore size distribution of 0.4-100.0nm.

[0012] In one embodiment, the preparation method of the solid catalyst includes the following steps: under an inert gas atmosphere, a) at 263-473 K, a free radical initiator is added to a solvent of a polysubstituted triarylphosphine monomer, and the mixture is stirred for 0.5-96 h; b) at 293-473 K, the solution from step a) is hydrothermally polymerized in a hydrothermal autoclave under an inert gas atmosphere for 0.5-96 h. After polymerization, the solvent is removed under vacuum at 283-473 K, resulting in a porous organic polymer; c) under an inert gas atmosphere, at 273-473 K, the above polymer and the metal active component are added to a solvent, and the mixture is stirred for 0.5-100 h. After stirring, the solvent is removed under vacuum at 273-473 K, resulting in a heterogeneous catalyst.

[0013] The solvents used in steps a) and c) above are one or more of benzene, toluene, tetrahydrofuran, methanol, ethanol, dichloromethane, dichloroethane, or deionized water; the free radical initiator used in step a) is one or more of cyclohexanone peroxide, benzoyl peroxide, tert-butyl hydroperoxide, azobisisobutyronitrile, or azobisisoheptanenitrile.

[0014] The solvent mentioned in step c) is one or more of water, benzene, toluene, tetrahydrofuran, methanol, ethanol, dichloromethane, or trichloromethane; the active component is one or more of Rh, Ru, Ir, Pd, Co, or Cu; wherein the precursor of Rh is one or more of Rh(CH3COO)2, RhH(CO)(PPh3)3, Rh(CO)2(acac), or RhCl3; and the precursor of Ru is Ru3(CO). 12 The catalyst contains one or more of the following: RuCl3, Rh(acac)3; Ir precursors include one or more of Ir(CO)3(acac), Ir(CH3COO)3, Ir(acac)3, and IrCl4; Pd precursors include one or more of PdCl2, Pd(CH3COO)2, and Pd(acac)2; Co precursors include one or more of Co(CH3COO)2, Co(CO)2(acac), Co(acac)2, and CoCl2; Cu precursors include one or more of Cu(CH3COO)2, Cu(acac)2, CuCl, and CuCl2. The metal loading in the catalyst ranges from 0.01 to 10 wt%.

[0015] In one embodiment, the weight ratio of the free radical initiator to the organic ligand is 1:600-1:5 (preferably 1:100-1:20).

[0016] The inert atmosphere gas mentioned above is one or more of nitrogen, argon, and helium.

[0017] This invention introduces multiple groups with different electronegativity or steric hindrance effects onto the benzene ring of a typical monodentate phosphine ligand, such as triphenylphosphine, using a multi-substituted triarylphosphine ligand as the monomer. The polymer is then polymerized in an autoclave using a solvothermal polymerization method to form a porous organic polymer with a high surface area and a hierarchical pore structure. Because this organic polymer backbone has a large number of exposed phosphorus atoms containing lone pairs of electrons, it can act as a catalyst support to form multiple coordination bonds with active transition metals, thereby forming catalytically active sites. In this catalyst, the multi-substituted porous organic polymer simultaneously possesses the dual functions of support and ligand. The active metal component is highly dispersed in this support, forming multiple coordination bonds with a high concentration of exposed phosphorus. The active metal component is highly dispersed in the organophosphine polymer support in a single-atom form, greatly improving the metal utilization efficiency and preventing the active component from being lost, resulting in a long catalyst lifetime. The multiple substituents in the backbone endow the catalyst with strong π-electron acceptor ability and steric hindrance effect, and the prepared catalyst can significantly improve reaction activity and regioselectivity.

[0018] Substituents can affect the dispersion forces and electron transfer within ligand molecules, and have a remote control effect on the electronic properties and steric hindrance of metal sites, thereby improving the catalytic performance of the catalyst. The metal component exists stably on the support by coordinating with the abundant P atoms on the surface of the polymer support, thus enabling the heterogeneous catalyst of the present invention to exhibit excellent catalytic activity and stability in the reaction. Furthermore, the catalyst is easy to separate from the reactants and products, and has great potential for industrial application.

[0019] The beneficial effects of this invention include, but are not limited to, the following:

[0020] The heterogeneous catalyst framework described in this invention contains multi-substituted monodentate organophosphorus ligand structural units. The polymer surface has a high degree of exposed phosphorus (P), and active metal ions form multiple coordination bonds with the exposed P on the polymer, preventing the active components from easily leaching. The active components of the catalyst are Rh, Ru, Ir, Pd, Co, or Cu. This type of catalyst exhibits high reactivity. The polymer has a high specific surface area and a hierarchical porous structure, possessing the dual functions of a support and ligand. The active metal components may be highly dispersed in single-atom form within the pores or on the surface of the multi-substituted porous organic polymer support, improving the utilization efficiency of the metal components. It has broad prospects for industrial applications. Attached Figure Description

[0021] Figure 1 This is a schematic diagram of the heterogeneous catalyst synthesis route in Example 3 of this invention.

[0022] Figure 2These are the N2 adsorption-desorption isotherms and pore size distribution curves of the heterogeneous catalysts in Example 7 and Comparative Example 1 of this invention.

[0023] Figure 3 These are X-ray photoelectron spectroscopy (XPS)-Rh3d orbital electron binding energy diagrams of the heterogeneous catalysts in Examples 2, 3, and Comparative Example 1 of this invention. Detailed Implementation

[0024] To better illustrate the preparation method and application of the catalyst of the present invention, some examples of catalyst sample preparation and their application in reaction processes are given below, but the present invention is not limited to the listed examples. Unless otherwise specified, the "percentages" used in this application are based on weight.

[0025] Example 1

[0026] Under an argon protective atmosphere at 298 K, 10.0 g of L1 ligand was dissolved in 100 ml of tetrahydrofuran solvent. 0.25 g of azobisisobutyronitrile (AIBN) free radical initiator was added to the solution, and the mixture was stirred for 0.5 hours. The stirred solution was then transferred to a hydrothermal autoclave and polymerized at 373 K under an inert atmosphere (nitrogen) for 24 hours using a solvothermal method. After polymerization, the solution was cooled to 333 K, and the solvent was removed under vacuum at 333 K to obtain a multi-substituted porous organic polymer. The polymer has a specific surface area of ​​1020 m². 2 / g, pore volume 1.61cm 3 / g and the volume ratio of micropores (pores with a diameter of less than 2 nanometers) is 22.2%, with a pore size distribution of 0.4-100.0 nm.

[0027] Under a protective atmosphere of 298 K and inert gas (nitrogen), 6.3 mg of Rh(CO)₂(acac) was dissolved in 50 ml of tetrahydrofuran solvent, and 1.0 g of the polysubstituted porous organic polymer prepared above was added. The mixture was stirred for 24 hours. Subsequently, the solvent was removed under vacuum at 333 K to obtain a heterogeneous catalyst with a metal component supported on the porous organic polymer. The metal component content relative to the porous organic polymer was 0.25 wt%. The X-ray photoelectron spectroscopy (XPS) of the heterogeneous catalyst of this invention shows the Rh3d orbital electron binding energy. Figure 3 The Rh3d orbital electron binding energies of this catalyst are 308.44 and 312.44 eV, which are significantly higher than those of comparative examples 1-3. This indicates that the fluorine substituent has the ability to remotely regulate electrons, reducing the outer electron density of the Rh active site, thereby improving the catalyst's conversion, yield, and TOF.

[0028] Example 2

[0029] In Example 2, the catalyst preparation process and conditions were the same as in Example 1, except that 10.0 g of L3 ligand was used to replace 10.0 g of L1 ligand. The polymer had a specific surface area of ​​1310 m². 2 / g, pore volume 1.72cm 3 The catalyst has a micropore volume fraction of 23.4% and a pore size distribution ranging from 0.4 to 100.0 nm. The metal component content is 0.25 wt%. The Rh3d orbital electron binding energies of this catalyst are 308.50 and 312.50 eV, significantly higher than those of Comparative Examples 1-3 and Example 1. This indicates that the increased number of fluorine substituents further reduces the outer electron density of the Rh active sites, thereby further improving the catalyst's conversion, yield, and TOF.

[0030] Example 3

[0031] In Example 3, the catalyst preparation process and conditions were the same as in Example 1, except that 10.0 g of L7 ligand was used to replace 10.0 g of L1 ligand. The polymer had a specific surface area of ​​1350 m². 2 / g, pore volume 1.76cm 3 The catalyst has a micropore volume fraction of 25.6% and a pore size distribution ranging from 0.4 to 100.0 nm. The metal component content relative to the porous organic polymer in this catalyst is 0.25 wt%. The Rh3d orbital electron binding energies of this catalyst are 308.70 and 312.70 eV, respectively, which are significantly higher than those of Comparative Examples 1-3 and Examples 1-2. This indicates that the increased number of fluorine substituents further reduces the outer electron density of the Rh active sites, thereby further improving the catalyst's conversion, yield, and TOF.

[0032] Example 4

[0033] In Example 4, the catalyst preparation process and conditions were the same as in Example 1, except that 10.0 g of L15 ligand was used in place of 10.0 g of L1 ligand. The polymer had a specific surface area of ​​1366 m². 2 / g, pore volume 1.78cm 3 The catalyst has a micropore volume fraction of 26.8% and a pore size distribution ranging from 0.4 to 100.0 nm. The metal component content relative to the porous organic polymer in this catalyst is 0.25 wt%. The Rh3d orbital electron binding energies of this catalyst are 308.82 and 312.82 eV, which are significantly higher than those of Comparative Examples 1-3 and Examples 1-3. This indicates that the increased number of fluorine substituents further reduces the outer electron density of the Rh active sites, thereby further improving the catalyst's conversion, yield, and TOF.

[0034] Example 5

[0035] In Example 5, the catalyst preparation process and conditions were the same as in Example 1, except that 10.0 g of L13 ligand was used in place of 10.0 g of L1 ligand. The polymer had a specific surface area of ​​1385 m². 2 / g, pore volume 1.80cm³ 3 The catalyst has a micropore volume fraction of 27.4% and a pore size distribution ranging from 0.4 to 100.0 nm. The metal component content relative to the porous organic polymer in this catalyst is 0.25 wt%. The Rh3d orbital electron binding energies of this solid catalyst are 308.90 and 312.90 eV, which are significantly higher than those of Comparative Examples 1-3 and Examples 1-4. This indicates that the increased number of fluorine substituents further reduces the outer electron density of the Rh active sites, thereby further improving the catalyst's conversion, yield, and TOF.

[0036] Example 6

[0037] In Example 6, the catalyst preparation process and conditions were the same as in Example 1, except that 10.0 g of L82 ligand was used in place of 10.0 g of L1 ligand. The polymer had a specific surface area of ​​872 m². 2 / g, pore volume 1.27cm 3 The micropore volume fraction was 46.2%, significantly higher than that of Examples 1-5 and Comparative Examples 1-3. This indicates that the large steric hindrance substituents are beneficial for increasing the micropore volume, resulting in excellent hydroformylation regioselectivity of the catalyst, with a pore size distribution of 0.4-100.0 nm. The metal component content relative to the porous organic polymer in this catalyst was 0.25 wt%. The Rh3d orbital electron binding energies of this solid catalyst were 308.42 and 312.42 eV.

[0038] Example 7

[0039] In Example 7, the catalyst preparation process and conditions were the same as in Example 1, except that 10.0 g of L96 ligand was used in place of 10.0 g of L1 ligand. The polymer had a specific surface area of ​​692 m². 2 / g, pore volume 0.92cm 3 The catalyst has a micropore volume fraction of 38.5% and a pore size distribution ranging from 0.4 to 100.0 nm. The metal component content relative to the porous organic polymer in this catalyst is 0.25 wt%. The Rh3d orbital electron binding energies of this solid catalyst are 308.85 and 312.85 eV, respectively. This catalyst exhibits higher micropore volume fraction and Rh3d orbital electron binding energies than the catalysts in Comparative Examples 1-3, indicating that multiple substituents can simultaneously modulate the electronic properties and steric hindrance effects of the Rh active sites, thereby enabling the catalyst to possess excellent hydroformylation activity and regioselectivity.

[0040] Example 8

[0041] In Example 8, the catalyst preparation process and conditions were the same as in Example 1, except that 10.0 g of L101 ligand was used in place of 10.0 g of L1 ligand. The polymer had a specific surface area of ​​898 m². 2 / g, pore volume 134cm³ 3 The catalyst has a micropore volume fraction of 43.2% and a pore size distribution ranging from 0.4 to 100.0 nm. The metal component content relative to the porous organic polymer in this catalyst is 0.25 wt%. The Rh3d orbital electron binding energies of this solid catalyst are 308.78 and 312.78 eV. This catalyst exhibits a higher micropore volume fraction and Rh3d orbital electron binding energy than the catalysts in Comparative Examples 1-3, indicating that multiple substituents can simultaneously modulate the electronic properties and steric hindrance effects of the Rh active sites, thereby giving the catalyst excellent hydroformylation activity and regioselectivity.

[0042] Example 9

[0043] In Example 9, the catalyst preparation process and conditions were the same as in Example 1, except that 12.6 mg of Rh(CO)₂(acac) was used to replace 6.3 mg of Rh(CO)₂(acac). The polymer had a specific surface area of ​​10¹⁰ m². 2 / g, pore volume 1.60cm³ 3 The catalyst has a micropore volume fraction of 22.3% and a pore size distribution ranging from 0.4 to 100.0 nm. The metal component content relative to the porous organic polymer in this catalyst is 0.5 wt%. The Rh3d orbital electron binding energies of this solid catalyst are 308.44 and 312.44 eV. The physical properties of this catalyst are similar to those of the catalyst in Example 1 and are greater than those of Comparative Examples 1-3, indicating that the porous organic polymer catalyst still exhibits good catalytic performance when the metal loading is increased.

[0044] Example 10

[0045] In Example 10, the polymer synthesis process was identical to that in Example 1, except that 24 hours of stirring was replaced with 0.5 hours of stirring. The polymer had a specific surface area of ​​1000 m². 2 / g, pore volume 1.60cm³ 3 The catalyst has a micropore volume fraction of 22.1% and a pore size distribution ranging from 0.4 to 100.0 nm. The metal component content relative to the porous organic polymer in this catalyst is 0.25 wt%. The Rh3d orbital electron binding energies of this solid catalyst are 308.44 and 312.44 eV. The physical properties of this catalyst are similar to those of the catalyst in Example 1 and are greater than those of the catalysts in Comparative Examples 1-3. This indicates that the porous organic polymer catalyst still exhibits good catalytic performance when the stirring time during polymer synthesis is reduced.

[0046] Example 11

[0047] In Example 11, the catalyst preparation process and conditions were the same as in Example 1, except that benzoyl peroxide was used instead of azobisisobutyronitrile as the free radical initiator. The polymer had a specific surface area of ​​1039 m². 2 / g, pore volume 1.62cm 3 The catalyst has a micropore volume fraction of 22.6% and a pore size distribution ranging from 0.4 to 100.0 nm. The metal component content relative to the porous organic polymer in this catalyst is 0.25 wt%. The Rh3d orbital electron binding energies of this solid catalyst are 308.44 and 312.44 eV. The physical properties of this catalyst are similar to those of the catalyst in Example 1, and greater than those of the catalysts in Comparative Examples 1-3. This indicates that when the free radical initiator is replaced with benzoyl peroxide, the porous organic polymer catalyst still exhibits good catalytic performance.

[0048] Comparative Example 1

[0049] In Comparative Example 1, the catalyst preparation and conditions were the same as in Example 1, except that 10.0 g of tris(4-vinylphenyl)phosphine ligand was used to replace 10.0 g of L1 ligand monomer. The polymer had a specific surface area of ​​1001 m². 2 / g, pore volume 1.70cm³ 3 The micropore volume fraction was 22.0%, significantly lower than that of porous organic polymer catalysts containing sterically hindered substituents (Examples 6-8), resulting in lower regioselectivity and a pore size distribution of 0.4-100.0 nm. The metal component content in this catalyst relative to the porous organic polymer was 0.25 wt%. The Rh3d orbital electron binding energies of this solid catalyst were 308.40 and 312.40 eV, significantly lower than those in Examples 1-5 and 7-11, indicating that the Rh active sites in this catalyst have a higher outer electron density, leading to lower conversion, yield, and TOF compared to porous organic polymer catalysts containing fluorine substituents.

[0050] Comparative Example 2

[0051] In Comparative Example 2, except that 10.0 g of tris(2-vinylphenyl)phosphine ligand was used to replace 10.0 g of L1 ligand monomer, the catalyst preparation and conditions were the same as in Example 1. The catalyst had a specific surface area of ​​890 m². 2 / g, pore volume is 1.39cm 3The micropore volume fraction was 27.0%, significantly lower than that of porous organic polymer catalysts containing sterically hindered substituents (Examples 6-8), resulting in lower regioselectivity and a pore size distribution of 0.4-100.0 nm. The metal component in this catalyst was 0.25 wt% relative to the porous organic polymer. The Rh3d orbital electron binding energies of this solid catalyst were 308.43 and 312.43 eV, significantly lower than or equal to those in Examples 1-5 and 7-11, indicating that the Rh active sites in this catalyst have a higher outer electron density, leading to lower conversion, yield, and TOF compared to porous organic polymer catalysts containing fluorine substituents.

[0052] Comparative Example 3

[0053] In Comparative Example 3, except that 10.0 g of tris(3-vinylphenyl)phosphine ligand was used to replace 10.0 g of L1 ligand monomer, the catalyst preparation and conditions were the same as in Example 1. The catalyst had a specific surface area of ​​520 m². 2 / g, pore volume 0.53cm 3 The micropore volume fraction was 14.7%, significantly lower than that of porous organic polymer catalysts containing sterically hindered substituents (Examples 6-8), resulting in lower regioselectivity and a pore size distribution of 0.4-100.0 nm. The metal component content relative to the porous organic polymer in this catalyst was 0.25 wt%. The Rh3d orbital electron binding energies of this solid catalyst were 308.35 and 312.35 eV, significantly lower than those in Examples 1-5 and 7-11, indicating that the Rh active sites in this catalyst have a higher outer electron density, leading to lower conversion, yield, and TOF compared to porous organic polymer catalysts containing fluorine substituents.

[0054] 0.125 g of the heterogeneous catalysts prepared above (the heterogeneous catalysts prepared in Examples 1-15 and Comparative Examples 1-3) were respectively loaded into fixed-bed reactors, with quartz sand loaded at both ends of the bed. A reaction mixture (C3H6:H2:CO = 1:1:1, volume ratio) was introduced, and the reaction was carried out at 120°C, 1.0 MPa, and a gas hourly space velocity of 2000 h⁻¹. -1 The hydroformylation reaction was carried out under the specified conditions. The reaction mixture was collected in a collection vessel. The resulting product was added to ethanol as an internal standard and analyzed by an HP-7890N gas chromatograph equipped with an HP-5 capillary column and an FID detector. The reaction results are listed in Table 1. The physical properties of the catalyst are listed in Table 2.

[0055] The experimental results of Examples 1-11 and Comparative Examples 1-3 show that the heterogeneous catalysts prepared with fluorinated phosphine ligands (Examples 1-5 and 7-11) exhibit higher Rh3d orbital electron binding energies than those prepared with fluorinated phosphine ligands (Comparative Examples 1-3), as shown in Table 2. This indicates that fluorine substituents can reduce the outer electron density of the Rh active sites, and the more fluorine substituents there are, the more significant the reduction (Examples 1-5). This results in superior reaction performance in the hydroformylation reaction, especially in terms of reactivity, where the heterogeneous catalysts prepared with fluorinated phosphine ligands can achieve a maximum TOF of 3523 h⁻¹. -1 The highest TOF of the heterogeneous catalyst prepared with fluorine-free phosphine ligands is only 1566 h⁻¹. -1 The heterogeneous catalysts prepared with sterically hindered substituent phosphine ligands (Examples 6-8) exhibit a larger micropore volume ratio than those prepared with sterically hindered substituent phosphine ligands (Comparative Examples 1-3), as shown in Table 2. This results in their superior selectivity for straight-chain aldehydes in the hydroformylation reaction. The heterogeneous catalysts prepared with large-volume sterically hindered substituent phosphine ligands have a maximum positive-to-negative ratio of 16.2, while the catalysts prepared with sterically hindered substituent phosphine ligands have a ratio of only 8.9. The catalysts prepared with fluorine-containing and sterically hindered phosphine ligands (Examples 7 and 8) exhibit higher micropore volume fraction and Rh3d orbital electron binding energy compared to those prepared with fluorine-free and sterically hindered phosphine ligands (Comparative Examples 1-3). This results in significantly superior hydroformylation activity and linear aldehyde selectivity compared to the catalysts prepared with fluorine-free and sterically hindered phosphine ligands (Comparative Examples 1-3). The catalyst prepared with fluorine-containing and sterically hindered phosphine ligands achieves a TOF as high as 3462 h⁻¹. -1 The positive-to-negative ratio is as high as 14.1, while the TOF of catalysts prepared from fluorine-free and sterically hindered phosphine ligands is only 1566 h⁻¹. -1 The positive-to-negative ratio is only 8.9.

[0056] Table 1. propylene reaction data of the catalysts synthesized in Examples 1-15 and Comparative Examples 1-3 above.

[0057]

[0058] The experimental conditions were: 0.125 g catalyst, 120 °C, 1 MPa, reactant gas (C3H6:CO:H2 = 1:1:1 volume ratio), and space velocity 2000 h⁻¹. -1 In TOF calculations, all metals are considered as active sites, and the reaction takes place in a fixed-bed reactor.

[0059] Table 2 shows the physical properties of the catalysts synthesized in Examples 1-15 and Comparative Examples 1-3 above.

[0060]

[0061] The present invention has been described in detail above, but it is not limited to the specific embodiments described herein. Those skilled in the art will understand that other modifications and variations can be made without departing from the scope of the invention. The scope of the invention is defined by the appended claims.

Claims

1. A multi-substituent porous organic polymer catalyst, characterized by: The heterogeneous catalyst comprises or consists of a metal active component and a polysubstituted porous organic polymer, wherein the metal active component is one or two or more of metals Rh, Ru, Ir, Pd, Co or Cu; The polysubstituted porous organic polymer is a porous polymer generated by solvothermal copolymerization of a polysubstituted triarylphosphine (or polysubstituted triphenylphosphine) monomer; The polysubstituted triarylphosphine (or polysubstituted triphenylphosphine) refers to a triarylphosphine (or triphenylphosphine) having 1-3 vinyl groups (and 2 or 3 vinyl groups are on different benzene rings) and one or two or more other substituents, which are one or two or more of fluoro, trifluoromethyl, tert-butyl.

2. The catalyst of claim 1, wherein: The weight content of the metal active component in the porous organic polymer is 0.01%-20% (preferably 0.1%-5%).

3. The catalyst of claim 1, wherein: The polysubstituted triarylphosphine monomer is one or two or more of the following L1-L114 ligands:

4. The catalyst of claim 1, wherein: The specific surface area of the porous organic polymer is 200-2000 m 2 / g, and the pore volume is 0.1-5.0 cm 3 / g, and the pore size distribution is 0.4-100.0 nm.

5. A method for preparing the catalyst of any one of claims 1-4, the method comprising: a) 263-473K (preferably 283-423K), adding a free radical initiator in a solvent containing the polysubstituted triarylphosphine monomer, stirring for 0.5-96h (preferably 3-48h); b) 293-473K (preferably 333-423K), solvothermal polymerization of the solution of step a) in a solvothermal autoclave for 0.5-96h (preferably 5-48h), after polymerization, 283-473K (preferably 333-433K) vacuum extraction of the solvent to obtain the porous organic polymer; c) 273-473K (preferably 293-433K), adding the polymer obtained in step b) into a solvent containing the metal active component, stirring for 0.5-100h (preferably 5-50h), after stirring, 273-473K (preferably 333-433K) vacuum extraction of the solvent to obtain the heterogeneous catalyst.

6. The method of claim 5, wherein, The solvent used in step a) is one or two or more of benzene, toluene, tetrahydrofuran, methanol, ethanol, dichloromethane, dichloroethane or deionized water; The free radical initiator used in step a) is one or two or more of cyclohexanone peroxide, dibenzoyl peroxide, tert-butyl hydroperoxide, azobisisobutyronitrile or azobisisoheptyl nitrile.

7. The method according to claim 5 or 6, characterized in that, The weight ratio of the free radical initiator to the polysubstituted triarylphosphine monomer is 1:600-1:5 (preferably 1:100-1:20); The content of the polysubstituted triarylphosphine monomer in the solvent is 0.01-2g / ml (preferably 0.05-1g / ml).

8. The method of claim 4, wherein: The solvent in step c) is one or more of water, benzene, toluene, N,N- dimethylformamide, tetrahydrofuran, methanol, ethanol, dichloromethane or trichloromethane, and the active component is one or more of Rh, Ru, Ir, Pd, Co or Cu, and the solvent containing the metal active component is formed by adding a precursor of the active component to the solvent, wherein the precursor of Rh is one or more of Rh(CH3COO)2, RhH(CO)(PPh3)3, Rh(CO)2(acac), RhCl3; the precursor of Ru is one or more of Ru3(CO) 12 , RuCl3, Rh(acac)3; the precursor of Ir is one or more of Ir(CO)3(acac), Ir(CH3COO)3, Ir(acac)3, IrCl4; the precursor of Pd is one or more of PdCl2, Pd(CH3COO)2, Pd(acac)2; the precursor of Co is one or more of Co(CH3COO)2, Co(CO)2(acac), Co(acac)2, CoCl2; and the precursor of Cu is one or more of Cu(CH3COO)2, Cu(acac)2, CuCl, CuCl2. The content of the active component in the solvent is 0.01mg / ml-5mg / ml (preferably 0.1mg / ml-1mg / ml).

9. Use of the catalyst of any one of claims 1-4 in catalyzing an olefin hydroformylation reaction.

10. Use according to claim 9, characterized in that, The olefin is one or more of ethylene, propylene, butene, pentene, hexene, octene, nonene and decene, and the reaction conditions are: volume ratio of the reaction mixture gas olefin:H2:CO = 1:0.5:0.5 to 1:5000:5000 (preferably 1:1:1 to 1:1000:1000), reaction temperature 50 to 160°C (preferably 80 to 140°C), pressure 0.1 to 8 MPa (preferably 0.5 to 6 MPa), reaction mixture gas space velocity 100 to 8000 h -1 (preferably 500 to 6000 h -1 ).

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