A method for hydrogenating α, β-unsaturated aldehydes or ketones

Abstract

The present invention belongs to the field of heterogeneous catalysis, and specifically relates to a catalyst for hydrogenation of α, β-unsaturated aldehydes and ketones, and a preparation method and application thereof. The present invention introduces an olefin group into a phosphine oxide organic monomer, and utilizes the polymerization reaction of the olefin group on the monomer molecule to prepare a functional polymer with a high bulk concentration of phosphine oxide and developed pores. The high concentration of phosphine oxide monomers in the polymer bulk can be used as a ligand to coordinate with a metal to form a heterogeneous catalyst. After the phosphine oxide monomer is coordinated with the metal, a hydroxyl group connected to P can be formed, which can play the role of an acidic functional site, a positioning effect group, or a modifiable site. Thanks to the synergistic effect of the ligand and the metal in the prepared catalyst, the catalyst finally prepared can catalyze the selective hydrogenation of α, β-unsaturated aldehydes under mild conditions.

Description

Technical Field

[0001] The invention belongs to the field of heterogeneous catalysis, and specifically relates to an alpha, beta-unsaturated aldehyde and ketone hydrogenation catalyst and a preparation method and application thereof. Background Art

[0002] Unsaturated alcohols are important raw materials for fine chemicals such as medicines and fragrances. Currently, they are mainly produced by reducing α- and β-unsaturated aldehydes and ketones with lithium aluminum tetrahydride, sodium borohydride, etc. This reaction requires a large amount of solvent, making it difficult to separate the products and generating a lot of three wastes. Therefore, it is imperative to develop a clean production process for unsaturated alcohols (Acc. Chem. Res., 2007, 40, 1309-1319).

[0003] Selective hydrogenation of α, β-unsaturated aldehydes and ketones is a green and efficient solution for obtaining unsaturated alcohols. However, the bond energy of C=O in α, β-unsaturated aldehydes and ketones is larger than that of C=C, and selective hydrogenation of C=O double bonds is much more difficult than that of C=C double bonds. Therefore, the development of selective hydrogenation catalysts with high selectivity and high stability for C=O bonds is the key to clean production of unsaturated alcohols (CIESC Journal, 2019, 70, 3396-3403).

[0004] In 2012, Rojas et al. (J. Mol. Catal. A: Chem., 2012, 363 / 364, 122-128) applied SiO2-supported Ir nanocatalysts to catalyze the selective hydrogenation of cinnamaldehyde and benzylidene acetone. The results showed that when the conversion rate of the reactants was 5%, the SiO2-supported Ir nanocatalyst had a hydrogenation selectivity of 57% for the C═O bond of cinnamaldehyde.

[0005] In 2014, Guo et al. (ACS Catalysis, 2014, 4, 1340-1328) encapsulated 10.7% Pt inside UIO-66-NH2 and obtained a catalyst that could be reused 10 times for the hydrogenation reaction of cinnamaldehyde.

[0006] In 2017, Wang et al. (Journal of Nanoparticle Research, 2017, 19, 153) used atomic deposition to highly disperse Pt nanoparticles on different carriers. Under the conditions of 70°C, 1 MPa, and 12 hours of reaction time, Pt / SiO2 can achieve complete conversion of citral, with a selectivity of nerol to geraniol of 58%, and can be catalytically cycled more than 3 times.

[0007] When traditional hydrogenation catalysts reported in the literature are applied to the selective hydrogenation reaction of α, β-unsaturated aldehydes and ketone molecules, they face the problems of insufficient catalytic activity and poor selectivity.

[0008] Secondary phosphine oxide (SPO) ligands are stronger electron-donating ligands, more stable in air and easier to synthesize than traditional triphenylphosphine ligands. In essence, SPO ligands exist in a balance between pentavalent phosphine oxide and trivalent phosphorous acid. SPO generally tends to exist in the pentavalent phosphorus state, but when coordinated with a metal, it will be converted into the trivalent phosphorous acid state (Formula 1).

[0009]

[0010]

[0011] This unique property makes SPO have a structure similar to that of bidentate chelate ligands after coordination with metal. In 2015, Piet WNM van Leeuwen's research group reported that diphenyl SPO can be used as a good stabilizing group to stabilize Au nanoparticles (J.Am.Chem.Soc.2014,136,2520-2528; J.Am.Chem.Soc.2015,137,7718-7727), and the prepared Au nanoparticles have good results for the hydrogenation of aldehydes (unsaturated alcohol selectivity 99%). This is mainly due to the fact that after diphenyl SPO is coordinated with Au nanoparticles, O can activate and crack hydrogen through synergistic action with Au (Formula 2). The synergistic catalytic effect of Au and SPO ligands makes this type of Au nanocatalyst highly selective in the selective hydrogenation reaction of α, β-unsaturated aldehydes and ketone molecules.

[0012]

[0013] The Au nanoparticles prepared by Piet WNMvan Leeuwen and others in their beautiful work can be used as catalysts in catalytic reactions. However, the catalysts face the problems of insufficient catalytic activity, difficulty in recycling, and loss of active components of the catalyst. How to solve these problems is a great challenge.

[0014] In recent years, the rapid development of POPs materials has provided an opportunity for the heterogeneity and recycling of catalysts. In 2014, our research group worked together with Xiao Fengshou's research group at Zhejiang University (Chem. Commun., 2014, 50, 11844-11847; J. Mol. Catal. A-Chem., 2015, 404, 211-217; React. Kinet. Mech. Cat., 2015, 116 (1), 223-234) to successfully prepare a polymer-supported heterogeneous hydroformylation catalyst. Studies have shown that the Rh active center on the heterogeneous catalyst is in a single-point dispersed state, which gives the catalyst good activity, and the reason for the catalyst's ultra-high stability is the presence of multiple Rh-P coordination bonds. Summary of the invention

[0015] In order to solve the above problems, the object of the present invention is to provide an α, β-unsaturated aldehyde, ketone hydrogenation catalyst and a preparation method and application thereof.

[0016] The technical solution of the present invention is:

[0017] A catalyst for hydrogenation of α, β-unsaturated aldehydes and ketones and a preparation method and application thereof, the technical scheme is: an olefin-functionalized phosphine oxide monomer is subjected to polymerization reaction initiated by an initiator to obtain a porous organic polymer of phosphine oxide. P in the prepared polymer body coordinates with metal to prepare a multiphase catalyst with a porous organic polymer of phosphine oxide as a carrier. Thanks to the ligand and metal synergistic effect in the prepared catalyst, this type of catalyst can achieve highly selective conversion of α, β-unsaturated aldehydes and ketones under mild conditions.

[0018] The olefin group is preferably a vinyl group, and the olefin functionalized phosphine oxide (one or more than one of AF) and the synthesis route are one or more of the following:

[0019]

[0020] The phosphine oxide porous organic polymer has a multi-level pore structure and a specific surface area of ​​10 to 3000 m 2 / g, preferably in the range of 30 to 1000 m 2 / g, containing macropores, mesopores and micropores, with a pore volume of 0.1 to 10.0 cm 3 / g, preferably 0.2 to 2.0 cm 3 / g, and the pore size distribution is 0.01 to 100.0 nm, preferably 0.2 to 5.0 nm.

[0021] The specific preparation steps of the phosphine oxide porous organic polymer are as follows:

[0022] a) adding a vinyl functionalized phosphine oxide monomer, with or without a crosslinking agent, and a free radical initiator to a solvent under an inert gas atmosphere at 273 to 473 K, and stirring the mixture for 0.1 to 100 hours to obtain a prepolymer solution, preferably in a stirring time range of 0.1 to 20 hours;

[0023] b) transferring the prepolymer mixed solution obtained in step a) into a synthesis autoclave, and carrying out polymerization reaction by solvent thermal polymerization under an inert gas atmosphere at 273 to 473 K, stirring for 1 to 100 hours to obtain a phosphine-containing organic polymer;

[0024] c) removing the solvent from the phosphine-containing organic polymer obtained in step b) under vacuum at room temperature to obtain an organic polymer having a multi-level pore structure and containing phosphine oxide functional sites.

[0025] The solvent described in step a) is one or more of water, methanol, ethanol, dichloromethane, chloroform, benzene, toluene, xylene or tetrahydrofuran; the crosslinking agent described in step a) is one or more of styrene, divinylbenzene, tris-phenylene, ethylene, propylene or butadiene; the free radical initiator is one or more of tert-butyl hydroperoxide, azobisisobutyronitrile, azobisisoheptylnitrile, cyclohexanone peroxide or dibenzoyl peroxide.

[0026] In step a), when a crosslinking agent is added, the molar ratio of the vinyl functionalized phosphine oxide monomer to the crosslinking agent is 0.01:1 to 10:1, and the molar ratio of the vinyl functionalized phosphine oxide monomer to the free radical initiator is 1000:1 to 10:1. Before polymerizing into an organic polymer, the concentration range of the vinyl functionalized phosphine oxide monomer in the solvent is 0.1-100 g / L; the inert gas in steps a) and b) is selected from one or more of Ar, He, N2 and CO2.

[0027] In addition to bulk polymerization, the polymerization method can also be solution polymerization, suspension polymerization and emulsion polymerization. The polymerization operating temperature range is selected to be 273-473K. The polymerization monomer can be selected from one or more of the phosphine ligands; the polymerized phosphine oxide polymer can be used as a carrier of a multiphase catalyst to prepare a high-performance catalyst for the selective hydrogenation reaction of α, β-unsaturated aldehydes and ketones. The preparation method of the α, β-unsaturated aldehyde and ketone hydrogenation catalyst is: the active metal precursor is prepared into an impregnation solution, added to the carrier, and an equal volume impregnation method or an excess solution impregnation method is adopted, and after reduction and drying steps, a catalyst suitable for the hydrogenation reaction of α, β-unsaturated aldehydes is finally prepared. .

[0028] The active metal precursor is selected from one or more of Au, Pd, Co, and Ir, wherein the precursor of Au is one or more of AuCl, (dimethyl sulfide) gold chloride (I), triphenylphosphine gold chloride (I), (tetrahydrothiophene) gold chloride (I), AuCl3, and di(trifluoroacetyl) gold (III); the precursor of Pd is Pd(CH3COO)2, Pd(acac)2, PdCl2, Pd(PPh3)4, and PdCl2(CH3CN)2; the precursor of Co is one or more of Co(CH3COO)2, Co(CO)2(acac), Co(acac)2, and CoCl2; the precursor of Ir is The driving body is one or more of Ir(CO)3(acac), Ir(CH3COO)3, Ir(acac)3, and IrCl4, and the metal loading range of the finally prepared catalyst is 0.01-10wt%; the solvent for preparing the impregnation liquid is one or more of water, benzene, toluene, tetrahydrofuran, methanol, ethanol, dichloromethane or chloroform; the impregnation operation temperature is 243-373K; NaBH4, AlLiH4, or H2 calcination reduction method is adopted for catalyst reduction; vacuum drying method is adopted for catalyst drying, the drying operation temperature is 303-403K, and the operating absolute pressure is maintained below 10kPa during drying.

[0029] The invention is applied in the catalytic selective hydrogenation reaction of α, β-unsaturated aldehydes and ketones. The prepared phosphine oxide polymer supported catalyst is loaded into a reactor, and hydrogen and raw olefin are introduced. The purity of hydrogen is 0.1% to 100%, and the space velocity is 100 to 20000 h -1 , the preferred range is 1000~20000h -1 The raw materials are C4~C30 α, β-unsaturated aldehydes and ketones, and the selective hydrogenation reaction is carried out under the conditions of reaction temperature of 303~573K (the reaction temperature is preferably 323~423K) and reaction pressure of 0.1~10.0MPa (the reaction pressure is preferably 0.5~5MPa).

[0030] The hydrogen may also contain one or more other gases selected from Ar, CO2, He or N2, and the reactor may be a fixed bed reactor, a fluidized bed reactor or a slurry bed reactor. The raw material α, β-unsaturated aldehydes and ketones have a purity of 20 to 100%.

[0031] Reaction principle of the present invention:

[0032] Secondary phosphine oxide (SPO) ligand is a strong electron-donating ligand, which is more stable and easier to synthesize than traditional triphenylphosphine ligand in air atmosphere. In essence, SPO ligand exists in a balance between pentavalent phosphine oxide and trivalent phosphorous acid. SPO generally tends to exist in the state of pentavalent phosphorus, but when the phosphine oxide monomer is coordinated with the metal, a hydroxyl group connected to P can be formed, which can play the role of acidic functional site, positioning effect group, or modifiable site, and the ligand and the central metal can cooperate to achieve mild activation of hydrogen. The present invention introduces olefin groups into phosphine oxide organic monomers, and utilizes the polymerization reaction of olefin groups on monomer molecules to prepare functional polymers with high bulk concentration of phosphine oxide and developed pores. The high concentration of phosphine oxide monomers in the polymer body can be used as ligands to coordinate with metals to form a multiphase catalyst. Thanks to the synergistic effect of ligands and metals in the prepared catalyst, the finally prepared catalyst can catalyze the selective hydrogenation of α, β-unsaturated aldehydes under mild conditions.

[0033] The beneficial effects of the present invention are:

[0034] Since the bond energy of C=O in α, β-unsaturated aldehyde and ketone molecules is larger than that of C=C, it is much more difficult to selectively hydrogenate C=O double bonds than C=C double bonds. The present invention utilizes the synergistic effect of the unique properties of phosphine oxide monomers and central metals to prepare a catalyst that can highly selectively hydrogenate C=O double bonds while retaining C=C double bonds. By introducing olefin groups into phosphine oxide organic monomers, a functional polymer with high bulk concentration and developed pores of phosphine oxide is prepared by utilizing the polymerization reaction of the olefin groups on the monomer molecules. In the final prepared catalyst, the metal active components form a firm coordination bond with the high concentration of exposed P, and the metal active components are not easy to lose, which gives the catalyst a higher stability, greatly prolongs the catalyst life, and fundamentally solves the problem of catalyst deactivation and active metal loss. The active metal components are highly dispersed in the phosphine-containing organic polymer carrier, which greatly improves the utilization efficiency of the metal and the catalyst activity. The final catalyst is multiphase, which is different from the homogeneous reaction system. The separation of reactants and products from the catalyst is simple and efficient, which greatly reduces the cost of subsequent industrial production. BRIEF DESCRIPTION OF THE DRAWINGS

[0035] Figure 1 It is distyrylphosphine oxide 1 H NMR spectrum.

[0036] Figure 2 It is distyrylphosphine oxide 13 C NMR spectrum.

[0037] Figure 3 It is distyrylphosphine oxide 31 P NMR spectrum.

[0038] Figure 4 Schematic diagram of typical cross-linking agents L1-L20 used in polymerization.

[0039] Figure 5 This is the physical adsorption diagram of CPOL-1SPO10DVB.

[0040] Figure 6 This is the pore size distribution diagram of CPOL-1SPO10DVB.

[0041] Figure 7 This is the physical adsorption diagram of POL-SPO.

[0042] Figure 8 This is the pore size distribution diagram of POL-SPO.

[0043] Fig. 9 They are reaction substrates for different α, β-unsaturated aldehydes and ketones. DETAILED DESCRIPTION

[0044] The following examples are provided to better illustrate the present invention, but are not intended to limit the scope of the present invention.

[0045] The synthesis process of olefin functionalized phosphine oxide AF is shown in the following figure:

[0046]

[0047] Specific preparation steps of monomer A: Under argon protection at 273K, 9g of p-chlorostyrene is dissolved in 50ml of 2-methyltetrahydrofuran, stirred evenly and set aside. 1.7g of magnesium chips are put into a flask, the temperature of the flask is raised to 333K, and about 5ml of a mixed solution of p-chlorostyrene and 2-methyltetrahydrofuran is added dropwise. After the Grignard reagent is initiated, the mixed solution is continued to be added dropwise, and the dropping temperature is maintained at 65°C. After the addition is completed, the Grignard reagent solution of p-chlorostyrene is obtained by keeping the temperature for 1 hour. Then the temperature is lowered to 0 degrees Celsius, and 4.5g of diethyl phosphite and 50ml of the mixed solution are added. After the addition is completed, the reaction is continued for 1 hour. 10 ml of saturated NH4Cl solution was added to quench the reaction, and the mixed solution was separated into two layers. The upper oil layer was taken out, and the solvent was distilled off at 60°C to obtain a light yellow oily liquid. 10 ml of n-heptane was added to heat the mixed solvent to 60°C to fully dissolve it, and then cooled to 0°C for recrystallization and drying to obtain 6.05 g of distyrylphosphine oxide (yield of about 73%, the product was confirmed by nuclear magnetic resonance and high-resolution mass spectrometry), attached Figure 1-3 The NMR of distyrylphosphine oxide A is 1 H. 13 C and 31 P spectrum.

[0048] By replacing p-chlorostyrene with the same molar number of m-chlorostyrene, o-chlorostyrene, 4-vinyl-1-chlorocyclohexane, 3-vinyl-1-chlorocyclohexane and 2-vinyl-1-chlorocyclohexane, and keeping the other preparation steps and conditions the same, monomer BF (the product was confirmed by NMR and high-resolution mass spectrometry) can be prepared with yields of 70%, 39%, 55%, 53% and 38%, respectively.

[0049] Example 1

[0050] Preparation of diphenylphosphine oxide porous organic polymer: 5.0 g of diphenylphosphine oxide monomer and 50.0 g of crosslinking agent divinylbenzene (attached) were mixed at 298 K and in an inert gas atmosphere. Figure 4 L1) was dissolved in 550.0 ml of tetrahydrofuran solvent, 0.05 g of azobisisobutyronitrile as a free radical initiator was added to the above solution, and stirred for 2 hours to obtain a prepolymer. The prepolymer was transferred to an autoclave and polymerized by solvent thermal polymerization at 373K and in an inert gas atmosphere for 24 hours. After the autoclave was cooled to room temperature, the solvent was vacuum-evacuated at room temperature to obtain a polymer CPOL-1SPO10DVB copolymerized by distyrylphosphine oxide and divinylbenzene, with a yield of 100%. Figure 5 is the N2 physical adsorption curve of CPOL-1SPO10DVB, attached Figure 6 This is the pore size distribution diagram of CPOL-1SPO10DVB.

[0051] Polymer self-supported highly dispersed Au metal catalyst: 21.0 mg of tetrahydrothiophene gold chloride (I) was weighed and dissolved in 10.0 ml of tetrahydrofuran solvent, 1.0 g of the above-prepared CPOL-1SPO10DVB polymer was added, and stirred at 298K for 5 hours. Then 60.5 mg of NaBH4 powder was added, and stirring was continued for 5 hours under argon atmosphere at 323K. The solvent was removed in vacuo at room temperature to obtain a phosphine oxide polymer self-supported highly dispersed Au-based catalyst.

[0052] Example 2

[0053] In Example 2, except that 50.0 g of the crosslinking agent divinylbenzene ( Figure 4 Except for L1), the rest of the synthesis process is the same as that of Example 1. The physical adsorption curve and pore size distribution diagram of the prepared POL-SPO are shown in the attached figure. Figure 7 and attached Figure 8 shown.

[0054] Example 3

[0055] In Example 3, the synthesis process is the same as that of Example 1 except that the same mole number of benzoyl peroxide is weighed to replace the free radical initiator azobisisobutyronitrile during the polymerization.

[0056] Example 4

[0057] In Example 4, the synthesis process was the same as that of Example 1 except that 50.0 ml of tetrahydrofuran solvent was used instead of 100.0 ml of tetrahydrofuran solvent during the polymerization.

[0058] Example 5

[0059] In Example 5, the synthesis process was the same as that of Example 1 except that 100.0 ml of dichloromethane was used instead of 100.0 ml of tetrahydrofuran during polymerization.

[0060] Example 6

[0061] In Example 6, except that the polymerization temperature of 393K was used instead of 373K, the rest of the synthesis process was the same as that of Example 1.

[0062] Example 7

[0063] In Example 7, except that the bulk polymerization method was replaced by the suspension polymerization method, the remaining methods and catalyst synthesis process were the same as those in Example 1.

[0064] Example 8

[0065] In Example 8, except that m-chlorostyrene is used instead of p-chlorostyrene, the rest of the synthesis process is the same as that of Example 1.

[0066] Example 9

[0067] In Example 9, except that the same molar number of palladium acetate is used to replace tetrahydrothiophene gold (I) chloride, the rest of the synthesis process is the same as that of Example 1, and a highly dispersed Pd-based catalyst can be obtained.

[0068] Example 10

[0069] In Example 10, except that iridium tricarbonyl acetylacetonate is used in place of tetrahydrothiophene gold (I) chloride in the same molar amount, the rest of the synthesis process is the same as in Example 1, and a highly dispersed Ir-based catalyst can be obtained.

[0070] Embodiment 11

[0071] In Example 11, except that the same molar number of cobalt dicarbonyl acetylacetonate is used to replace tetrahydrothiophene gold(I) chloride, the rest of the synthesis process is the same as that of Example 1, and a highly dispersed Co-based catalyst can be obtained.

[0072] Example 12

[0073] In Example 12, except that the same molar number of gold (III) chloride was used to replace tetrahydrothiophene gold (I) chloride, the rest of the synthesis process was the same as that of Example 1.

[0074] Embodiment 13

[0075] In Example 13, we prepared SPO-stabilized Au nanoparticle catalysts according to the literature (J. Am. Chem. Soc. 2014, 136, 2520-2528; J. Am. Chem. Soc. 2015, 137, 7718-7727).

[0076] Embodiment 14

[0077] 0.01mmol (the amount of catalyst added according to the molar amount of active metal) of the catalyst prepared in the above Examples 1-13 was placed in a 50mL reactor, 2mmol of the reactant cinnamaldehyde (CAS No. 104-55-2) was added, 5ml of tetrahydrofuran was added as the reaction solvent, and the reactor was replaced with hydrogen 6 times, and then 4MPa of hydrogen was filled, and the reactor was heated to 60°C for 10 hours. The reactor was cooled in an ice-water bath, ethanol was added as an internal standard, and gas chromatography was performed for analysis. The reaction results are listed in Table 1.

[0078] Table 1 Specific surface area of ​​the catalysts synthesized in Examples 1-13 and cinnamaldehyde hydrogenation reaction data

[0079]

[0080] Embodiment 15

[0081] 0.5 g of the catalyst prepared in Example 1 was loaded into a fixed bed reactor, and quartz sand was added at both ends. The raw gas (H2 / N2=50:50) was set at a space velocity of 2000 h -1 , liquid raw material (see attached for structural formula Fig. 9 ) Liquid speed is 5h -1 , hydrogenation reaction was carried out at 343K, 5.0MPa. The product was collected in a 60ml constant temperature (273K) collection tank. The obtained product was analyzed by HP-7890N gas chromatography equipped with HP-5 capillary column and FID detector, using n-propanol as internal standard. The reaction results are listed in Table 2.

[0082] Table 2 Attachment Fig. 9 Hydrogenation reaction data of different α, β-unsaturated aldehydes and ketones

[0083]

Claims

1. A method for hydrogenating an α, β-unsaturated aldehyde or ketone, characterized in that: In the presence of a supported heterogeneous catalyst, one or more of α, β-unsaturated aldehydes or α, β-unsaturated ketones undergo a selective hydrogenation reaction; the catalyst preparation method comprises: preparing an active metal precursor into an impregnation solution, adding the solution to a carrier, adopting an equal volume impregnation method or an excess solution impregnation method, and performing reduction and drying steps to finally prepare a catalyst suitable for the hydrogenation reaction of α, β-unsaturated aldehydes; The supported heterogeneous catalyst carrier is an olefin-functionalized phosphine oxide monomer, and the olefin groups in the phosphine oxide monomer are polymerized by an initiator to obtain a porous organic polymer of phosphine oxide; The olefin-functionalized phosphine oxide monomer is one or more of the following structural formulas AF; ； The active metal is selected from one or more of Au, Pd, Co and Ir, and the metal loading amount in the catalyst is in the range of 0.01 to 10 wt%.

2. The method according to claim 1, characterized in that: The porous organic polymer has a multi-level pore structure and a specific surface area of ​​10-3000 m 2 / g, pore volume is 0.1~10.0 cm 3 / g, and the pore size distribution is 0.01~100.0 nm.

3. The method according to claim 2, characterized in that: The specific surface area of ​​the porous organic polymer is 30-1000 m 2 / g, pore volume is 0.2~2.0 cm 3 / g, and the pore size distribution is between 0.2 and 5.0 nm.

4. The method according to claim 1, characterized in that: The specific preparation steps of porous organic polymer are as follows: a) adding a vinyl functionalized phosphine oxide monomer, with or without a crosslinking agent, and a free radical initiator to a solvent under an inert gas atmosphere at 273-473 K, and stirring the mixture for 0.1-100 hours to obtain a prepolymer solution; The molar ratio of the vinyl functionalized phosphine oxide monomer to the free radical initiator is 1000:1 to 10:1; before polymerizing into an organic polymer, the concentration range of the vinyl functionalized phosphine oxide monomer in the solvent is 0.1 to 100 g / L; In step a), when a cross-linking agent is added, the molar ratio of the vinyl functionalized phosphine oxide monomer to the cross-linking agent is 0.01:1 to 10:1; b) transferring the prepolymer mixed solution obtained in step a) into a synthesis autoclave, and carrying out polymerization reaction by solvent thermal polymerization under an inert gas atmosphere at 273-473 K, stirring for 1-100 hours to obtain a phosphine-containing organic polymer; c) removing the solvent from the phosphine-containing organic polymer obtained in step b) to obtain an organic polymer having a multi-level pore structure and containing phosphine oxide functional sites.

5. The method according to claim 4, characterized in that: The crosslinking agent in step a) is one or both of divinylbenzene and butadiene; the free radical initiator is one or both of tert-butyl hydroperoxide, azobisisobutyronitrile, azobisisoheptanenitrile, cyclohexanone peroxide or dibenzoyl peroxide; The inert gas in steps a) and b) is selected from one or more of Ar, He, N2 and CO2; The solvent in step a) is one or more of water, methanol, ethanol, dichloromethane, chloroform, benzene, toluene, xylene or tetrahydrofuran.

6. The method according to claim 1, characterized in that: The active metal is one or more of Au, Pd, Co and Ir; wherein the precursor of Au is one or more of AuCl, (dimethyl sulfide) gold chloride (I), triphenylphosphine gold chloride (I), (tetrahydrothiophene) gold chloride (I), AuCl3, di(trifluoroacetyl) gold (III); the precursor of Pd is Pd(CH3COO)2, Pd(acac)2, PdCl2, Pd(PPh3)4, PdCl2(CH3CN)2; the precursor of Co is one or more of Co(CH3COO)2, Co(CO)2 (acac), Co(acac)2, CoCl2; the precursor of Ir is one or more of Ir(CO)3(acac), Ir(CH3COO)3, Ir(acac)3, IrCl4, and the metal loading range of the finally prepared catalyst is 0 .01~10wt%; the solvent for preparing the impregnation solution is selected from one or more of water, benzene, toluene, tetrahydrofuran, methanol, ethanol, dichloromethane or chloroform; the impregnation operation temperature is 243~373 K; The catalyst is reduced by using NaBH4 and / or AlLiH4. The catalyst is dried by using vacuum drying. The drying operation temperature is 303-403 K. The absolute operating pressure is maintained below 10 kPa during drying.

7. The method according to any one of claims 1 to 6, characterized in that: The supported heterogeneous catalyst is loaded into the reactor, and hydrogen-containing gas and raw materials are introduced at a space velocity of 100-20000 h -1 ; The raw materials are one or more of C4~C30 α, β-unsaturated aldehydes and C4~C30 α, β-unsaturated ketones, and the liquid hourly space velocity is 0.01~100h -1 ; The selective hydrogenation reaction is carried out under the conditions of reaction temperature of 303~573K and reaction pressure of 0.1~10.0MPa.

8. The method according to claim 7, characterized in that: The supported heterogeneous catalyst is loaded into the reactor, and hydrogen-containing gas and raw materials are introduced at a space velocity of 1000-20000 h -1 ; The selective hydrogenation reaction is carried out under the conditions of reaction temperature of 323~423K and reaction pressure of 0.5~5 MPa.

9. The method according to claim 7, characterized in that: The hydrogen-containing gas is hydrogen or a mixture of hydrogen and other gases, and the other gases are selected from one or more of Ar, CO2, He or N2, and the purity of the feed hydrogen is 0.1%~100%; The reactor is a fixed bed reactor, a fluidized bed reactor or a slurry bed reactor.

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