A catalyst and method for the methoxycarbonylation of unsaturated olefins

Abstract

The present invention discloses a catalyst and a method for the methoxycarbonylation of unsaturated olefins. The catalyst comprises the following components: (1) a Group VIB and / or Group VIIIB metal active component; (2) a copolymerized framework support. Among them, the Group VIB or Group VIIIB metal includes one or more of Cr, Mo, W, Fe, Co, Ni, Ru, Rh, Os, Ir, Pt, and Pd, preferably selected from Ni, Pt, and Pd; the copolymerized framework support is a polymer of an aromatic compound containing phosphorus and / or nitrogen and a carbonyl group. By providing a coordination center through the copolymerized framework structure and forming a supported methoxycarbonylation heterogeneous catalyst after coordination bonding with the active site, it can exhibit high activity and stability when used in the methoxycarbonylation reaction of unsaturated olefins. Compared with the traditional homogeneous catalyst system, it can effectively reduce the subsequent separation difficulty and energy consumption and reduce the production cost.

Description

Technical Field

[0001] The present invention relates to the field of methoxycarbonylation of unsaturated olefins, and specifically relates to a catalyst for methoxycarbonylation of unsaturated olefins, a preparation method thereof, and an application thereof. Background Art

[0002] At present, the research on carbonylation reactions has been relatively mature. It mainly realizes the hydroformylation of unsaturated hydrocarbons and fatty acids under the action of transition metal catalysts using syngas as the carbonyl source. At the same time, many domestic and foreign patent studies have reported that in a system of alcohol or water, using only CO as the carbonyl source can carbonylate olefinic unsaturated compounds to obtain corresponding esters or carboxylic acids, achieving the carbonylation and esterification processes in one step. The catalyst system includes Group VIII metals and phosphine ligands such as alkylphosphines, cycloalkylphosphines, arylphosphines, or bidentate phosphines, etc. Using carbon monoxide in a system of alcohol or water can carbonylate ethylene to prepare corresponding carboxylic acids or esters.

[0003] Conventional carbonylation reaction processes are mostly homogeneous catalytic reactions, facing the problem of poor stability caused by the inactivation of active sites due to reduction and precipitation. For example, the bidentate phosphine ligand catalyst system disclosed in EP-A-0227160, etc. As the reaction progresses, it is necessary to frequently supplement the catalyst to maintain the reaction activity. During the reaction, the active metals precipitated by reduction are prone to agglomeration to form a mirror image, resulting in difficult recovery and expensive catalyst costs during industrialization. In addition, homogeneous catalytic reactions face the problem of catalyst recycling, resulting in a complex separation process. For example, EP-A-0411721 reported the separation process for preparing alkyl propionate. First, the catalyst is recycled by removing heavy components, and the product is further purified by distillation. During the industrialization process, there are problems of increasing the cost of device construction and energy consumption. At the same time, homogeneous catalysts have relatively poor stability during the separation process, which will inevitably increase the complexity of subsequent product refining.

[0004] CN112892605B discloses a preparation technique of a heterogeneous catalyst with basicity for the formylation reaction. The catalyst consists of a metal component and a copolymer of an organic ligand. The copolymer of the organic ligand is formed by copolymerizing a vinyl-containing phosphine ligand and a vinyl-containing organic base monomer, which can effectively improve the catalytic activity and stability; CN114522730A discloses a preparation technique of a heterogeneous catalyst for the morpholine formylation reaction. The catalyst consists of a metal and an organic polymer. The organic polymer is formed by dehydration polymerization of a nitrogen-containing monomer with an aldehyde group or an amine group, which can improve the high dispersion of the active component and the binding force with the carrier; CN109806911B discloses a preparation process of a phosphine-containing organic polymer self-supported highly dispersed metal catalyst. The organic polymer is formed by copolymerizing a monodentate or polydentate phosphine ligand functionalized with an olefin group. The catalyst shows high selectivity when applied to the preparation of linear aldehydes; CN114588949A discloses a preparation process of a phosphine ligand polymer-supported eggshell-type metal catalyst. The polymer is formed by self-polymerization or copolymerization of a monodentate, polydentate or secondary phosphine oxide ligand, and has excellent performance in the hydroformylation reaction of olefins; CN105754060B discloses a preparation method of an organic polymer containing phosphorus and nitrogen, which is formed by dehydration polymerization of an organic monomer containing phosphorus, nitrogen and an aldehyde group with a copolymer containing an amine group, which can effectively improve the activity and stability of the catalyst; CN114539058A discloses a method for the heterogeneous catalysis of methanol and light olefins to prepare methyl esters. The catalyst support is formed by copolymerizing a vinyl-containing phosphine ligand and a vinyl organic sulfonate, which can improve the activity and stability of the catalyst. The carriers described in the above patent technologies are of organic polymer structure, or are prepared by copolymerization of ligands functionalized with olefin groups, or are obtained by dehydration polymerization of ligands functionalized with aldehyde groups and amine groups, which can immobilize the active components, realize the heterogeneousization of homogeneous catalysts, reduce the subsequent separation difficulty, and improve the catalytic activity to a certain extent; however, for reactions with complex reaction mechanisms and reaction activities affected by mass transfer and internal and external diffusion, the promoting effect is limited. Summary of the Invention

[0005] To solve the above problems, an object of the present invention is to provide a catalyst for the methoxycarbonylation of unsaturated olefins. Through the catalyst prepared by the present invention, the loss of metal active sites during the reaction process can be effectively inhibited, the stability of the catalyst is significantly improved, ensuring low loss and high recovery rate of precious metals during the operation of the catalyst, thereby reducing the catalyst cost. In addition, rapid and low-energy consumption separation of the catalyst and the product can be achieved during product refining, reducing the product separation cost.

[0006] Another object of the present invention is to provide a method for using the catalyst to catalyze the preparation of carboxylic esters of unsaturated olefins. The catalyst has excellent catalytic activity and stability when applied to the methoxycarbonylation reaction of unsaturated olefins.

[0007] To achieve the above object, the present invention adopts the following solutions.

[0008] An unsaturated olefin methoxycarbonylation catalyst, comprising the following components:

[0009] (1) Group VI B and / or Group VIII B metal active components;

[0010] (2) Copolymerized skeletal carrier;

[0011] Among them, the Group VI B or Group VIII B metal includes one or more of Cr, Mo, W, Fe, Co, Ni, Ru, Rh, Os, Ir, Pt, and Pd, preferably selected from Ni, Pt, and Pd;

[0012] The copolymerized skeletal carrier is a polymer of an aromatic compound containing phosphine and / or nitrogen, and carbonyl.

[0013] The Group VI B and / or Group VIII B metal active components are derived from salts corresponding to the respective metals, including one or more of nitrates, chlorides, acetates, sulfonates, and phosphates, etc., preferably acetates. More preferably one or more of palladium acetate, palladium chloride, and palladium nitrate.

[0014] As a preferred method, the raw materials for preparing the copolymerized skeletal carrier include: one or more of polyhydroxy compounds and polyamino compounds, and polycarboxyl aromatic compounds.

[0015] The polycarboxyl aromatic compounds described in the present invention include but are not limited to the following substances:

[0016]

[0017] The polyhydroxy compounds described in the present invention include but are not limited to the following substances:

[0018]

[0019] The polyamino compounds described in the present invention include but are not limited to the following substances:

[0020]

[0021] The preparation method of the copolymerized skeletal carrier described in the present invention includes the following steps: in the presence of a solvent, one or more of polyhydroxy compounds and polyamino compounds react with polycarboxyl aromatic compounds by dehydration reaction.

[0022] The molar ratio of one or more of the polyhydroxy compounds and polyamino compounds to the polycarboxyl aromatic compounds in the present invention is 1:2 - 2:1, preferably 1:1.

[0023] The solvent described in the present invention is a lower aliphatic alcohol, and suitable examples include but are not limited to methanol, ethanol, propanol, n-butanol, or isobutanol with 4 or less carbon atoms, etc.

[0024] Preferably, the total concentration of the solute in the dehydration reaction of the present invention is 20-40 wt%.

[0025] Preferably, the temperature of the dehydration reaction of the present invention is 50-100 °C.

[0026] Preferably, the pressure of the dehydration reaction of the present invention is normal pressure.

[0027] Preferably, the time of the dehydration reaction of the present invention is 5-10 h.

[0028] The dehydration reaction of the present invention is preferably carried out under the catalysis of a strongly acidic resin. A strongly acidic resin with a working exchange capacity of 1000-3000 mmol / L is preferred, including but not limited to Rohm and Haas SR1L Na strongly acidic cation exchange resin, etc.

[0029] As a preferred embodiment, the dehydration reaction is carried out in an inert atmosphere, and the inert atmosphere includes but not limited to nitrogen, helium, etc.

[0030] As a preferred embodiment, the product after the dehydration reaction is washed with a solvent and dried in an inert atmosphere. The solvent includes but not limited to methanol, ethanol, propanol, n-butanol or isobutanol with 4 or less carbon atoms, etc. The drying temperature is 80-100 °C, and the drying time is 2-20 h.

[0031] As a preferred embodiment, in the preparation of the catalyst of the present invention, the active component is combined with the copolymerized backbone carrier by the method of equal-volume impregnation.

[0032] As a preferred embodiment, the preparation method of the catalyst includes the following steps: under the protection of an inert atmosphere, the copolymerized backbone carrier is mixed evenly with the solution of the metal active component, left to stand and impregnated for 1-5 h, and the solvent is removed.

[0033] Preferably, the loading amount of the metal active component is 0.1 wt%-5 wt%, preferably 0.5 wt%-2 wt%.

[0034] In the preparation method of the catalyst, the solvent of the solution is one or more of lower aliphatic alcohols such as methanol and ethanol, lower aliphatic esters such as ethyl acetate and methyl acetate, aromatic compounds such as benzene, toluene and xylene, and water, etc.

[0035] In the preparation method of the catalyst, the impregnation temperature is preferably 0-100 °C, more preferably 20-40 °C.

[0036] The catalyst system prepared by the method of the present invention can exhibit excellent catalytic activity and stability in the catalytic methoxycarbonylation reaction of unsaturated olefins. The loss of metal active sites during the reaction can be effectively inhibited, and the catalyst stability is significantly improved, ensuring low loss and high recovery rate of precious metals during the operation of the catalyst, thereby reducing the catalyst cost.

[0037] The present invention also provides the application of the above catalyst, specifically referring to a method for methoxycarbonylating unsaturated olefins with carbon monoxide as the carbonylating reagent in the presence of a hydroxy compound under the conditions of the catalyst of the present invention.

[0038] The unsaturated olefin described in the present invention is a straight-chain or branched-chain olefin containing one or more unsaturated bonds, preferably 1-3 unsaturated bonds, preferably a C1-C4 straight-chain olefin, and more preferably ethylene.

[0039] The hydroxy compound described in the present invention includes water or an organic molecule containing a hydroxy group, preferably an alkanol, and more preferably methanol and / or ethanol.

[0040] In the method for methoxycarbonylating unsaturated olefins of the present invention, the reaction is preferably carried out in a solvent. Suitable solvents include one or more of ketones, ethers, esters, amides, and aromatic compounds and their derivatives. Preferably, a non-protic solvent with a dielectric constant in the range of 3-8 at 298.15K and 1*10 5 Nm -2 is used, and more preferably the reaction solvent is anisole.

[0041] In the method for methoxycarbonylating unsaturated olefins of the present invention, the mass ratio of the solvent to the hydroxy compound is 100:1-1:100, preferably 20:1-1:20.

[0042] In the method for methoxycarbonylating unsaturated olefins of the present invention, the reaction can be carried out in a fixed-bed, slurry-bed and other reactors, preferably a slurry-bed.

[0043] As a preferred embodiment, the catalyst concentration in the slurry-bed is 0.1 wt%-10 wt%, preferably 0.5 wt%-2 wt%.

[0044] In the method for methoxycarbonylating unsaturated olefins of the present invention, the reaction is carried out at 50-150 °C, and the preferred reaction temperature is 70-100 °C.

[0045] In the method for methoxycarbonylating unsaturated olefins of the present invention, the reaction pressure is 0-5 MPa, and the preferred reaction pressure is 0.5-3.5 MPa.

[0046] In the method for methoxycarbonylating unsaturated olefins of the present invention, the reaction time is 5-50 h, and the preferred reaction time is 10-20 h.

[0047] The catalyst of the present invention is applied to the above-mentioned methoxycarbonylation reaction of unsaturated olefins. From the reaction mechanism, it can be known that there is a breakage of the methanol alkoxy group and hydrogen bond during the reaction process. The presence of carbonyl groups in the copolymer backbone structure can cause an electron cloud shift with the benzene ring, and this electron cloud shift is beneficial to catalyze the breakage of the alkoxy group and hydrogen bond. Therefore, this step is the rate-determining step, which can increase the intrinsic reaction rate.

[0048] In addition, the copolymer backbone structure contains not only nitrogen or phosphine heteroatoms, but also oxygen heteroatoms formed by dehydration. Oxygen has a relatively strong electronegativity. On the one hand, it can further improve the binding force with the active metal and enhance the stability of the catalyst; on the other hand, it can increase the polarity of the copolymer backbone structure, which is beneficial to improving the wettability of the catalyst to methanol and increasing the external diffusion rate.

[0049] Therefore, the catalyst of the present invention not only has excellent catalytic activity and stability, but also has a relatively high reaction rate. In addition, during product refining, rapid and low-energy consumption separation of the catalyst and the product can be achieved, reducing the product separation cost. Detailed implementation mode

[0050] The following examples further illustrate the preferred specific implementation modes within the scope of the present invention. These examples are merely illustrative and do not limit the scope of the present invention. The purpose of the following examples is to further introduce and demonstrate the specific implementation modes within the scope of the present invention. Therefore, the examples should be understood as only being used to more detailedly display the present invention without limiting the content of the present invention in any way.

[0051] The present invention quantitatively analyzes the metal content in the reaction solution by an inductively coupled plasma optical emission spectrometer (ICP-OES).

[0052] The present invention analyzes the composition of the reaction solution by gas chromatography GC-2014. The turnover number TON is calculated by formula (1) to compare the catalyst stability, the TOF is calculated by formula (2) to compare the catalyst reaction rate, the reaction selectivity is calculated by formula (3), and the palladium loss rate before and after the reaction is calculated by formula (4).

[0053] (1) TON = the amount of methyl propionate (MeP) accumulated during the reaction process in mol / the total added amount of metal in mol;

[0054] (2) TOF = the molar amount of methyl propionate generated per unit time in mol / the amount of metal required for the reaction in mol;

[0055] (3) Selectivity % = the amount of reactant consumed to produce the target product in mol / the amount of reactant participating in the reaction in mol * 100.

[0056] (4) Palladium loss rate % = (mol of palladium in the catalyst before reaction - mol of palladium in the catalyst after reaction) / mol of palladium in the catalyst before reaction * 100.

[0057] Example 1

[0058] Preparation of copolymer backbone support:

[0059] Take 18 g of polycarboxylic compound of formula 1-1 and 39.2 g of polyamine compound of formula 3-1, add them to 190.67 g of methanol, and add SR1L Na strongly acidic resin. Under a nitrogen atmosphere, at normal pressure, react at 70 °C for 8 h, then filter out the polymer under a nitrogen atmosphere and dry it at 90 °C for 10 h to obtain the copolymer backbone support.

[0060] Catalyst preparation:

[0061] Take 1.086 g of palladium acetate, dissolve it in methanol by the equal-volume impregnation method, add the above support, react at normal pressure of 30 °C under a nitrogen atmosphere, and rotary dry at 64.8 °C to evaporate the solvent to obtain catalyst A.

[0062] Example 2

[0063] Preparation of copolymer backbone support:

[0064] Take 17.9 g of polycarboxylic compound of formula 1-2 and 12.4 g of polyhydroxyphosphine compound of formula 2-1, add them to 151.5 g of ethanol, and add SR1L Na strongly acidic resin. Under a nitrogen atmosphere, at normal pressure, react at 50 °C for 5 h, then filter out the polymer under a nitrogen atmosphere and dry it at 80 °C for 2 h to obtain the copolymer backbone support.

[0065] Catalyst preparation:

[0066] Take 0.252 g of palladium chloride, dissolve it in ethanol by the equal-volume impregnation method, add the above support, react at normal pressure of 20 °C under a nitrogen atmosphere, and rotary dry at 78.3 °C to evaporate the solvent to obtain catalyst B.

[0067] Example 3

[0068] Preparation of copolymer backbone support:

[0069] Take 29.6 g of polycarboxylic compound of formula 1-3 and 8.35 g of polyhydroxy compound of formula 2-2, add them to 94.9 g of propanol, and add SR1L Na strongly acidic resin. Under a nitrogen atmosphere, at normal pressure, react at 100 °C for 10 h, then filter out the polymer under a nitrogen atmosphere and dry it at 100 °C for 20 h to obtain the copolymer backbone support.

[0070] Catalyst preparation:

[0071] Take 1.64 g of palladium nitrate, dissolve it in ethanol by equal-volume impregnation method, add the above carrier, react at normal pressure and 40 °C under a nitrogen atmosphere, and spin-dry at 78.3 °C to evaporate the solvent to obtain catalyst C.

[0072] Comparative Example 1

[0073] Preparation of copolymer backbone support:

[0074] Add 14.8 g and 39.2 g of the polyamino compound of formula 3-1 to 180 g of methanol, add SR1L Na strongly acidic resin, react at normal pressure and 70 °C for 8 h under a nitrogen atmosphere, filter out the polymer under a nitrogen atmosphere, and dry at 90 °C for 10 h to obtain the copolymer backbone support.

[0075] Catalyst preparation:

[0076] Take 1.025 g of palladium acetate, dissolve it in methanol by equal-volume impregnation method, add the above carrier, react at normal pressure and 30 °C under a nitrogen atmosphere, and spin-dry at 64.8 °C to evaporate the solvent to obtain catalyst D.

[0077] Comparative Example 2

[0078] Preparation of copolymer backbone support:

[0079] Add the 13.5 g described in CN 114522730 A, 10.9 g to 81.33 g of methanol, add SR1L Na strongly acidic resin, react at normal pressure and 70 °C for 8 h under a nitrogen atmosphere, filter out the polymer under a nitrogen atmosphere, and dry at 90 °C for 10 h to obtain the copolymer backbone support.

[0080] Catalyst preparation:

[0081] Take 0.463 g of palladium acetate, dissolve it in methanol by equal-volume impregnation method, add the above carrier, react at normal pressure and 30 °C under a nitrogen atmosphere, and spin-dry at 64.8 °C to evaporate the solvent to obtain catalyst E.

[0082] Comparative Example 3

[0083] Preparation of copolymer backbone support:

[0084] Take 16.61 g of terephthalic acid and 12.61 g of phloroglucinol, add them to 97.4 g of methanol, add SR1L strongly acidic resin. Under nitrogen atmosphere, at normal pressure, react for 8 h at 70 °C, then filter out the polymer under nitrogen atmosphere and dry it at 90 °C for 10 h to prepare the copolymer backbone support.

[0085] Catalyst preparation:

[0086] Take 0.555 g of palladium acetate, dissolve it in methanol by equal - volume impregnation method, add the above - mentioned support, react at normal pressure and 30 °C under nitrogen atmosphere, and rotary dry at 64.8 °C to evaporate the solvent to prepare catalyst G.

[0087] Example 4

[0088] Weigh 160 g of methanol and 160 g of anisole, add them to the reaction kettle, add catalyst A to form a slurry with a catalyst concentration of 1.5 wt%, after purging with nitrogen, heat up to 80 °C, add a mixture of ethylene and CO with a molar ratio of 1:1 to the reaction kettle to form a reaction pressure of 2 MPa, continuously inject the mixture through the pressure difference, stop the reaction after reacting for 15 h and reuse it. Reuse it 10 times in total. Calculate that the average TOF within the first 5 h is 50260 mol MeP·mol Pd -1 ·h -1 , and the total TON after 10 - time reuse is 788296 molMeP·mol Pd -1 . Calculate that the palladium loss amount before and after the reaction is 2.9% after 10 - time reuse.

[0089] Example 5

[0090] Weigh 160 g of methanol and 800 g of anisole, add them to the reaction kettle, add catalyst B to form a slurry with a catalyst concentration of 1 wt%, after purging with nitrogen, heat up to 70 °C, add a mixture of ethylene and CO with a molar ratio of 1:1 to the reaction kettle to form a reaction pressure of 0.5 MPa, continuously inject the mixture through the pressure difference, stop the reaction after reacting for 15 h and reuse it. Reuse it 10 times in total. Calculate that the average TOF within the first 5 h is 48132 mol MeP·mol Pd -1 ·h -1 , and the total TON after 10 - time reuse is 709466 molMeP·mol Pd -1 . Calculate that the palladium loss amount before and after the reaction is 3.2% after 10 - time reuse.

[0091] Example 6

[0092] Weigh 320 g of methanol and 64 g of anisole, add them to a reaction kettle, add catalyst C to form a slurry with a catalyst concentration of 0.5 wt%, after purging with nitrogen, heat up to 100 °C, add a 1:1 mixture of ethylene and CO to the reaction kettle to form a reaction pressure of 3.5 MPa, continuously inject the mixture through the pressure difference, stop the reaction after 15 h and reuse the reaction mixture. Reuse it 10 times in total. Calculate that the average TOF within the first 5 h is 51002 mol MeP·mol Pd -1 ·h -1 , and the total TON after 10 times of reuse is 886833 mol MeP·molPd -1 . After 10 times of reuse, calculate that the palladium loss before and after the reaction is 3.0%.

[0093] Comparative Example 4

[0094] Weigh 160 g of methanol and 160 g of anisole, add them to a reaction kettle, add catalyst D to form a slurry with a catalyst concentration of 1.5 wt%, after purging with nitrogen, heat up to 80 °C, add a 1:1 mixture of ethylene and CO to the reaction kettle to form a reaction pressure of 2 MPa, continuously inject the mixture through the pressure difference, stop the reaction after 15 h and reuse the reaction mixture. Reuse it 10 times in total. Calculate that the average TOF within the first 5 h is 45000 mol MeP·mol Pd -1 ·h -1 , and the total TON after 10 times of reuse is 635438 mol MeP·molPd -1 . After 10 times of reuse, calculate that the palladium loss before and after the reaction is 4.8%.

[0095] Comparative Example 5

[0096] Weigh 160 g of methanol and 160 g of anisole, add them to a reaction kettle, add catalyst E to form a slurry with a catalyst concentration of 1.5 wt%, after purging with nitrogen, heat up to 80 °C, add a mixture of ethylene and CO with a molar ratio of 1:1 to the reaction kettle to form a reaction pressure of 2 MPa, continuously inject the mixture through the pressure difference, stop the reaction after 15 h and reuse the reaction mixture. Reuse it 10 times in total. Calculate that the average TOF within the first 5 h is 30825 mol MeP·mol Pd -1 ·h -1 , and the total TON after 10 times of reuse is 510030 molMeP·mol Pd -1 . After 10 times of reuse, calculate that the palladium loss before and after the reaction is 8.5%.

[0097] Comparative Example 6

[0098] Weigh 160 g of methanol and 160 g of anisole, add them to the reaction kettle, add catalyst G to form a slurry with a catalyst concentration of 1.5 wt%, after purging with nitrogen, heat up to 80 °C, add a mixture of ethylene and CO with a molar ratio of 1:1 to the reaction kettle to form a reaction pressure of 2 MPa, continuously introduce the mixture through the pressure difference, stop the reaction after reacting for 15 h and reuse it. Reuse it 10 times in total. Calculate that the average TOF within the first 5 h is 29320 mol MeP·mol Pd -1 ·h -1 , and the total TON after reusing 10 times is 453820 molMeP·mol Pd -1 . After reusing it 10 times, calculate that the palladium loss before and after the reaction is 12.6%.

[0099] By comparing the activities and stabilities of the unsaturated olefin methoxycarbonylation catalysts prepared in the above examples and comparative examples, it can be obtained that the catalysts prepared by this patent have excellent catalytic activity and stability, and at the same time, the reaction rate is relatively fast. In addition, the catalyst is immobilized, and rapid and low-energy consumption separation of the catalyst and the product can be achieved during product refining, reducing the product refining cost.

Claims

1. An unsaturated olefin methoxycarbonylation catalyst, comprising the following components: (1) Group VI B and / or Group VIII B metal active components; (2) A copolymerized skeleton support; Wherein, The Group VI B or Group VIII B metal includes one or more of Cr, Mo, W, Fe, Co, Ni, Ru, Rh, Os, Ir, Pt, and Pd; The copolymerized skeleton support is a polymer of an aromatic compound containing phosphorus and / or nitrogen, and a carbonyl group; The raw materials for preparing the copolymerized skeleton support include: one or more of a polyhydroxy compound and a polyamino compound, and a polycarboxy aromatic compound; The polycarboxy aromatic compound is selected from the following substances: The polyhydroxy compound is selected from the following substances: The polyamino compound is selected from the following substances:

2. The catalyst according to claim 1, Characterized in that, The Group VI B and / or Group VIII B metal active components are derived from salts corresponding to the respective metals, including one or more of nitrates, chlorides, acetates, sulfonates, and phosphates.

3. The catalyst according to claim 1, Characterized in that, The Group VI B and / or Group VIII B metal active components are derived from one or more of palladium acetate, palladium chloride, and palladium nitrate.

4. The catalyst according to claim 1, Characterized in that, The method for preparing the copolymerized skeleton support includes the following steps: in the presence of a solvent, one or more of a polyhydroxy compound and a polyamino compound react with a polycarboxy aromatic compound by dehydration reaction.

5. The catalyst according to claim 4, Characterized in that, The method for preparing the catalyst includes the following steps: under the protection of an inert atmosphere, the copolymerized skeleton support is mixed uniformly with a solution of the metal active component, allowed to stand and impregnate for 1 - 5 h, and the solvent is removed.

6. The catalyst according to claim 1, Characterized in that, The loading amount of the metal active component is 0.1 wt% - 5 wt%.

7. The catalyst according to claim 1, Characterized in that, The loading amount of the metal active component is 0.5 wt% - 2 wt%.

8. A method for the methoxycarbonylation of an unsaturated olefin, Comprising the following steps: In the presence of the catalyst according to any one of claims 1 - 7, using carbon monoxide as a carbonylation reagent, in the presence of a hydroxy compound, subjecting the unsaturated olefin to methoxycarbonylation.

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