Sulfonic acid resin-based Pd catalyst, preparation method thereof, and application thereof in olefin hydroesterification reaction

Abstract

The present invention belongs to the technical field of olefin hydroesterification reactions and catalysts thereof, and specifically relates to a sulfonic acid resin-based Pd catalyst dually modified with a sulfonic acid group and a phosphine ligand, a preparation method thereof, and its application in olefin hydroesterification reactions. The preparation method of the sulfonic acid resin-based Pd catalyst comprises: adding a halogen to a sulfonic acid resin in the dark, and refluxing an alkaline solution to obtain a halogenated sulfonic acid resin; refluxing a phosphine ligand with a deprotonating agent to obtain a phosphine ligand precursor; dropwise adding the phosphine ligand precursor to the halogenated sulfonic acid resin for reaction, adding an acidic solution to obtain a dual-modified sulfonic acid resin; adding the sulfonic acid and phosphine ligand dual-modified sulfonic acid resin to a Pd compound, impregnating the sulfonic acid and phosphine ligand dual-modified sulfonic acid resin, and drying to obtain the sulfonic acid resin-based Pd catalyst. The sulfonic acid resin-based Pd catalyst of the present invention is suitable for preparing organic carboxylic acid esters, and the product is easily separated, has low corrosion to equipment, has a high reusability of the sulfonic acid resin-based Pd catalyst, has a wide range of reaction conditions and temperature, and is applicable to a wide range of raw materials, and has high product selectivity.

Description

Technical Field

[0001] The invention belongs to the technical field of olefin hydroesterification reaction and catalysts thereof, and particularly relates to a sulfonic acid resin-based Pd catalyst double-modified with sulfonic acid groups and phosphine ligands, a preparation method thereof, and application in olefin hydroesterification reaction. Background Art

[0002] The carbonylation of olefins offers an efficient, direct, and green method for functionalizing double bonds in olefins, resulting in the production of a variety of high-value-added carbonyl compounds, including nonsteroidal and anti-inflammatory drug intermediates such as ibuprofen and naproxen. Transition metal complexes, such as those of Ni, Co, Rh, and Pd, can be used as catalysts for olefin carbonylation reactions. In particular, Pd complexes, such as Pd(OTs)2(PPh3)2 and [Pd(MeCN)2(PPh3)2](BF4)2, offer high activity and selectivity for the hydroesterification of olefins in homogeneous reactors under mild conditions. Although these homogeneous systems exhibit outstanding catalytic activity and selectivity, difficulties in catalyst isolation and reuse have severely limited their industrialization. To address these challenges, supported palladium catalysts have garnered significant attention. Palladium complexes immobilized on supports such as montmorillonite, graphite, and silica have been shown to be useful for the hydroesterification of olefins.

[0003] As we all know, Acids are commonly used as additives in the hydroesterification of olefins. In traditional processes, soluble acids such as hydrochloric acid, oxalic acid, methanesulfonic acid, and p-toluenesulfonic acid (p-TsOH) are often used. Recently, Acidic ionic liquids are also used in the reaction. Furthermore, insoluble acids such as polymeric sulfonic acid and Pd-1,2-bis(di-tert-butylphosphino-methyl)benzene complexes have demonstrated excellent catalytic performance in the hydroesterification of styrene. Strongly acidic cation exchange resins are generally considered less corrosive and easier to recycle than traditional, harmful homogeneous acids. Therefore, they are often used as acidic adjuvants and supports in hydrogenation, H2O2 synthesis, and other applications.

[0004] Currently, most olefin hydroesterification reactions rely on a simple impregnation method to load Pd onto a sulfonic acid resin support. However, this method results in weak Pd-support binding, easy loss of metallic Pd, and the need for the addition of a phosphine ligand, which complicates the process and increases investment costs. Furthermore, the catalyst prepared using this method exhibits poor stability, and Pd loss is difficult to recover and reuse, resulting in significant waste.

[0005] CN104761451A discloses a preparation method of methyl propionate, using a gel-type strongly acidic ion exchange resin catalyst, which is a hydrogen-type styrene-stilbene copolymer with a sulfonate group, and the pore size of the resin is less than 8nm. Gel-type strongly acidic ion exchange resin is Dowex 50WX 2hydrogen form resin, Dowex 50WX 4hydrogen form resin or Dowex 50WX 8hydrogen form resin, using gel-type strongly acidic ion exchange resin as catalyst, reaction conversion rate is high, selectivity is high, and by-products are few. However, the catalyst system is only sulfonic acid resin substituted for methanesulfonic acid, and palladium acetate and phosphine ligand are still in solution, that is, reaction is still a homogeneous reaction, and the separation of catalyst and reaction system is difficult.

[0006] CN114849786A discloses an imidazole sulfonic acid ionic liquid-based palladium phosphine complex catalyst for synthesizing methyl propionate from ethylene hydromethyl ester. The catalyst is composed of a central atom of palladium coordinated with a bidentate phosphine ligand and an imidazole sulfonic acid ionic liquid. The structural formula of the imidazole sulfonic acid ionic liquid-modified palladium phosphine complex is as follows: R1 represents an alkyl group with a sulfonic acid group, and R2 represents H or an alkyl group. This method effectively overcomes the shortcomings of existing palladium phosphine catalyst systems, such as poor stability and short catalyst life. However, the synthesis cost of ionic liquid catalysts is high, resulting in poor economic efficiency. Furthermore, the use of imidazole as the modified substrate for Pd modification presents significant reaction difficulties. Summary of the Invention

[0007] The technical problem to be solved by the present invention is to overcome the deficiencies of the prior art and provide a sulfonic acid resin-based Pd catalyst. The catalyst is used to prepare organic carboxylic acid esters, and the product is easy to separate and has low corrosion to equipment. The sulfonic acid resin-based Pd catalyst has a high reusability, a wide range of reaction conditions and raw materials, and high product selectivity.

[0008] The preparation method of the sulfonic acid resin-based Pd catalyst of the present invention comprises the following steps:

[0009] (1) placing a sulfonic acid resin in a solvent, adding a halogen in the dark to react, washing, and then treating with alkaline solution to obtain a halogenated sulfonic acid resin;

[0010] (2) reacting the phosphine ligand with a deprotonating agent in a solvent to obtain a phosphine ligand precursor;

[0011] (3) adding a phosphine ligand precursor to the halosulfonic acid resin and reacting the precursor to obtain a phosphine ligand-modified sulfonic acid resin;

[0012] (4) adding an acidic solution to the phosphine ligand-modified sulfonic acid resin to react and obtain a sulfonic acid and phosphine ligand-double-modified sulfonic acid resin;

[0013] (5) The Pd compound is dissolved in a solvent, and a sulfonic acid resin double-modified with sulfonic acid and phosphine ligands is added, impregnated, and dried to obtain a sulfonic acid resin-based Pd catalyst.

[0014] The sulfonic acid resin in step (1) is one of Dowex 50W, Resin P, and Amberlyst 15; the halogen is one of Cl, Br, and I; the solvent is one of tetrahydrofuran, toluene, acetonitrile, and n-hexane; the alkali solution is one of ammonia water, sodium hydroxide solution, and ethylenediamine solution, with a concentration of 0.1-2 mol / L, and the treatment time is 2-12 h.

[0015] The mass ratio of the sulfonic acid resin to the halogen in step (1) is (50-200):(1-50).

[0016] The reaction temperature for adding halogen in step (1) is 30-120° C., and the reaction time is 2-24 h.

[0017] The phosphine ligand in step (2) is one of PPh2Cl, PPh2OCH3, and HPPh2; the deprotonating agent is one of butyllithium, butylaluminum, and lithium; the solvent is anhydrous tetrahydrofuran or toluene; and the mass ratio of the phosphine ligand to the deprotonating agent in step (2) is (1-5):(1-10).

[0018] The reaction temperature of step (2) is -50-10°C, and the reaction time is 1-36h.

[0019] The mass ratio of the phosphine ligand precursor to the halosulfonic acid resin in step (3) is (0.1-1): (5-10), the reaction temperature is -78-0°C, and the reaction time is 2-24h.

[0020] The acidic solution in step (4) is one of hydrochloric acid, sulfuric acid, oxalic acid, and acetic acid, with a mass fraction of 0.01-0.5%. Stirring is carried out at room temperature for 1-6 hours to obtain a sulfonic acid resin double-modified with sulfonic acid and phosphine ligands.

[0021] The Pd compound in step (5) is one of palladium acetate, palladium chloride, palladium acetylacetonate, and allylpalladium chloride; the solvent is one of methanol, toluene, ethanol, and deionized water, and the Pd concentration is 50-100 mmol / L.

[0022] The mass ratio of the Pd compound in step (5) to the sulfonic acid resin double-modified with sulfonic acid and phosphine ligands is 0.02-0.1.

[0023] The impregnation reaction time of step (5) is 6h-72h, the drying temperature is 50-120°C, and the drying time is 2-24h.

[0024] A sulfonic acid resin-based Pd catalyst is prepared by the preparation method of the sulfonic acid resin-based Pd catalyst.

[0025] A sulfonic acid resin-based Pd catalyst is used in an olefin hydroesterification reaction, comprising the following steps: mixing an alcohol and a sulfonic acid resin-based Pd catalyst, adding a terminal olefin, applying pressure, raising the temperature, and reacting. The pressurized gas is CO or a mixture of CO and N2, with a purity of 90-100%. The alcohol is one of methanol, ethanol, ethylene glycol, and glycerol, and the alcohol compound also serves as the solvent for the reaction system. The terminal olefin is one of ethylene, propylene, butylene, butadiene, and styrene, with a purity of 90-100%. The reaction temperature is controlled at 50-180°C, preferably 80-120°C; the reaction pressure is controlled at 1-10 MPa, preferably 1-5 MPa; and the reaction time is controlled at 2-10 hours.

[0026] Specifically, the use of the sulfonic acid resin-based Pd catalyst in the olefin hydroesterification reaction comprises the following steps:

[0027] (1) placing a sulfonic acid resin in a solvent, adding Cl2 or Br2 or I2 in a light-shielded manner for reaction at a mass ratio of (50-200):(1-50), reacting at 30-120°C for 2-24 hours, washing with deionized water, and treating with 0.1-2 mol / L alkali solution for 2-12 hours to remove unreacted halogen to obtain a halogenated sulfonic acid resin.

[0028] (2) The phosphine ligand and the deprotonating agent are reacted in a mass ratio of (1-5):(1-10) in a solvent under N2 protection at -50-10°C for 1-36 hours to obtain a phosphine ligand precursor.

[0029] (3) Add the phosphine ligand precursor dropwise to the halosulfonic acid resin under stirring, the mass ratio of the phosphine ligand to the halosulfonic acid resin is (0.1-1): (5-10), and stir the reaction at -78-0°C for 2-24 hours to obtain the phosphine ligand-modified sulfonic acid resin.

[0030] (4) Add 50 mL of an acidic solution with a mass fraction of 0.01-0.5% to 10 g of the phosphine ligand-modified sulfonic acid resin, and stir at room temperature for 1-6 h to obtain a sulfonic acid and phosphine ligand-double-modified sulfonic acid resin.

[0031] (5) Dissolve the Pd compound in a solvent to obtain a Pd concentration of 50-100 mmol / L, add a sulfonic acid resin double-modified with sulfonic acid and phosphine ligands, impregnate for 6-72 hours, and dry at 50-120° C. for 2-24 hours to obtain a sulfonic acid resin-based Pd catalyst.

[0032] The above reaction path is:

[0033]

[0034] (6) In a 250 ml autoclave, alcohol (methanol, ethanol, ethylene glycol, propylene glycol) and a sulfonic acid resin-based Pd catalyst were mixed. The autoclave was sealed and replaced three times with pressurized gas (CO or a mixture of CO and N2). Terminal olefins (ethylene, propylene, butylene, butadiene, styrene) were added and pressurized to 1-10 MPa. The temperature was slowly raised to 50-180°C using a temperature controller. The reaction was carried out for 2-10 h, cooled to room temperature, and the autoclave was unloaded. The resulting liquid was quantitatively analyzed using an Agilent 6890.

[0035] The sulfonic acid resin-based Pd catalyst of the present invention comprises the steps of halogenation of a sulfonated styrene resin and modification with a P ligand, and a sulfonic acid resin carrier double-modified with a sulfonic acid group and a phosphine ligand is prepared. The Pd compound is impregnated onto the carrier to prepare the sulfonic acid resin-based Pd catalyst, which is then used for the hydroesterification reaction of olefins. This not only solves the problem of rapid corrosion of strong acid adjuvants, but also solves the problem of difficulty in recovering homogeneous hydroesterification catalysts. In addition, the catalyst system can also achieve higher reaction efficiency for the hydroesterification reaction of olefins. The present invention uses a cheap sulfonic acid resin as a matrix and prepares a heterogeneous hydroformylation catalyst by modifying the sulfonic acid resin with a phosphine ligand. The operating method is simple, the catalyst activity is good, the stability is high, and the sulfonic acid resin-based Pd catalyst has a low preparation cost.

[0036] Compared with the prior art, the present invention has the following beneficial effects:

[0037] (1) The preparation method of the sulfonic acid resin-based Pd catalyst of the present invention modifies and fixes the phosphine ligand and the sulfonate group on the sulfonic acid resin carrier, which is beneficial to the synergistic effect between Pd and phosphine and H ions, thereby improving the reaction activity of the Pd site.

[0038] (2) The sulfonic acid resin-based Pd catalyst prepared by the present invention is a multiphase catalyst with a sulfonic acid resin as a carrier, which is beneficial to the separation between the catalyst system and the reaction raw materials and products, reduces the separation energy consumption, and realizes the recovery and reuse of the catalyst.

[0039] (3) In the olefin hydroesterification reaction, the benzene ring of the sulfonic acid resin prepared by the method of the present invention undergoes a variety of functionalization reactions, and the structure and properties are flexibly adjustable, which is beneficial to improving the reaction activity and stability of the catalyst. DETAILED DESCRIPTION

[0040] The present invention will be further described below with reference to specific embodiments.

[0041] In the following examples and comparative examples, the mass purity of the alcohol is 90%-100%, the mass purity of CO or the mixture of CO and N2 is 90%-100%, and the other chemical reagents used are all commercially available products, and the equipment used is all existing equipment.

[0042] Example 1

[0043] The use of the sulfonic acid resin-based Pd catalyst in the olefin hydroesterification reaction comprises the following steps:

[0044] (1) Place 100 g of Amberlyst 15 in a 150 ml round-bottom flask, add 50 ml of tetrahydrofuran, and slowly add 0.5 g of Cl2 in the dark. React at 30 °C for 24 h, wash with deionized water, and then stir and wash with 1 mol / L NaOH solution for 4 h to remove unreacted halogen to obtain a halosulfonic acid resin.

[0045] (2) 1 g of PPh2Cl and 1 g of lithium were reacted in anhydrous tetrahydrofuran at -50 °C under N2 protection for 36 h to obtain the phosphine ligand precursor PPh2Li.

[0046] (3) Under stirring, 1 g of phosphine ligand precursor was added dropwise to 100 g of halosulfonic acid resin, and the mixture was stirred at -10°C for 18 h to obtain phosphine ligand-modified sulfonic acid resin.

[0047] (4) Add 50 ml of 0.01% by mass hydrochloric acid solution to 10 g of phosphine ligand-modified sulfonic acid resin and react for 1 h to obtain a sulfonic acid and phosphine ligand-double-modified sulfonic acid resin.

[0048] (5) 0.224 g of palladium acetate was dissolved in 20 mL of deionized water, 10 g of sulfonic acid and phosphine ligand-modified sulfonic acid resin was added, the mixture was stirred for 6 h, and dried at 50 °C for 24 h to obtain a sulfonic acid resin-based Pd catalyst.

[0049] (6) In a 250 ml autoclave, 100 ml of methanol and 1 g of a sulfonic acid resin-based Pd catalyst were mixed. The autoclave was sealed and replaced with CO three times. 0.08 mol of ethylene was introduced and pressurized to 4 MPa. The temperature was slowly raised to 110°C using a temperature controller. The reaction was allowed to proceed for 4 h. The autoclave was cooled to room temperature, the autoclave was unloaded, and the resulting liquid was quantitatively analyzed using an Agilent 6890. The ethylene conversion was 98%, and the selectivity for the product methyl propionate was 99%.

[0050] Example 2

[0051] The use of the sulfonic acid resin-based Pd catalyst in the olefin hydroesterification reaction comprises the following steps:

[0052] (1) Place 100 g of Dowex 50W in a 150 ml round-bottom flask, add 50 mL of toluene, add 15 g of I2 in a dark place, react at 80 °C for 12 h, wash with deionized water, and then stir and wash with 2 mol / L ammonia solution for 2 h to remove unreacted halogen to obtain a halogenated sulfonic acid resin.

[0053] (2) 1 g of PPh2Cl and 5 g of butylaluminum were reacted in anhydrous tetrahydrofuran at 0°C for 24 h under N2 protection to obtain the phosphine ligand precursor PPh2Li.

[0054] (3) Under stirring, 1 g of phosphine ligand precursor was added dropwise to 5 g of halosulfonic acid resin, and the mixture was stirred at -20°C for 12 h to obtain phosphine ligand-modified sulfonic acid resin.

[0055] (4) Add 50 ml of 0.05% by mass sulfuric acid solution to 10 g of phosphine ligand-modified sulfonic acid resin and react for 2 h to obtain a sulfonic acid and phosphine ligand-double-modified sulfonic acid resin.

[0056] (5) 0.88 g of palladium chloride was dissolved in 50 mL of methanol, 10 g of sulfonic acid and phosphine ligand-modified sulfonic acid resin was added, the mixture was immersed for 6 h, and dried at 120 °C for 2 h to obtain a sulfonic acid resin-based Pd catalyst.

[0057] (6) In a 250 ml autoclave, 100 ml of methanol and 1 g of a sulfonic acid resin-based Pd catalyst were mixed. The autoclave was sealed and replaced three times with a mixture of CO and N2. 0.08 mol of styrene was introduced and pressurized to 3 MPa. The temperature was slowly raised to 110°C using a temperature controller. The reaction was allowed to proceed for 3 h. The autoclave was then cooled to room temperature and the reaction mixture was unloaded. The resulting liquid was quantitatively analyzed using an Agilent 6890. The styrene conversion was 95%, and the selectivity for the product, methyl phenylpropionate, was 98%.

[0058] Example 3

[0059] The use of the sulfonic acid resin-based Pd catalyst in the olefin hydroesterification reaction comprises the following steps:

[0060] (1) 10 g of sulfonic acid resin Dowex 50W was placed in a 150 ml round-bottom flask, 50 mL of n-hexane was added, 10 g of Br2 was added in a dark atmosphere, and the mixture was reacted at 120 °C for 2 h. After washing with deionized water, the mixture was stirred and washed with 0.1 mol / L ammonia water for 12 h to remove unreacted halogen to obtain a halogenated sulfonic acid resin.

[0061] (2) 1 g of HPPh2 was reacted with 10 g of butyl lithium in toluene at -20 °C under N2 protection for 24 h to obtain the phosphine ligand precursor PPh2Li.

[0062] (3) Under stirring, 1 g of phosphine ligand precursor was added dropwise to 50 g of halosulfonic acid resin, and the mixture was stirred at -78°C for 24 h to obtain phosphine ligand-modified sulfonic acid resin.

[0063] (4) Add 50 ml of 0.5% by mass acetic acid solution to 10 g of phosphine ligand-modified sulfonic acid resin and react for 6 h to obtain a sulfonic acid and phosphine ligand-double-modified sulfonic acid resin.

[0064] (5) Dissolve 1 g of acetylacetonate palladium in 50 mL of ethanol, add 10 g of sulfonic acid and phosphine ligand-modified sulfonic acid resin, soak for 72 h, and dry at 80 °C for 12 h to obtain a sulfonic acid resin-based Pd catalyst.

[0065] (6) In a 250 ml autoclave, 50 ml of methanol and 1 g of a sulfonic acid resin-based Pd catalyst were mixed. The autoclave was sealed and replaced with CO or the autoclave was replaced three times. 0.2 mol of ethylene was introduced and the pressure was increased to 2 MPa. The temperature was slowly raised to 100°C using a temperature controller. The reaction was allowed to proceed for 4 h. The autoclave was cooled to room temperature, the autoclave was unloaded, and the resulting liquid was quantitatively analyzed using an Agilent 6890. The ethylene conversion was 98%, and the selectivity for the product methyl propionate was 96%.

[0066] Example 4

[0067] The use of the sulfonic acid resin-based Pd catalyst in the olefin hydroesterification reaction comprises the following steps:

[0068] (1) 50 g of Resin P was placed in a 150 ml round-bottom flask, 50 mL of acetonitrile was added, 15 g of Cl2 was added in a dark place, and the mixture was reacted at 100 °C for 12 h. After washing with deionized water, the mixture was stirred and washed with 1 mol / L ethylenediamine solution for 8 h to remove unreacted halogen to obtain a halogenated sulfonic acid resin.

[0069] (2) 1 g of PPh2OCH3 was reacted with 8 g of lithium in anhydrous tetrahydrofuran at 10°C for 1 h under N2 protection to obtain the phosphine ligand precursor PPh2Li.

[0070] (3) Add 1 g of phosphine ligand precursor dropwise to 10 g of halosulfonic acid resin under stirring, and react at 0° C. for 2 h to obtain phosphine ligand-modified sulfonic acid resin.

[0071] (4) Add 50 ml of 0.1% by mass oxalic acid solution to 10 g of phosphine ligand-modified sulfonic acid resin and react for 4 h to obtain a sulfonic acid and phosphine ligand-double-modified sulfonic acid resin.

[0072] (5) Dissolve 1 g of allyl palladium chloride in 50 mL of toluene, add 10 g of sulfonic acid and phosphine ligand-modified sulfonic acid resin, soak for 36 h, and dry at 100 °C for 12 h to obtain a sulfonic acid resin-based Pd catalyst.

[0073] (6) In a 250 ml autoclave, 50 ml of methanol and 1 g of a sulfonic acid resin-based Pd catalyst were mixed. The autoclave was sealed and replaced with CO three times. 0.1 mol of styrene was introduced and pressurized to 2 MPa. The temperature was slowly raised to 110°C using a temperature controller. The reaction was allowed to proceed for 4 h. The autoclave was cooled to room temperature, the autoclave was unloaded, and the resulting liquid was quantitatively analyzed using an Agilent 6890. The styrene conversion was 95%, and the selectivity for the product, ethyl phenylpropionate, was 99%.

[0074] Comparative Example 1

[0075] To a 250ml autoclave, PdCl2(PPh3)2 (0.05mmol) and methanol (100ml) were added sequentially. The autoclave was sealed and replaced with CO3 three times. Ethylene (0.6mol) was then introduced, and CO2 gas was then added to the autoclave until the pressure reached 4MPa. The temperature was slowly raised to 80°C using a temperature controller. The reaction was continued for 10h, cooled to room temperature, and the autoclave was unloaded. The resulting liquid was quantitatively analyzed using an Agilent 6890. No methyl propionate was detected.

[0076] Comparative Example 2

[0077] To a 250ml autoclave, Pd(OAc)2 (0.05mmol), methanesulfonic acid (0.5mmol), 1,2-bis[(di-tert-butylphosphino)methyl]benzene (0.4mmol), and methanol (100ml) were added in sequence. The autoclave was sealed, replaced with CO3 three times, flushed with ethylene (0.2mol), and then filled with CO2 until the pressure reached 3MPa. The temperature was slowly raised to 80°C using a temperature controller. The reaction was continued for 6h, cooled to room temperature, and the autoclave was unloaded. The resulting liquid was quantitatively analyzed using an Agilent 6890. The ethylene conversion was 92%, and the selectivity for the product methyl propionate was 90%.

[0078] Comparative Example 3

[0079] The same method as in Example 1 was used, except that 0.1 g of Cl2 was added. The conversion of ethylene was 56%, and the selectivity of the product methyl propionate was 80%.

[0080] Comparative Example 4

[0081] The same method as in Example 1 was used, except that 0.1 g of metallic lithium was added. The conversion of ethylene was 36%, and the selectivity of the product methyl propionate was 66%.

[0082] Comparative Example 5

[0083] The same method as in Example 1, except that the mass concentration of hydrochloric acid was 1%, the conversion of ethylene was 76%, and the selectivity of the product methyl propionate was 75%.

[0084] Of course, the above contents are only preferred embodiments of the present invention and should not be considered as limiting the scope of the embodiments of the present invention. The present invention is not limited to the above examples. Equivalent changes and improvements made by ordinary technicians in this technical field within the essential scope of the present invention should all fall within the scope of the patent of the present invention.

Claims

1. A method for preparing a sulfonic acid resin-based Pd catalyst, characterized in that: The following steps are involved: (1) placing a sulfonic acid resin in a solvent, adding a halogen in the dark to react, washing, and treating with alkaline solution to obtain a halogenated sulfonic acid resin; the mass ratio of the sulfonic acid resin to the halogen is (50-200):(1-50); (2) reacting a phosphine ligand with a deprotonating agent in a solvent to obtain a phosphine ligand precursor; the mass ratio of the phosphine ligand to the deprotonating agent is (1-5): (1-10); (3) adding a phosphine ligand precursor to the halosulfonic acid resin and reacting the precursor to obtain a phosphine ligand-modified sulfonic acid resin; (4) adding an acidic solution to the phosphine ligand-modified sulfonic acid resin to react and obtain a sulfonic acid and phosphine ligand-double-modified sulfonic acid resin; the mass fraction of the acidic solution is 0.01-0.5%; (5) The Pd compound is dissolved in a solvent, and a sulfonic acid resin double-modified with sulfonic acid and phosphine ligands is added, impregnated, and dried to obtain a sulfonic acid resin-based Pd catalyst.

2. The method for preparing a sulfonic acid resin-based Pd catalyst according to claim 1, wherein: The sulfonic acid resin in step (1) is one of Dowex 50W, Resin P, and Amberlyst 15; the solvent is one of tetrahydrofuran, toluene, acetonitrile, and n-hexane; the alkali solution is one of ammonia water, sodium hydroxide solution, and ethylenediamine solution, with a concentration of 0.1-2 mol / L, and the treatment time is 2-12 h.

3. The method for preparing a sulfonic acid resin-based Pd catalyst according to claim 1, wherein: The reaction temperature for adding halogen in step (1) is 30-120°C, and the reaction time is 2-24h.

4. The method for preparing a sulfonic acid resin-based Pd catalyst according to claim 1, wherein: In step (2), the deprotonating agent is one of butyl lithium, butyl aluminum, and lithium.

5. The method for preparing a sulfonic acid resin-based Pd catalyst according to claim 1, wherein: The reaction temperature of step (2) is -50-10°C, and the reaction time is 1-36h.

6. The method for preparing a sulfonic acid resin-based Pd catalyst according to claim 1, wherein: The mass ratio of the phosphine ligand precursor to the halosulfonic acid resin in step (3) is (0.1-1): (5-10), the reaction temperature is -78-0°C, and the reaction time is 2-24h.

7. The method for preparing a sulfonic acid resin-based Pd catalyst according to claim 1, wherein: The acidic solution in step (4) is one of hydrochloric acid, sulfuric acid, oxalic acid and acetic acid.

8. The method for preparing a sulfonic acid resin-based Pd catalyst according to claim 1, wherein: The Pd compound in step (5) is one of palladium acetate, palladium chloride, palladium acetylacetonate, and allylpalladium chloride; the solvent is one of methanol, toluene, ethanol, and deionized water, and the Pd concentration is 50-100 mmol / L; the impregnation reaction time is 6h-72h, the drying temperature is 50-120°C, and the drying time is 2-24h.

9. A sulfonic acid resin-based Pd catalyst, characterized in that: The catalyst is prepared by the preparation method of the sulfonic acid resin-based Pd catalyst according to any one of claims 1 to 8.

10. Use of the sulfonic acid resin-based Pd catalyst according to claim 9 in olefin hydroesterification, characterized in that: The following steps are involved: Mix the alcohol and sulfonic acid resin-based Pd catalyst, add the terminal olefin, apply pressure, increase the temperature, and react.

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