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

Abstract

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 by a sulfonic acid group and a phosphine ligand, a preparation method of the sulfonic acid resin-based Pd catalyst and application of the sulfonic acid resin-based Pd catalyst in olefin hydroesterification reaction. The preparation method of the sulfonic acid resin-based Pd catalyst comprises the following steps: adding halogen into sulfonic acid resin in a dark place, and refluxing alkali liquor to obtain halogenated sulfonic acid resin; carrying out reflux reaction on the phosphine ligand and a deprotonation agent to obtain a phosphine ligand precursor; dropwise adding a phosphine ligand precursor into the halogenated sulfonic acid resin for reaction, and adding an acidic solution to obtain dual-modified sulfonic acid resin; and adding sulfonic acid and phosphine ligand double-modified sulfonic acid resin into the Pd compound, carrying out impregnation reaction, and drying to obtain the sulfonic acid resin-based Pd catalyst. When the sulfonic acid resin-based Pd catalyst is used for preparing organic carboxylic ester, the product is easy to separate, the corrosion to equipment is small, the repeated utilization rate of the sulfonic acid resin-based Pd catalyst is high, the reaction conditions are mild, the raw material application range is wide, and the product selectivity is high.

Description

Technical Field

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

[0002] The carbonylation of olefins provides an efficient, direct and green method for the functionalization of olefin double bonds, which is used to produce a variety of high-value-added carbonyl compounds, including non-steroidal and anti-inflammatory drug intermediates, such as ibuprofen, naproxen, etc. Transition metal complexes such as 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 provide high activity and selectivity for the hydroesterification of olefins under mild conditions in homogeneous reactors. Although homogeneous systems show outstanding catalytic activity and selectivity, the difficulty in catalyst separation and reuse has seriously restricted their industrialization process. In order to solve these problems, supported palladium catalysts have received widespread attention. It has been found that palladium complexes fixed on supports such as montmorillonite, graphite, and silica can be used 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. In addition, insoluble acids such as polymer sulfonic acid and Pd-1,2-bis(di-tert-butylphosphine-methyl)benzene complexes show excellent catalytic performance in the hydroesterification of styrene. In general, strongly acidic cation exchange resins are considered to be less corrosive and easier to recycle than traditional harmful homogeneous acids. Therefore, they are often used as acidic additives and carriers in hydrogenation, H2O2 synthesis, etc.

[0004] At present, most of the olefin hydroesterification reactions use a simple impregnation method to load Pd onto a sulfonic acid resin carrier. However, the Pd in ​​this way has a weak binding force with the carrier, the metal Pd is easy to lose, and additional phosphine ligands need to be added, which increases the complexity of the process and the investment cost. In addition, the catalyst prepared by this method has poor stability, and it is difficult to recycle and reuse Pd after it is lost, resulting in serious 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. The 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 a gel-type strongly acidic ion exchange resin as a catalyst, high reaction conversion rate, high selectivity, and few by-products. However, the catalyst system is only to replace methanesulfonic acid with sulfonic acid resin, palladium acetate and phosphine ligands are still in the solution, that is, the reaction is still a homogeneous reaction, and the separation of the catalyst and the 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 palladium coordinated with a bidentate phosphine ligand and an imidazole sulfonic acid ionic liquid. The structural formula of the palladium phosphine complex modified with the imidazole sulfonic acid ionic liquid is: R1 represents an alkyl group with a sulfonic acid group, and R2 represents H or an alkyl group. The disadvantages of poor stability and short service life of the existing palladium phosphine catalyst system can be overcome well. However, the synthesis cost of the ionic liquid catalyst is high, the economy is poor, and the Pd modification using imidazole as the modification matrix is ​​difficult to react. 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, which is used to prepare organic carboxylic acid esters, has easy product separation, low corrosion to equipment, high reusability of the sulfonic acid resin-based Pd catalyst, wide application range of reaction conditions and temperature, 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 a dark environment to react, washing, and then treating with an 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 to react 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-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 butyl lithium, butyl aluminum, 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%, and is stirred 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 concentration of Pd 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] The invention discloses an application of a sulfonic acid resin-based Pd catalyst in an olefin hydroesterification reaction, comprising the following steps: mixing an alcohol and a sulfonic acid resin-based Pd catalyst, charging a terminal olefin, pressurizing, heating, and reacting. The pressurized gas is CO or a mixture of CO and N2, and its mass purity is 90-100%. The alcohol is one of methanol, ethanol, ethylene glycol, and glycerol, and the alcohol compound is also used as a solvent for the reaction system. The terminal olefin is one of ethylene, propylene, butylene, butadiene, and styrene, and the terminal olefin mass purity is 90-100%. The reaction temperature is controlled at 50-180°C, preferably 80-120°C; the reaction pressure is controlled at 1-10MPa, preferably 1-5MPa; and the reaction time is controlled at 2-10h.

[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-proof manner for reaction, adding the Cl2 or Br2 or I2 in a mass ratio of (50-200):(1-50), reacting at 30-120° C. for 2-24 h, washing with deionized water, and treating with 0.1-2 mol / L alkali solution for 2-12 h to remove unreacted halogen, thereby obtaining 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) Under stirring, add a phosphine ligand precursor to the halosulfonic acid resin, the mass ratio of the phosphine ligand to the halosulfonic acid resin is (0.1-1):(5-10), and react at -78-0°C with stirring for 2-24 hours to obtain a phosphine ligand-modified sulfonic acid resin.

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

[0031] (5) dissolving the Pd compound in a solvent to obtain a Pd concentration of 50-100 mmol / L, adding a sulfonic acid resin double-modified with sulfonic acid and phosphine ligands, impregnating and reacting for 6-72 hours, and drying 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 sulfonic acid resin-based Pd catalyst are mixed, the autoclave is sealed, and the autoclave is replaced three times with pressurized gas (CO or a mixture of CO and N2), and terminal olefins (ethylene, propylene, butylene, butadiene, styrene) are charged, and the pressure is increased to 1-10 MPa. The temperature is slowly raised to 50-180°C by a temperature controller, and the reaction is carried out for 2-10 hours. The reaction is cooled to room temperature, the autoclave is unloaded, and the liquid obtained by the reaction is quantitatively analyzed using Agilent 6890.

[0035] The sulfonic acid resin-based Pd catalyst of the present invention comprises the steps of halogenation of sulfonated styrene resin and modification of P ligand, a sulfonic acid resin carrier double-modified with sulfonic acid group and phosphine ligand is prepared, and a Pd compound is impregnated on the carrier to prepare a sulfonic acid resin-based Pd catalyst, which is used for the hydroesterification reaction of olefins, and the problem of fast corrosion of strong acid auxiliary agents can be solved, and the problem of difficulty in recycling homogeneous hydroesterification catalysts can also be solved. In addition, the catalyst system can also obtain higher reaction efficiency for the hydroesterification reaction of olefins. The present invention uses cheap sulfonic acid resin as a matrix, and prepares a multiphase hydroformylation catalyst by modifying the sulfonic acid resin with a phosphine ligand, and the operation method is simple, the catalyst activity is good, the stability is high, and the preparation cost of the sulfonic acid resin-based Pd catalyst is low.

[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, and improves 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 of the catalyst system from 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 in conjunction with 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 mixed gas of CO and N2 is 90%-100%, and the other chemical reagents used are all commercially available products, and the equipment used are 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) 100 g of Amberlyst 15 was placed in a 150 ml round-bottom flask, 50 ml of tetrahydrofuran was added, 0.5 g of Cl2 was slowly added in a dark environment, and the mixture was reacted at 30° C. for 24 h. After washing with deionized water, 1 mol / L NaOH solution was stirred and washed for 4 h to remove unreacted halogen, thereby obtaining a halogenated sulfonic acid resin.

[0045] (2) 1 g of PPh2Cl and 1 g of lithium were reacted in anhydrous tetrahydrofuran at -50°C for 36 h under N2 protection 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, and 10 g of sulfonic acid resin double-modified with sulfonic acid and phosphine ligands 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, the autoclave was replaced with CO for three times, 0.08 mol of ethylene was charged, the pressure was increased to 4 MPa, the temperature was slowly raised to 110° C. by a temperature controller, the reaction was carried out for 4 h, the autoclave was cooled to room temperature, the autoclave was unloaded, and the liquid obtained by the reaction was quantitatively analyzed by Agilent 6890. The ethylene conversion rate was 98%, and the selectivity of 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) 100 g of Dowex 50W was placed in a 150 ml round-bottom flask, 50 mL of toluene was added, 15 g of I2 was added in a dark environment, the mixture was reacted at 80° C. for 12 h, the mixture was washed with deionized water, and then stirred and washed with a 2 mol / L ammonia solution for 2 h to remove unreacted halogen, thereby obtaining a halogenated sulfonic acid resin.

[0053] (2) 1 g of PPh2Cl and 5 g of butylaluminum were reacted in anhydrous tetrahydrofuran under N2 protection at 0°C for 24 h 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 the 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-double-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, the autoclave was replaced with a mixture of CO and N2 three times, 0.08 mol of styrene was charged, the pressure was increased to 3 MPa, the temperature was slowly raised to 110° C. by a temperature controller, the reaction was carried out for 3 h, the autoclave was cooled to room temperature, the autoclave was unloaded, and the liquid obtained by the reaction was quantitatively analyzed by Agilent 6890. The styrene conversion rate was 95%, and the selectivity of 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 environment, the mixture was reacted at 120° C. for 2 h, the mixture was washed with deionized water, and then stirred and washed with 0.1 mol / L ammonia water for 12 h to remove unreacted halogen, thereby obtaining 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 the 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 palladium acetylacetonate in 50 mL of ethanol, add 10 g of sulfonic acid and phosphine ligand dual-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, the autoclave was replaced with CO or the autoclave was replaced three times, 0.2 mol of ethylene was charged, the pressure was increased to 2 MPa, the temperature was slowly raised to 100° C. by a temperature controller, the reaction was carried out for 4 h, the autoclave was cooled to room temperature, the autoclave was unloaded, and the liquid obtained by the reaction was quantitatively analyzed by Agilent 6890. The ethylene conversion rate was 98%, and the selectivity of 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 environment, 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 and obtain a halogenated sulfonic acid resin.

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

[0070] (3) Under stirring, 1 g of phosphine ligand precursor was added dropwise to 10 g of halosulfonic acid resin, and the mixture was stirred 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 the 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 allylpalladium chloride in 50 mL of toluene, add 10 g of sulfonic acid and phosphine ligand dual-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, the autoclave was replaced with CO for three times, 0.1 mol of styrene was charged, the pressure was increased to 2 MPa, the temperature was slowly raised to 110° C. by a temperature controller, the reaction was carried out for 4 h, the autoclave was cooled to room temperature, the autoclave was unloaded, and the liquid obtained by the reaction was quantitatively analyzed by Agilent 6890. The styrene conversion rate was 95%, and the selectivity of the product ethyl phenylpropionate was 99%.

[0074] Comparative Example 1

[0075] In a 250ml autoclave, PdCl2(PPh3)2 (0.05mmol) and methanol (100ml) were added in sequence. The autoclave was sealed, replaced with CO for 3 times, ethylene (0.6mol) was added, and CO gas was added until the pressure of the autoclave reached 4MPa. The temperature was slowly raised to 80℃ by a temperature controller, and the reaction was continued for 10h. The reaction was cooled to room temperature, the autoclave was unloaded, and the liquid obtained by the reaction was quantitatively analyzed by Agilent6890. The product methyl propionate was not detected.

[0076] Comparative Example 2

[0077] In a 250ml high-pressure reactor, 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 reactor was sealed, replaced with CO for 3 times, ethylene (0.2mol) was flushed in, and then CO gas was filled in until the pressure of the reactor reached 3MPa. The temperature was slowly raised to 80℃ by a temperature controller, and the reaction was continued for 6h. The reaction was cooled to room temperature, the reactor was unloaded, and the liquid obtained by the reaction was quantitatively analyzed by Agilent 6890. The ethylene conversion rate was 92%, and the selectivity of the product methyl propionate was 90%.

[0078] Comparative Example 3

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

[0080] Comparative Example 4

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

[0082] Comparative Example 5

[0083] The same as Example 1, except that the mass concentration of hydrochloric acid was 1%. The conversion rate 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 cannot be considered to limit the scope of the embodiments of the present invention. The present invention is not limited to the above examples, and equal changes and improvements made by ordinary technicians in the technical field within the essential scope of the present invention should all fall within the scope of the patent coverage 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 to react in the dark, washing, and treating with alkaline solution to obtain a halogenated sulfonic acid resin; (2) reacting the phosphine ligand with a deprotonating agent in a solvent to obtain a phosphine ligand precursor; (3) adding a phosphine ligand precursor to the halosulfonic acid resin to react 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-modified sulfonic acid resin; (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, characterized in that: 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, the concentration is 0.1-2 mol / L, and the treatment time is 2-12 h; the mass ratio of the sulfonic acid resin to the halogen is (50-200):(1-50).

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

4. The method for preparing a sulfonic acid resin-based Pd catalyst according to claim 1, characterized in that: In step (2), the mass ratio of the phosphine ligand to the deprotonating agent is (1-5):(1-10); the deprotonating agent is one of butyl lithium, butyl aluminum, and lithium.

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

6. The method for preparing the sulfonic acid resin-based Pd catalyst according to claim 1, characterized in that: 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, characterized in that: 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%.

8. The method for preparing a sulfonic acid resin-based Pd catalyst according to claim 1, characterized in that: The Pd compound in step (5) is one of palladium acetate, palladium chloride, palladium acetylacetonate, and allyl palladium 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 method for preparing 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 reaction, 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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