CN119425791A

CN119425791A - A resin catalyst and its preparation method and its application in bisphenol A synthesis

Info

Publication number: CN119425791A
Application number: CN202411568988.1A
Authority: CN
Inventors: 王建黎; 梁圣; 楼政; 陈望彬; 徐晓航
Original assignee: Ningbo Zhengguang Resin Co ltd; Zhejiang University of Technology ZJUT
Current assignee: Ningbo Zhengguang Resin Co ltd; Zhejiang University of Technology ZJUT
Priority date: 2024-11-05
Filing date: 2024-11-05
Publication date: 2025-02-14

Abstract

The invention relates to the technical field of chemical industry, in particular to a resin catalyst, a preparation method thereof and application thereof in bisphenol A synthesis. Swelling macroporous crosslinked polystyrene microsphere to obtain swelled microsphere, mixing the swelled microsphere with fuming sulfuric acid and sulfonic acid reagent, stirring to obtain modified resin, mixing the modified resin with N, N, N-trimethyl-3-mercaptopropyl quaternary ammonium salt, and heat treating under the protection of inert gas to obtain the resin catalyst. The preparation method of the resin catalyst provided by the invention has the advantages of simple steps, low cost, environment friendliness, no pollution, high utilization rate of active components, good preparation repeatability, and excellent performances of bisphenol A (more than or equal to 95%) selectivity and stability of more than or equal to 120 days, and the yield is more than or equal to 85% under the mild condition (70 ℃ and 1h ^‑1) by combining with a continuous flow fixed bed reactor. Can realize the separation of the catalyst and the product, has simple production process and high product purity, and greatly reduces the production cost.

Description

Resin catalyst, preparation method thereof and application thereof in bisphenol A synthesis

Technical Field

The invention relates to the technical field of chemical industry, in particular to a resin catalyst, a preparation method thereof and application thereof in bisphenol A synthesis.

Background

Bisphenol A [ also known as 2, 2-bis (4-hydroxyphenyl) propane ] is an important chemical raw material, is mainly used for producing various high polymer materials such as polycarbonate, epoxy resin, polysulfone resin, polyphenyl ether resin, unsaturated polyester resin and the like, and has important effects in the production of fine chemical products, namely plasticizers, flame retardants, antioxidants, rubber antioxidants, pesticides, paint dyes and the like.

Bisphenol a is generally prepared by condensing phenol and acetone in the presence of an acid catalyst. In the early bisphenol A production process, common catalysts included inorganic acids such as hydrogen chloride and sulfuric acid. The catalyst used in the hydrogen chloride method is anhydrous hydrogen chloride, has higher reaction selectivity, and can produce bisphenol A products with better quality, so the process is more commonly used in industry. However, this method has the disadvantage that hydrogen chloride is extremely corrosive, which places stringent demands on the choice of materials for the piping and equipment, resulting in the process being gradually eliminated. The sulfuric acid method adopts 75 to 80 percent of sulfuric acid, and the bisphenol A can be produced, but the product has deeper color, lower purity and high material consumption, and a large amount of waste water and waste acid containing phenol and acid are produced in the production process, so that the serious pollution to the environment is gradually eliminated (Meng Jian. Chemical design communication, 2021,47 (02): 140-141). Because of the disadvantages of the hydrogen chloride method and the sulfuric acid method, respectively, researchers have developed various heterogeneous catalysts to achieve the cleanliness of bisphenol A production. For example, a sulfonic acid functionalized mesoporous MCM-41 molecular sieve prepared by Debasish Das (Das D.al., chemical Communications,2001 (21): 2178-2179) catalyzes the condensation of phenol and acetone to synthesize bisphenol A at a lower temperature, and has high selectivity. Chen Qun (Chen Qun et al, CN 1544152A, 2003) introducing electron withdrawing groups such as F ^-、Cl^-、Br^-、NO₃ ^- or C=O on resins modified with mercaptoalkylamine, researches show that the resins have the advantages of obviously improved heat resistance, reduced degradation rate of sulfonic acid groups, high utilization rate of active centers, difficult blockage of catalyst pore channels, and meeting the requirements of bisphenol A production, namely catalytic activity, selectivity and service life. Krystyna (Krystyna Nowinska. Al., APPLIED CATALYSIS A,2000, 203:91-100) studied mesoporous molecular sieve MCM-41 supported cesium/ammonium salt heteropolyacid catalyst, and the heteropolyacid atoms are fixed inside the mesoporous molecular sieve MCM-41 by Soled method so that the yield of bisphenol A synthesized by the catalyst is stable. Heterogeneous catalysts for the catalytic synthesis of bisphenol A are various in variety, but the strongly acidic ion exchange resin has the advantages of high reactivity and good selectivity, low production cost, easiness in separation from reaction products, environmental friendliness, low corrosiveness and the like, and is widely applied to large-scale production.

The common strong acid ion exchange resin is sulfonated polystyrene-divinylbenzene copolymer or its modified product, and in order to raise the activity of the resin catalyst, one uses mercapto group-containing organic compound as promoter together with ion exchange resin to raise the reaction speed greatly. For example, the addition of alkyl mercaptan to the reaction solution greatly increases bisphenol A yield. However, thiol compounds have been rarely used later due to their high toxicity, unpleasant odor and complex subsequent separation. The mercapto promoter is usually fixed on the resin catalyst by chemical bonding. For example, faler (faler.al., US 4294995,1981) and the like are used for performing acylation reaction on resin chlorine sulfonyl chloride and then bis-aminoethyl disulfide, and then the resin is reduced to form a thiol type strong acid resin synthesized through S-N covalent bond, wherein the selectivity of the resin for catalyzing phenol and acetone to synthesize bisphenol a can reach 98%, but the preparation process is complex, and the ratio of mercapto and sulfonic acid groups is not easy to control in an optimal state, so that the thiol type strong acid resin is not widely used. The catalyst activity is greatly improved by acylating part of the sulfonic acid groups in the strongly acidic cation exchange resin with chlorosulfonic acid to sulfonyl chloride and then reducing the sulfonyl chloride to thiophenol with metallic tin in concentrated hydrochloric acid (Romeo B Wagner. Al., U.S. 3172916,1965), but because thiophenol has poor chemical stability and is very easily oxidized, the catalyst has a short service life. FRANCIS NAPEL (Francis napel. Al., US 3153001,1964) proposes that alkyl mercaptan is grafted onto a strongly acidic cation exchange resin by esterification, which shows good catalytic activity at higher temperatures, but the mercapto group attached by sulfonate structure is easily hydrolyzed and lost, and has poor stability. He Mingyang (He Mingyang et al, CN 1583269 a.2005) uses a mercaptoalkyl quaternary ammonium salt as a mercapto agent, and modifies the base resin by an ion exchange method to obtain a bisphenol a synthesis catalyst. The prepared catalyst has the characteristics of high catalytic activity, good selectivity, long service life and the like, and is a main preparation method of the modern bisphenol A catalyst due to simple preparation mode.

The reaction equipment for producing bisphenol A by the resin method mainly adopts a fixed bed reaction process. The reactor is generally a fixed bed reactor, the catalyst is not easy to abrade in the fixed bed reactor, the service life is longer, the residence time is easy to control, the equipment structure is simple, the operation is stable, and the like. However, the control requirement on water is high, because water molecules are very easy to form hydrogen bonds with sulfonic acid groups in the resin to occupy the active center of the catalyst, thereby hindering the phenol-acetone condensation reaction. The activity and selectivity of the various cation exchange resin catalysts developed by the above technology are high. However, the resin catalysts are relatively hydrophilic, acetone molecules in raw materials easily enter the resin catalysts and contact active sites in the process of catalyzing the condensation of phenol and acetone to synthesize bisphenol A, but phenol molecules are difficult to diffuse into and contact the active sites, the service efficiency of the catalysts is reduced, and water which is a byproduct generated by the products is easily combined with the active sites and is not easy to remove, so that the catalytic activity and stability of the catalysts are reduced.

Disclosure of Invention

In order to solve the problems, the invention provides a resin catalyst, a preparation method thereof and application thereof in bisphenol A synthesis, wherein macroporous crosslinked polystyrene microspheres are adopted as a carrier, so that acetone and phenol molecules are facilitated to diffuse into the resin catalyst to contact active sites, the generated bisphenol A is facilitated to diffuse out, and the hydrophilicity and hydrophobicity of the resin catalyst are regulated and controlled by regulating the chain length of perfluoroalkyl sulfonyl grafted to the carrier (the higher the carbon number is, the higher the hydrophobicity is represented), so that water occupying the active sites is easier to remove, and the phenol molecules are easier to contact the active sites. The resin catalyst prepared by the invention not only shows high catalytic activity in the synthesis of bisphenol A by catalyzing the condensation of phenol and acetone, but also has excellent catalytic stability.

In order to achieve the above object, the present invention provides the following technical solutions:

the invention provides a preparation method of a resin catalyst, which comprises the following steps:

1) Swelling the macroporous crosslinked polystyrene microspheres to obtain swelled microspheres;

2) Mixing the swelling microsphere obtained in the step 1) with fuming sulfuric acid and a sulfonic acid reagent, and then stirring for reaction to obtain modified resin;

The sulfonic acid reagent comprises one or more of trifluoromethanesulfonic acid, pentafluoroethane sulfonic acid, perfluoropropane sulfonic acid and perfluorobutane sulfonic acid;

3) And 2) mixing the modified resin obtained in the step 2) with N, N, N-trimethyl-3-mercaptopropyl quaternary ammonium salt, and performing heat treatment under the protection of inert gas to obtain the resin catalyst.

Preferably, the particle size of the macroporous crosslinked polystyrene microsphere in the step 1) is 800-1000 mu m, the pore diameter is 50-100 nm, and the crosslinking degree is 10-20%;

The swelling condition comprises that the macroporous crosslinked polystyrene microsphere is mixed with dichloroethane and then swelled for 40min;

the volume ratio of the mass of the macroporous crosslinked polystyrene microsphere to the dichloroethane is 100 g/500 mL.

Preferably, the mass ratio of the fuming sulfuric acid, the sulfonic acid reagent and the macroporous crosslinked polystyrene microspheres in the step 2) is 6:2:1.

Preferably, the stirring reaction condition in the step 2) comprises the temperature of 90 ℃, the time of 12 hours and the rotating speed of 300rpm.

Preferably, the mass ratio of the modified resin in the step 3) to the N, N, N-trimethyl-3-mercaptopropyl quaternary ammonium salt is 100:5.49.

Preferably, the heat treatment conditions in the step 3) comprise the temperature of 80 ℃, the time of 8 hours and the rotating speed of 300rpm;

washing and drying the resin catalyst after the heat treatment in sequence to obtain a resin catalyst;

Washing with deionized water to neutrality;

The drying condition comprises that the temperature is 80-100 ℃ and the time is 24 hours.

The invention also provides a resin catalyst prepared by the preparation method in the technical scheme, wherein the resin catalyst is provided with active groups, and the active groups comprise sulfonate, perfluoroalkyl sulfonyl and mercapto alkylamine.

The invention also provides application of the resin catalyst in bisphenol A synthesis.

Preferably, the application comprises the steps of:

1) Mixing the resin catalyst with phenol, and swelling to obtain a swelled substance;

the mass ratio of the volume of the resin catalyst to the mass of the phenol is 5mL to 40g;

the swelling conditions include stirring at a temperature of 70 ℃ for 3 hours;

2) Mixing the swelled material obtained in the step 1) with acetone, and then reacting to obtain bisphenol A;

The mass ratio of the acetone to the phenol is 2.5:40;

the reaction conditions included a temperature of 70℃for a period of 4 hours.

Preferably, the application comprises the steps of:

filling the resin catalyst into a stainless steel fixed bed reactor, and continuously reacting the phenol-acetone mixed solution at 70 ℃ for ^-1 hours at a space velocity to obtain bisphenol A;

the inner diameter of the stainless steel fixed bed reactor is 30mm, and the length is 200mm;

the residence time of the phenol-acetone mixed solution in the catalyst bed layer of the stainless steel fixed bed reactor is 1h;

the molar ratio of phenol to acetone in the phenol-acetone mixed solution is 10:1.

The invention adopts macroporous crosslinked polystyrene microsphere as a carrier, grafts sulfonate and perfluoroalkyl sulfonyl onto the carrier, and adsorbs sulfhydryl alkylamine on the carrier through ionic bond formed by sulfonate, and the prepared resin catalyst overcomes the problems that water molecules are easy to combine with active sites and difficult to remove in bisphenol A synthesis by catalyzing phenol and acetone condensation. The prepared catalyst has high catalytic activity and excellent stability.

The resin catalyst has high catalytic activity and selectivity and good stability, wherein the macroporous crosslinked polystyrene microsphere has large pore diameter, is favorable for the diffusion of reactants and products, is used as a carrier for preparing the resin catalyst, and is grafted on the carrier through a covalent bond to serve as an acid active site, and the perfluoroalkyl sulfonyl is grafted on the carrier through the covalent bond. Because the catalyst has hydrophobic functional groups, the catalyst is used as functional groups for regulating the hydrophilicity and hydrophobicity of the resin catalyst, and the mercapto alkylamine is adsorbed on a carrier through forming an ionic bond with a sulfonate and is used as a cocatalyst for catalyzing the condensation of phenol and acetone to synthesize bisphenol A.

The invention utilizes the function of grafting perfluoroalkyl sulfonyl to resin, can change the hydrophilicity and hydrophobicity of the resin, and regulates and controls the hydrophilicity and hydrophobicity of the resin catalyst by regulating and controlling the chain length (carbon number) of the perfluoroalkyl sulfonyl grafted to the carrier, so that the resin catalyst has high catalytic activity and strong stability.

The invention has the beneficial effects that:

(1) The macroporous crosslinked polystyrene microsphere is used as a carrier, so that acetone and phenol molecules can be diffused into the resin catalyst to contact with active sites, bisphenol A which is a product is diffused out, and the hydrophilicity and hydrophobicity of the resin catalyst can be regulated and controlled by regulating and controlling the chain length (carbon number) of perfluoroalkyl sulfonyl grafted on the carrier, so that water occupying the active sites is easier to remove, and the phenol molecules can be contacted with the active sites more easily. The prepared resin catalyst not only shows high catalytic activity in the synthesis of bisphenol A by catalyzing the condensation of phenol and acetone, but also has excellent catalytic stability.

(2) The preparation method of the resin catalyst provided by the invention has the advantages of simple steps, low cost, environment friendliness, no pollution, high utilization rate of active components, good preparation repeatability, and excellent performances of bisphenol A (more than or equal to 95%) selectivity and stability of more than or equal to 120 days, and the yield is more than or equal to 85% under the mild condition (70 ℃ and 1h ^-1) by combining with a continuous flow fixed bed reactor. Can realize the separation of the catalyst and the product, has simple production process and high product purity, and greatly reduces the production cost.

Drawings

In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are required to be used in the embodiments will be briefly described below.

FIG. 1 is a schematic diagram of a resin catalyst synthesis;

FIG. 2 is a graph of static contact angle of resin catalyst A, B, C, D, E, F in example 5;

FIG. 3 is a graph of stability test data for catalyst C of example 7;

FIG. 4 is a graph of stability test data for catalyst E of comparative example 2.

Detailed Description

The invention swells the macroporous crosslinked polystyrene microsphere to obtain the swelled microsphere.

The invention utilizes the macroporous crosslinked polystyrene microsphere synthesized by the conventional method of the large pore cation exchange resin synthesis method of which the application number is CN 1583269A.2005, wherein the porous crosslinked polystyrene microsphere has rich pore structures inside and outside, can uniformly graft sulfonic acid functional groups, perfluoroalkyl sulfonyl groups and mercapto alkylamine, and can realize catalytic condensation reaction by enabling reactants to reach the inside of a carrier through a porous structure and contact active sites during catalytic reaction. In the invention, the particle size of the macroporous crosslinked polystyrene microsphere is 800-1000 mu m, the pore diameter is 50-100 nm, and the crosslinking degree is 10% -20%.

In the present invention, the swelling condition preferably includes swelling the macroporous crosslinked polystyrene microspheres for 40 minutes after mixing with dichloroethane. In the present invention, the mass to dichloroethane volume ratio of the macroporous crosslinked polystyrene microspheres is preferably 100g:500mL.

The obtained swelling microsphere is mixed with fuming sulfuric acid and sulfonic acid reagent and then stirred for reaction, so that the modified resin is obtained. In the invention, the mass ratio of fuming sulfuric acid, sulfonic acid reagent and macroporous crosslinked polystyrene microsphere is preferably 6:2:1. In the present invention, the sulfonating agent provides one or more of trifluoromethylsulfonyl, pentafluoroethanesulfonyl, perfluoropropane sulfonyl and perfluorobutane sulfonyl. In the present invention, the conditions for the stirring reaction preferably include a temperature of 90℃for 12 hours and a rotation speed of 300rpm.

The obtained modified resin is mixed with N, N, N-trimethyl-3-mercaptopropyl quaternary ammonium salt, and is subjected to heat treatment under the protection of inert gas to obtain the resin catalyst.

In the invention, the N, N, N-trimethyl-3-mercaptopropyl quaternary ammonium salt is derived from SAGECHEM LIMITED, CAS of Jiashan road 8 of Hangzhou, zhejiang province and is 14617-77-7. In the present invention, the mass ratio of the modified resin to the N, N, N-trimethyl-3-mercaptopropyl quaternary ammonium salt is preferably 100:5.49. In the present invention, the conditions for the heat treatment preferably include a temperature of 80℃for 8 hours at a rotational speed of 300rpm. In the invention, the resin catalyst is obtained after the heat treatment, washing and drying in sequence. The present invention preferably uses deionized water to wash to neutrality. In the invention, the drying condition preferably comprises the temperature of 80-100 ℃ and the time of 24 hours.

In the present invention, the application preferably includes the steps of:

The mass ratio of the acetone to the phenol is 2.5:40;

the reaction conditions included a temperature of 70℃for a period of 4 hours.

In the present invention, the application preferably includes the steps of:

The present invention will be described in detail with reference to examples for further illustration of the invention, but they should not be construed as limiting the scope of the invention.

The yield and selectivity calculation method for bisphenol A produced by the reaction of phenol and acetone is as follows:

Yield Y (%) =c _BPA (94.11×r+58.08)/228.28 ×100·· (1) wherein C _BPA is the bisphenol a content in the reaction solution, 94.11 is the phenol molecular weight, R is the molar ratio of phenol to acetone in the starting material, 58.08 is the acetone molecular weight, and 228.28 is the bisphenol a molecular weight.

The selectivity S (%) =c _BPA/(C_BPA+C_{Chroman of}+C_{2,4- Bisphenol A A}+C_Triphenols+C_Others) ·· (2) is C _BPA、C_{Chroman of}、C_{2,4- Bisphenol A A}、C_Triphenols、C_Others, which is the content of bisphenol a, chroman, 2, 4-bisphenol a, triphenol, and other impurities in the reaction solution.

Example 1

Preparing a catalyst:

Into a 1000mL four-necked flask, 100g of macroporous crosslinked polystyrene microspheres (average particle diameter: 850 μm, average pore diameter: 55nm, crosslinking degree: 10%), 500mL of dichloroethane, swelling for 40min, and 600g of fuming sulfuric acid and 200g of trifluoromethanesulfonic acid were added respectively, and the temperature was raised to 90℃and the reaction was stirred at 300rpm for 12 hours. Washing the product to neutrality by ethanol and deionized water in sequence to obtain modified resin;

1000mL of deionized water, 100g of modified resin and 5.49g of N, N-trimethyl-3-mercaptopropyl quaternary ammonium salt are added into a 2000mL four-neck flask, the mixture is stirred for 8 hours at 300rpm under the condition of inert gas protection and the temperature of 80 ℃, the product is washed to be neutral by the deionized water, and the resin catalyst A is obtained after vacuum drying for 24 hours at the temperature of 80 ℃.

Example 2

As in example 1, 200g of trifluoromethanesulfonic acid was changed to 266g of pentafluoroethane sulfonic acid to obtain resin catalyst B.

Example 3

As in example 1, 200g of trifluoromethanesulfonic acid was changed to 333g of perfluoropropane sulfonic acid, to obtain resin catalyst C.

Example 4

As in example 1, 200g of trifluoromethanesulfonic acid was changed to 400g of perfluorobutane sulfonic acid to obtain resin catalyst D.

Comparative example 1

Resin catalyst E was obtained as in example 1, except that trifluoromethanesulfonic acid was not added.

Comparative example 2

Resin catalyst F was obtained as in example 1, except that trifluoromethanesulfonic acid and N, N, N-trimethyl-3-mercaptopropyl quaternary ammonium salt were not added.

Example 5

Resin catalysts A, B, C, D, E, F g each were measured at a rate of 2g, ground into powder by a mortar, and pressed into tablets with a tablet press, the thickness of the tablets being about 0.5mm. Then, at room temperature, a plurality of different positions on the surface of the sample are selected by a contact angle measuring instrument to test the contact angle of deionized water drop on the surface of the sheet sample, and the average value is calculated to obtain the static contact angle data of the sample, and the result is shown in fig. 2. As can be seen from FIG. 2, the perfluoroalkyl sulfonyl groups are grafted onto the resin, which can make the resin more hydrophobic, the better the hydrophobicity as the number of carbons in the perfluoroalkyl sulfonyl groups increases.

Example 6

Adding A, B, C, D or E5 ml of dried resin catalyst and 40g of phenol into a 250ml four-neck flask which is provided with a 100 ℃ thermometer, a stirring paddle and is dried, sealing the reactor, placing the four-neck flask into a constant-temperature water bath at 70 ℃, stirring and preserving heat for 3 hours to enable the catalyst to fully swell, sucking 2.5g of accurately weighed acetone into the four-neck flask by using the injector, rapidly injecting into each reaction flask, reacting for 4 hours at 70 ℃, sampling, analyzing and measuring the content of each component in the reaction solution by a gas phase method, and calculating the yield and the selectivity of bisphenol A according to formulas (1) and (2). The results are shown in Table 1.

TABLE 1 comparison of resin catalyst Activity

Example 7

100G of resin catalyst C is filled in a stainless steel fixed bed reactor with the inner diameter of 30mm and the length of 200mm, phenol-acetone mixed solution (the molar ratio of phenol and acetone in the phenol-acetone mixed solution is 10:1) is continuously reacted at 70 ℃ for 1h ^-1, the residence time of the phenol-acetone mixed solution in the catalyst bed layer of the stainless steel fixed bed reactor is 1h, the reaction product is collected at the outlet of the reactor, the content of each component in the reaction solution is determined by a gas phase method analysis, and the yield and the selectivity of bisphenol A are calculated according to formulas (1) and (2). The results are shown in FIG. 3. As can be seen from fig. 3, bisphenol a was synthesized catalytically using resin catalyst C packed in a fixed bed reactor, and operated continuously for 120 days, the catalyst activity and selectivity were substantially unchanged, exhibiting excellent stability.

Comparative example 2

As in example 7, the resin catalyst C was changed to the resin catalyst E, the phenol-acetone mixture (the molar ratio of phenol to acetone in the phenol-acetone mixture was 10:1) was continuously reacted at 70℃at a space velocity of 1h ^-1, the reaction product was collected at the outlet of the reactor, the contents of the components in the reaction solution were determined by gas phase analysis, and the yield and selectivity of bisphenol A were calculated according to the formulas (1) and (2). The results are shown in FIG. 4. As can be seen from fig. 4, bisphenol a was synthesized catalytically by filling a fixed bed reactor with a resin catalyst E, the activity of which starts to decrease slowly after about 20 days, and after 120 days of operation, the BPA yield decreased from 83% to 64%, which is inferior to that of resin catalyst C.

Although the foregoing embodiments have been described in some, but not all, embodiments of the invention, it should be understood that other embodiments may be devised in accordance with the present embodiments without departing from the spirit and scope of the invention.

Claims

1. A method for preparing a resin catalyst, characterized in that it comprises the following steps:

1) swelling the macroporous cross-linked polystyrene microspheres to obtain swollen microspheres;

2) mixing the swollen microspheres obtained in step 1) with fuming sulfuric acid and a sulfonic acid reagent and stirring the mixture to react to obtain a modified resin;

The sulfonic acid reagent includes one or more of trifluoromethanesulfonic acid, pentafluoroethanesulfonic acid, perfluoropropanesulfonic acid and perfluorobutanesulfonic acid;

3) Mixing the modified resin obtained in step 2) with N,N,N-trimethyl-3-mercaptopropyl quaternary ammonium salt, and performing heat treatment under the protection of an inert gas to obtain a resin catalyst.

2. The preparation method according to claim 1, characterized in that the particle size of the macroporous cross-linked polystyrene microspheres in step 1) is 800-1000 μm, the pore size is 50-100 nm, and the cross-linking degree is 10-20%;

The swelling conditions include: mixing the macroporous cross-linked polystyrene microspheres with ethylene dichloride and swelling for 40 minutes;

The mass ratio of the macroporous cross-linked polystyrene microspheres to the volume ratio of ethylene dichloride is 100 g:500 mL.

3. The preparation method according to claim 1, characterized in that the mass ratio of oleum, sulfonic acid reagent and macroporous cross-linked polystyrene microspheres in step 2) is 6:2:1.

4. The preparation method according to claim 1, characterized in that the conditions of the stirring reaction in step 2) include: temperature of 90°C, time of 12h, and rotation speed of 300rpm.

5. preparation method according to claim 1, is characterized in that, the mass ratio of described step 3) modified resin and N,N,N-trimethyl-3-mercaptopropyl quaternary ammonium salt is 100:5.49.

6. The preparation method according to claim 1, characterized in that the conditions of the heat treatment in step 3) include: temperature of 80°C, time of 8h, and rotation speed of 300rpm;

After the heat treatment, the resin catalyst is obtained by washing and drying in sequence;

Wash with deionized water until neutral;

The drying conditions include: a temperature of 80-100° C. and a drying time of 24 hours.

7. A resin catalyst prepared by the preparation method according to any one of claims 1 to 6, wherein the resin catalyst has active groups, and the active groups include sulfonate, perfluoroalkylsulfonyl and mercaptoalkylamine.

8. Use of the resin catalyst according to claim 7 in the synthesis of bisphenol A.

9. The application according to claim 8, characterized in that the application comprises the following steps:

1) mixing the resin catalyst with phenol and swelling them to obtain a swollen product;

The mass ratio of the resin catalyst volume to phenol is 5 mL:40 g;

The swelling conditions include: stirring at 70° C. for 3 h;

2) mixing the swollen product obtained in step 1) with acetone and reacting the mixture to obtain bisphenol A;

The mass ratio of acetone to phenol is 2.5:40;

The reaction conditions include: temperature of 70° C. and reaction time of 4 h.

10. The application according to claim 8, characterized in that the application comprises the following steps:

The resin catalyst is loaded into a stainless steel fixed bed reactor, and a phenol-acetone mixed solution is continuously reacted at 70° C. and a space velocity of 1 h ^-1 to obtain bisphenol A;

The stainless steel fixed bed reactor has an inner diameter of 30 mm and a length of 200 mm;

The residence time of the phenol-acetone mixture in the catalyst bed of the stainless steel fixed bed reactor is 1 hour;