A resin catalyst for removing p-hydroxybenzenesulfonic acid from bisphenol a and a method for preparing the same

Abstract

This invention belongs to the field of resin catalyst preparation technology, and relates to a resin catalyst for the desorption of p-hydroxybenzenesulfonic acid from bisphenol A and its preparation method. This invention develops a novel functionalized resin catalyst. First, a fluorinated monomer, dodecafluoroheptyl methacrylate, is introduced into the styrene-divinylbenzene copolymer backbone. The strong electronegativity of fluorine atoms significantly enhances the chemisorption capacity for p-hydroxybenzenesulfonic acid, while the hydrophobic properties of the fluorocarbon chain reduce the non-specific adsorption of bisphenol A molecules, achieving selective deacidification. Second, a specially formulated polyethylene glycol-polysiloxane block copolymer is used as a dispersant. By precisely controlling the interfacial tension during polymerization, a resin structure with a pore size distribution concentrated in the 5-20 nm range is obtained, ensuring both efficient diffusion of p-hydroxybenzenesulfonic acid molecules and effectively blocking the entry of bisphenol A dimers. This provides an efficient, environmentally friendly, and economical purification solution for the industrial production of bisphenol A.

Description

Technical Field

[0001] This invention belongs to the field of resin catalyst preparation technology, and relates to a functionalized resin catalyst for removing p-hydroxybenzenesulfonic acid impurities in the bisphenol A production process and its preparation method. Background Technology

[0002] Bisphenol A (BPA) is an important chemical raw material. It is not only a monomer for manufacturing epoxy resins, polycarbonates, and polysulfones, but also a widely used raw material in the organic synthesis industry. Its quality directly affects the performance of the resins; therefore, the purification of BPA is a crucial issue in industry. During the ion-catalyzed synthesis of BPA, the resin catalyst releases free acid, causing corrosion and damage to equipment and instruments. Furthermore, the presence of free acid causes BPA to decompose during the high-temperature thin-film evaporation purification process, generating high-molecular-weight heavy components that affect the color and purity of BPA and increase the amount of tar residue such as these heavy components, thus impacting the unit consumption of the raw material phenol. Therefore, it is essential to remove the residual acidic catalyst from the BPA reaction solution.

[0003] Currently, the main methods for removing residual catalyst from bisphenol A reaction solutions are as follows:

[0004] (1) Weakly basic ion exchange method: A filter filled with a weakly basic anion exchange resin is used to capture and collect the free acid released during the reaction. (2) Alkali-acid reprecipitation method: Bisphenol A is highly soluble in alkali and can generate metal derivatives, while the byproducts are difficult to dissolve in alkali and can be removed by filtration. Then, acid is added to the solution to precipitate bisphenol A. (3) Adsorption method: The bisphenol A reaction solution is mixed with a deacidification aid (such as water or methanol, or a mixture of the two) and then adsorbed through an adsorber. The adsorber is filled with fiber membrane coalescing material, and hot water is introduced externally to keep the adsorption bed warm and dry. The acidity of the treated bisphenol A reaction solution can be reduced to below 0.1 mmol / L, which meets the requirements. These methods each have their advantages and disadvantages. In practical applications, the most suitable method needs to be selected according to the specific situation. The weakly basic ion exchange method is a relatively ideal deacidification method due to its simple operation, low energy consumption, and environmental friendliness.

[0005] Bisphenol A (BPA) is a key monomer in high-performance materials such as epoxy resins and polycarbonates, and its purity directly affects the quality of downstream products. In ion-based synthesis processes, residual acidic catalysts can lead to equipment corrosion, high-temperature product decomposition, and tar formation. While existing deacidification technologies such as weakly basic ion exchange and alkali-acid reprecipitation methods each have their advantages, they still suffer from technical bottlenecks such as insufficient deacidification efficiency, product loss, or high energy consumption. Summary of the Invention

[0006] In view of this, the purpose of this invention is to overcome the shortcomings of the prior art and provide a highly efficient, stable, and selective bisphenol A de-hydroxybenzenesulfonic acid resin catalyst and its preparation method. This invention specifically develops a resin catalyst with specific adsorption function, focusing on solving key technical problems in selective deacidification, catalyst stability, and industrial application of traditional methods, thus providing an innovative solution for the industrial high-purity production of bisphenol A.

[0007] It should be noted that this invention addresses the problems of equipment corrosion, high-temperature product decomposition, color difference, and tar formation caused by residual acidic catalysts during the ion-catalyst synthesis of bisphenol A. While existing weakly basic ion exchange methods are simple to operate, their adsorption capacity for strongly acidic p-hydroxybenzenesulfonic acid is limited. Alkali-acid reprecipitation methods easily lead to product loss and generate large amounts of wastewater, while adsorption methods suffer from low efficiency and difficult regeneration. This invention develops a novel functionalized resin catalyst. First, a fluorinated monomer, dodecafluoroheptyl methacrylate, is introduced into the styrene-divinylbenzene copolymer framework. The strong electronegativity of fluorine atoms significantly enhances the chemical adsorption capacity for p-hydroxybenzenesulfonic acid, while the hydrophobic properties of the fluorocarbon chain reduce the non-specific adsorption of bisphenol A molecules, achieving selective deacidification. Second, a specially formulated polyethylene glycol-polysiloxane block copolymer is used as a dispersant. By precisely controlling the interfacial tension during polymerization, a resin structure with a pore size distribution concentrated in the 5-20 nm range is obtained, ensuring both efficient diffusion of p-hydroxybenzenesulfonic acid molecules and effectively blocking the entry of bisphenol A dimers. This invention provides an efficient, environmentally friendly, and economical purification solution for the industrial production of bisphenol A.

[0008] To achieve the above objectives, the present invention adopts the following technical solution:

[0009] The first technical objective of this invention is to provide a resin catalyst for the removal of p-hydroxybenzenesulfonic acid from bisphenol A. The resin catalyst is prepared by suspending and copolymerizing styrene, divinylbenzene, and dodecyl fluoroheptyl methacrylate monomers in an aqueous solution in the presence of a porogen, an initiator, and a dispersant. An aqueous phase polymerization inhibitor is added to the aqueous solution. The copolymer white spheres are obtained by extraction, drying, and sieving. The bisphenol A purified resin is then obtained by amination and washing.

[0010] Optionally, the porogen is n-heptane, the initiator is benzoyl peroxide, the dispersant is polyethylene glycol-polysiloxane block copolymer, the aqueous polymerization inhibitor is methylene blue, and the amination is chloromethyl ether or trimethylamine.

[0011] Optionally, the polyethylene glycol-polysiloxane block copolymer is prepared as follows:

[0012] Hydroxyl-terminated polyethylene glycol (molecular weight 8000-12000) and excess diisocyanate (such as IPDI) were reacted in anhydrous toluene at 70°C for 3 hours, with the molar ratio of hydroxyl-terminated polyethylene glycol to diisocyanate being 1:3-10. Nitrogen gas was introduced for protection, and dibutyltin dilaurate (0.1%) was added as a catalyst to prepare isocyanate-terminated polyethylene glycol prepolymer. Simultaneously, amino-terminated polydimethylsiloxane (molecular weight 5000-8000) was coupled with an epoxy silane coupling agent. (e.g., KH-560) is reacted at 60°C for 2 hours to activate the end groups. The molar ratio of the amino-terminated polydimethylsiloxane to the epoxy silane coupling agent is 1:3-10. The two prepolymers are mixed at an amino to isocyanate molar ratio of 1:1.05 and reacted in toluene solvent at 80°C for 6-8 hours. After the reaction is completed, the solvent is removed by vacuum distillation. The product is purified by precipitation with a methanol / water mixed solvent (volume ratio 1:1) and vacuum dried at 60°C for 24 hours to obtain the target block copolymer.

[0013] The second technical objective of this invention is to provide a method for preparing a resin catalyst for the removal of p-hydroxybenzenesulfonic acid from bisphenol A as described above, the method specifically comprising the following steps:

[0014] (1) Aggregation

[0015] Styrene, divinylbenzene, porogen, and initiator are weighed and added to a mixing tank, and stirred for 2.0–6.0 hours until the liquid is homogeneously mixed to form the oil phase. Water and an aqueous phase inhibitor are added to a polymerization reactor, and the mixture is stirred and heated to 40–50°C until completely dissolved. Then, a mixture of styrene, divinylbenzene, and dodecyl fluoroheptyl methacrylate monomers is added. The stirring speed is adjusted to 120–150 rpm depending on the monomer dispersion, and polymerization is carried out at a rate of 20°C / hour to 80°C. After reacting for 10–20 hours, the mixture is cooled and discharged. The polymer is washed three times with hot and cold water respectively to separate the white spheres.

[0016] In step (1), the composition and amount of raw materials are as follows:

[0017]

[0018] (2) Extraction

[0019] Add the white spheres to the extraction vessel, add excess solvent to the distillation vessel and heat to evaporate the solvent. The evaporated solvent then flows into the extraction vessel through condensation. The solvent partially dissolves the pore-forming agent in the vessel, leaving a mixed solution in the extraction vessel. When the liquid level reaches 2 / 3 of the extraction vessel's height, transfer it to the distillation vessel and heat to evaporate again. Repeat this process 10-15 times to completely extract the pore-forming agent from the white spheres.

[0020] (3) Drying and sieving

[0021] Place the extracted white spheres in a ventilated area to allow most of the residual solvent to evaporate, and dry the white spheres to a water content of 5-10% as the amination matrix.

[0022] (4)Amination

[0023] The amination matrix was mixed with 3-5 times its volume of chloromethyl ether, and anhydrous zinc chloride (equivalent to 1.5-2.0% of the weight of the white spheres) was added as a catalyst. The mixture was reacted at a constant temperature of 45-50℃ for 8-12 hours under nitrogen protection. During the reaction, the chlorine content was measured intermittently to control the reaction process and ensure that the degree of chloromethylation was precisely controlled within the ideal range of 3.5-4.2 mmol / g. After the reaction was completed, the mother liquor was first discarded, and then the mixture was washed in a gradient with methanol, a methanol / water mixture (volume ratio 7:3), and pure methanol to completely remove unreacted chloromethyl ether and the byproduct dichloromethyl ether. Finally, the mixture was vacuum dried at 50℃ and -0.09 MPa for 6 hours to obtain the chloromethylated intermediate. The above-mentioned chloromethylation intermediate was pre-swollen with 2-3 times its volume of acetone for 2 hours to expand the internal pores of the resin. Then, it was reacted with 4 times its volume of 33% trimethylamine aqueous solution at 35-40°C for 24-36 hours, with the pH value controlled between 9 and 10. After the reaction was completed, the amination solution was drained first, and the solution was repeatedly washed with deionized water until the effluent was neutral, finally obtaining the resin catalyst for the de-hydroxybenzenesulfonic acid removal of bisphenol A.

[0024] Compared with the prior art, the beneficial effects of the present invention are:

[0025] 1) In the selection of dodecafluoroheptyl methacrylate as a monomer, the fluorinated group of this invention enhances the deacidification performance through a triple mechanism: First, the strong electronegativity of the fluorine atom enhances its chemical adsorption of p-hydroxybenzenesulfonic acid; second, the hydrophobic properties of the CF bond form a micro-hydrophobic region inside the resin, which can selectively repel the penetration of bisphenol A molecules, while preferentially adsorbing hydrophilic p-hydroxybenzenesulfonic acid groups, thereby improving adsorption selectivity; finally, the rigid structure of the fluorocarbon chain reduces the resin swelling rate and avoids the embedding of active sites caused by swelling.

[0026] 2) Regarding the improvement of dispersants, the polyethylene glycol segment in the polyethylene glycol-polysiloxane block copolymer can stabilize monomer droplets through hydrogen bonding, while the polysiloxane segment can significantly reduce the interfacial tension between oil and water. The final pore size distribution of the resin is concentrated in 5-20nm, which perfectly matches the diffusion requirements of p-hydroxybenzenesulfonic acid molecules, and effectively blocks the entry of bisphenol A. Detailed Implementation

[0027] The technical solutions in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative effort are within the scope of protection of the present invention.

[0028] The term "embodiment" used herein, as an example, is not necessarily to be construed as superior to or better than other embodiments. Performance testing in the embodiments of this application, unless otherwise specified, employs conventional testing methods in the art. It should be understood that the terminology used in this application is merely for describing particular implementations and is not intended to limit the scope of this disclosure.

[0029] Unless otherwise stated, the technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application pertains; other experimental methods and technical means not specifically mentioned herein refer to experimental methods and technical means commonly used by one of ordinary skill in the art.

[0030] To better illustrate the content of this application, numerous specific details are provided in the following detailed embodiments. Those skilled in the art should understand that this application can be implemented even without certain specific details. In the embodiments, some methods, means, instruments, and devices well-known to those skilled in the art are not described in detail in order to highlight the main points of this application.

[0031] Without conflict, the technical features disclosed in the embodiments of this application can be combined arbitrarily, and the resulting technical solution belongs to the content disclosed in the embodiments of this application.

[0032] This invention discloses a resin catalyst for the de-hydroxybenzenesulfonic acid removal of bisphenol A and its preparation method.

[0033] To better understand the present invention, the following embodiments are provided for further detailed description of the present invention, but they should not be construed as limiting the present invention. Any non-essential improvements and adjustments made by those skilled in the art based on the above-described invention are also considered to fall within the protection scope of the present invention.

[0034] Example 1:

[0035] (1) Aggregation

[0036] Styrene, divinylbenzene, porogen, and initiator were weighed and added to a mixing tank, and stirred for 2.0 h to ensure uniform mixing, which constitutes the oil phase. Water and aqueous phase additives were added to the polymerization reactor, and the mixture was stirred and heated to 40°C to ensure complete dissolution. Then, the mixed monomers were added, and the stirring speed was adjusted to 120 rpm based on the monomer dispersion. Polymerization was carried out at a rate of 20°C / h to 80°C. After reacting for 10 hours, the mixture was cooled and discharged. The polymer was washed three times with hot and cold water respectively to separate the white spheres.

[0037]

[0038] (2) Extraction

[0039] Add the white spheres to the extraction vessel, add excess solvent to the distillation vessel and heat to evaporate the solvent. The evaporated solvent then flows into the extraction vessel through condensation. The solvent partially dissolves the pore-forming agent in the vessel, and the resulting mixed solution remains in the extraction vessel. When the liquid level reaches 2 / 3 of the extraction vessel's height, transfer it to the distillation vessel and heat to evaporate again. Repeat this process 10 times to completely extract the pore-forming agent from the white spheres.

[0040] (3) Drying and sieving

[0041] Place the extracted white spheres in a ventilated area to allow most of the residual solvent to evaporate, and dry the white spheres to a water content of 5-10% as the amination matrix.

[0042] (4)Amination

[0043] The amination matrix was mixed with 3 times its volume of chloromethyl ether, and anhydrous zinc chloride (equivalent to 1.5% of the weight of the white spheres) was added as a catalyst. The reaction was carried out at 45°C for 8 hours under nitrogen protection. During the reaction, the chlorine content was measured intermittently to control the reaction process and ensure that the degree of chloromethylation was precisely controlled within the ideal range of 3.5-4.2 mmol / g. After the reaction was completed, the mother liquor was first decanted, and then the mixture was washed in a gradient with methanol, a methanol / water mixture (volume ratio 7:3), and pure methanol to completely remove unreacted chloromethyl ether and the byproduct dichloromethyl ether. Finally, the mixture was vacuum dried at 50°C and -0.09 MPa for 6 hours to obtain the chloromethylated intermediate. The above-mentioned chloromethylation intermediate was pre-swollen with 2 times the volume of acetone for 2 hours to expand the internal pores of the resin. Then, it was reacted with 4 times the volume of 33% trimethylamine aqueous solution at 35°C for 24 hours, with the pH value controlled at 9.0. After the reaction was completed, the amination solution was drained first, and the solution was repeatedly washed with deionized water until the effluent was neutral, finally obtaining the resin catalyst for the de-hydroxybenzenesulfonic acid removal of bisphenol A.

[0044] The results are shown in Tables 1 and 2.

[0045] Example 2:

[0046] (1) Aggregation

[0047] Styrene, divinylbenzene, porogen, and initiator were weighed and added to a mixing tank, and stirred for 6.0 h to ensure uniform mixing, which constitutes the oil phase. Water and aqueous phase additives were added to the polymerization reactor, and the mixture was stirred and heated to 50°C to ensure complete dissolution. Then, the mixed monomers were added, and the stirring speed was adjusted to 150 rpm based on the monomer dispersion. Polymerization was carried out at a rate of 20°C / h to 80°C. After reacting for 20 hours, the mixture was cooled and discharged. The polymer was washed three times with hot and cold water respectively to separate the white spheres.

[0048]

[0049]

[0050] (2) Extraction

[0051] Add the white pellets to the extraction vessel, add excess solvent to the distillation vessel and heat to evaporate the solvent. The evaporated solvent then flows into the extraction vessel through condensation. The solvent partially dissolves the pore-forming agent in the vessel, and the resulting mixed solution remains in the extraction vessel. When the liquid level reaches 2 / 3 of the extraction vessel's height, transfer it to the distillation vessel and heat to evaporate again. Repeat this process 15 times to completely extract the pore-forming agent from the white pellets.

[0052] (3) Drying and sieving

[0053] Place the extracted white spheres in a ventilated area to allow most of the residual solvent to evaporate, and dry the white spheres to a water content of 5-10% as the amination matrix.

[0054] (4)Amination

[0055] The amination matrix was mixed with 5 times its volume of chloromethyl ether, and anhydrous zinc chloride (equivalent to 2.0% of the weight of the white spheres) was added as a catalyst. The reaction was carried out at 50°C for 12 hours under nitrogen protection. During the reaction, the chlorine content was measured intermittently to control the reaction process and ensure that the degree of chloromethylation was precisely controlled within the ideal range of 3.5-4.2 mmol / g. After the reaction was completed, the mother liquor was first decanted, and then the mixture was washed in a gradient with methanol, a methanol / water mixture (volume ratio 7:3), and pure methanol to completely remove unreacted chloromethyl ether and the byproduct dichloromethyl ether. Finally, the mixture was vacuum dried at 50°C and -0.09 MPa for 6 hours to obtain the chloromethylated intermediate. The above-mentioned chloromethylation intermediate was pre-swollen with 3 times its volume of acetone for 2 hours to expand the internal pores of the resin. Then, it was reacted with 4 times its volume of 33% trimethylamine aqueous solution at 40°C for 36 hours, with the pH value controlled at 10.0. After the reaction was completed, the amination solution was drained first, and the solution was repeatedly washed with deionized water until the effluent was neutral, finally obtaining the resin catalyst for the de-hydroxybenzenesulfonic acid removal of bisphenol A.

[0056] The results are shown in Tables 1 and 2.

[0057] Example 3:

[0058] (1) Aggregation

[0059] Styrene, divinylbenzene, porogen, and initiator were weighed and added to a mixing tank, and stirred for 4.0 h to ensure uniform mixing, which constitutes the oil phase. Water and aqueous phase additives were added to the polymerization reactor, and the mixture was stirred and heated to 45°C to ensure complete dissolution. Then, the mixed monomers were added, and the stirring speed was adjusted to 130 rpm based on the monomer dispersion. Polymerization was carried out at a rate of 20°C / h to 80°C. After reacting for 15 hours, the mixture was cooled and discharged. The polymer was washed three times with hot and cold water respectively to separate the white spheres.

[0060] (2) Extraction

[0061] Add the white spheres to the extraction vessel, add excess solvent to the distillation vessel and heat to evaporate the solvent. The evaporated solvent then flows into the extraction vessel through condensation. The solvent partially dissolves the pore-forming agent in the vessel, and the resulting mixed solution remains in the extraction vessel. When the liquid level reaches 2 / 3 of the extraction vessel's height, transfer it to the distillation vessel and heat to evaporate again. Repeat this process 12 times to completely extract the pore-forming agent from the white spheres.

[0062] (3) Drying and sieving

[0063] Place the extracted white spheres in a ventilated area to allow most of the residual solvent to evaporate, and dry the white spheres to a water content of 5-10% as the amination matrix.

[0064]

[0065] (4)Amination

[0066] The amination matrix was mixed with 4 times its volume of chloromethyl ether, and anhydrous zinc chloride (equivalent to 1.8% of the weight of the white spheres) was added as a catalyst. The reaction was carried out at 48°C for 10 hours under nitrogen protection. During the reaction, the chlorine content was measured intermittently to control the reaction process and ensure that the degree of chloromethylation was precisely controlled within the ideal range of 3.5-4.2 mmol / g. After the reaction was completed, the mother liquor was first decanted, and then the mixture was washed in a gradient with methanol, a methanol / water mixture (volume ratio 7:3), and pure methanol to completely remove unreacted chloromethyl ether and the byproduct dichloromethyl ether. Finally, the mixture was vacuum dried at 50°C and -0.09 MPa for 6 hours to obtain the chloromethylated intermediate. The above-mentioned chloromethylation intermediate was pre-swollen with 2.5 times its volume of acetone for 2 hours to expand the internal pores of the resin. Then, it was reacted with 4 times its volume of 33% trimethylamine aqueous solution at 38°C for 30 hours, with the pH value controlled at 9.5. After the reaction was completed, the amination solution was drained first, and the solution was repeatedly washed with deionized water until the effluent was neutral, finally obtaining the resin catalyst for the de-hydroxybenzenesulfonic acid removal of bisphenol A.

[0067] The results are shown in Tables 1 and 2.

[0068] At a temperature of 85℃, a pressure of 1.0 MPa, and a space velocity of 2 h⁻¹ -1 Under the specified conditions, the reaction raw materials were 78.7% phenol, 11.5% 4,4-BPA, 2.8% 2,4-BPA, 6.4% triphenol, 0.6% water, and p-hydroxybenzenesulfonic acid with contents of 71.85 mg / L and 126.48 mg / L, respectively.

[0069] Table 1. Variation of p-hydroxybenzenesulfonic acid at the outlet with space velocity (71.85 mg / L)

[0070]

[0071] Table 2. Variation of p-hydroxybenzenesulfonic acid at the outlet with space velocity (126.48 mg / L)

[0072]

[0073] To further highlight the key technical aspects of this case, the inventors also conducted the following comparative studies, as detailed below:

[0074] Comparative Example 1:

[0075] The monomers used in this study did not contain dodecafluoroheptyl methacrylate, and all other components and process conditions were the same as in Example 1, ultimately yielding the resin catalyst described above for the removal of p-hydroxybenzenesulfonic acid from bisphenol A. The results are shown in Tables 3 and 4.

[0076] Comparative Example 2:

[0077] Polyethylene glycol was used as the dispersant, and all other components and process conditions were the same as in Example 1, ultimately yielding the resin catalyst described above for the removal of p-hydroxybenzenesulfonic acid from bisphenol A. The results are shown in Tables 3 and 4.

[0078] At a temperature of 85℃, a pressure of 1.0 MPa, and a space velocity of 2 h⁻¹ -1 Under the specified conditions, the reaction raw materials were 78.7% phenol, 11.5% 4,4-BPA, 2.8% 2,4-BPA, 6.4% triphenol, 0.6% water, and p-hydroxybenzenesulfonic acid with contents of 71.85 mg / L and 126.48 mg / L, respectively.

[0079] Table 3. Variation of p-hydroxybenzenesulfonic acid at the outlet with space velocity (71.85 mg / L)

[0080]

[0081] Table 4. Variation of p-hydroxybenzenesulfonic acid at the outlet with space velocity (126.48 mg / L)

[0082]

[0083] The above description of the disclosed embodiments enables those skilled in the art to make or use the invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the general principles defined herein may be implemented in other embodiments without departing from the spirit or scope of the invention. Therefore, the invention is not to be limited to the embodiments shown herein, but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.

Claims

1. A resin catalyst for the de-hydroxybenzenesulfonic acid removal of bisphenol A, characterized in that, The resin catalyst is made by styrene, divinylbenzene, and dodecyl fluoroheptyl methacrylate monomers, which are suspended copolymerized in an aqueous solution in the presence of a porogen, an initiator, and a dispersant. An aqueous phase polymerization inhibitor is added to the aqueous solution. After extraction, drying, and sieving, copolymer white spheres are obtained. After amination and washing, bisphenol A purified resin is obtained. The dispersant is a polyethylene glycol-polysiloxane block copolymer; The preparation method of the polyethylene glycol-polysiloxane block copolymer is as follows: 1) Hydroxyl-terminated polyethylene glycol is reacted with excess diisocyanate in anhydrous toluene, under nitrogen protection and with the addition of the catalyst dibutyltin dilaurate to obtain isocyanate-terminated polyethylene glycol prepolymer. 2) The amino-terminated polydimethylsiloxane is reacted with an epoxy silane coupling agent to activate the end groups; 3) The two prepolymers were mixed and reacted in toluene solvent. After the reaction was completed, the solvent was removed by vacuum distillation. The product was purified by precipitation with methanol / water mixed solvent and vacuum dried to obtain the target block copolymer.

2. The resin catalyst for the removal of p-hydroxybenzenesulfonic acid from bisphenol A according to claim 1, characterized in that, The porogen is n-heptane, the initiator is benzoyl peroxide, and the aqueous phase inhibitor is methylene blue.

3. The resin catalyst for the removal of p-hydroxybenzenesulfonic acid from bisphenol A according to claim 1, characterized in that, In step 1), the molecular weight of the hydroxyl-terminated polyethylene glycol is 8000-12000, and the diisocyanate is IPDI; the molar ratio of the hydroxyl-terminated polyethylene glycol to the diisocyanate is 1:3-10, and the amount of the catalyst dibutyltin dilaurate is 0.1% of the total mass of the hydroxyl-terminated polyethylene glycol and the diisocyanate; the reaction temperature is 70℃, and the reaction time is 3 hours.

4. The resin catalyst for the removal of p-hydroxybenzenesulfonic acid from bisphenol A according to claim 1, characterized in that, In step 2), the amino-terminated polydimethylsiloxane has a molecular weight of 5000-8000, the epoxy silane coupling agent is KH-560, the molar ratio of the amino-terminated polydimethylsiloxane to the epoxy silane coupling agent is 1:3-10, the reaction temperature is 60℃, and the reaction time is 2 hours.

5. The resin catalyst for the removal of p-hydroxybenzenesulfonic acid from bisphenol A according to claim 1, characterized in that, In step 3), the two prepolymers are mixed at a molar ratio of amino to isocyanate groups of 1:1.05 and reacted in toluene solvent at 80°C for 6-8 hours.

6. A method for preparing a resin catalyst for the removal of p-hydroxybenzenesulfonic acid from bisphenol A as described in claim 1, characterized in that, The method specifically includes the following steps: (1) Aggregation Styrene, divinylbenzene, pore-forming agent, and initiator are weighed and added to a mixing tank. The mixture is stirred until it is homogeneous, which is the oil phase. Water and aqueous phase polymerization inhibitor are added to the polymerization reactor. The mixture is stirred and heated until it is completely dissolved. Then, a mixture of styrene, divinylbenzene, and dodecyl fluoroheptyl methacrylate monomers is added. The stirring speed is adjusted according to the monomer dispersion, and the temperature is raised for polymerization. After the reaction is completed, the mixture is cooled and discharged. The polymer is washed three times with hot water and cold water respectively to separate the white spheres. (2) Extraction Add the white spheres prepared in step (1) to the extraction vessel, add excess solvent to the distillation vessel and heat it to evaporate the solvent in the vessel. The solvent then flows into the extraction vessel through condensation. The solvent partially dissolves the pore-forming agent in the vessel, and the resulting mixed solution remains in the extraction vessel. When the liquid level reaches 2 / 3 of the height of the extraction vessel, it is placed into the distillation vessel and heated to evaporate again. This process is repeated 10 to 15 times to completely extract the pore-forming agent from the white spheres. (3) Drying and sieving Place the extracted white balls in a ventilated place to allow most of the residual solvent to evaporate, and dry the white balls to a water content of 5-10% as the amination matrix; (4)Amination The amination matrix prepared in step (3) was mixed with 3-5 times its volume of chloromethyl ether, and anhydrous zinc chloride (equivalent to 1.5-2.0% of the weight of the white spheres) was added as a catalyst. The reaction was carried out at a constant temperature of 45-50℃ for 8-12 hours under nitrogen protection. During the reaction, the chlorine content was measured intermittently to control the reaction process and ensure that the degree of chloromethylation was precisely controlled within the ideal range of 3.5-4.2 mmol / g. After the reaction was completed, the mother liquor was first discarded, and then the mixture was washed successively with methanol, methanol / water mixture, and pure methanol to thoroughly remove unreacted chloromethyl ether and... The byproduct dichloromethyl ether was vacuum dried at 50°C and -0.09 MPa for 6 hours to obtain a chloromethylated intermediate. The chloromethylated intermediate was pre-swollen with 2-3 times its volume of acetone for 2 hours to expand the internal pores of the resin. Then, it was reacted with 4 times its volume of 33% trimethylamine aqueous solution at 35-40°C for 24-36 hours, with the pH value controlled between 9 and 10. After the reaction, the amination solution was drained and the solution was repeatedly washed with deionized water until the effluent was neutral, finally obtaining the resin catalyst for the de-hydroxybenzenesulfonic acid removal of bisphenol A.

7. The method for preparing the resin catalyst for the de-hydroxybenzenesulfonic acid removal of bisphenol A according to claim 6, characterized in that, In step (1), the composition and amount of raw materials by weight are as follows: 。 8. The method for preparing the resin catalyst for the de-hydroxybenzenesulfonic acid removal of bisphenol A according to claim 6, characterized in that, In step (1), the stirring speed is 120 rpm to 150 rpm, the temperature is increased to 80℃ at 20℃ / h, and the reaction time is 10 to 20 hours.

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