A method for preparing a polymer containing sulfone groups and sulfonic acid groups

Abstract

The present invention discloses a method for preparing a polymer containing sulfone groups and sulfonic acid groups. The method comprises synthesizing the sulfide group-containing polymer through a Friedel-Crafts alkylation reaction using an aromatic monomer containing a sulfide group as a raw material. After grinding, the polymer is placed in a sulfonating agent for sulfonation. The polymer is washed and dried to obtain the polymer containing sulfonic acid groups and sulfide groups. The polymer containing sulfonic acid groups and sulfide groups is then oxidized using an oxidizing agent. The polymer containing sulfone groups and sulfonic acid groups is washed and dried to obtain the polymer containing sulfone groups and sulfonic acid groups. The polymer has a rich pore structure and a large number of acidic oxygen-containing functional groups.

Description

Technical field:

[0001] The invention belongs to the technical field of polymer preparation, in particular to a method for preparing a polymer containing sulfone groups and sulfonic acid groups. Background technology:

[0002] Traditional inorganic acids, such as HCl and H2SO4, are widely used in reactions such as fine chemical synthesis and biomass conversion. However, liquid acids present a range of issues, including equipment corrosion and difficulty in regeneration. Compared to liquid acids, solid acids offer advantages such as ease of product separation, reusability, and resistance to corrosion of reaction equipment. Solid acids come in a variety of types, primarily macroporous resins, zeolites, heteropolyacids, metal oxides, carbon-based solid acids, and polymer solid acids. Among these, polymer solid acids have attracted widespread attention due to their easily tunable structure, excellent thermal stability, and high hydrophobicity.

[0003] Polystyrene sulfonic acid resin, a typical polymeric solid acid with a high sulfonic acid group density, exhibits good catalytic activity in cellulose hydrolysis, esterification, and olefin hydration reactions. However, polystyrene sulfonic acid resin suffers from poor thermal stability and low acid strength of the sulfonic acid group.

[0004] In order to solve the above problems, the introduction of a strong electron-withdrawing sulfone group into the polymer backbone can improve the stability and acid strength of the sulfonic acid group. Currently, polymers containing sulfone groups and sulfonic acid groups can be synthesized by the following methods. For example, Wang ZQ et al. proposed in the document "Sulfonated polyethersulfone directly synthesized throughsulfonic monomer as a new stable solid acid catalyst for esterification" (Catalysis Communications, 2012, 27: 164-168) that a polymer containing sulfone groups and sulfonic acid groups is obtained by first polymerizing, then exchanging ions, bis(4-chlorophenyl)sulfone, 4,4-dihydroxybiphenyl and 4,4-dichlorodiphenylsulfone-3,3-disulfonic acid disodium as raw materials. However, there are problems with the lack of pore structure and small specific surface area. Based on the above-mentioned literature, Wang ZQ et al., in the paper "A Cross-Linked and Swelling Polymer as an Effective Solid Acid Catalyst" (Industrial & Engineering Chemistry Research, 2015, 54: 7219-7225), used phloroglucinol as a crosslinking agent and the same raw materials and synthesis methods as the above-mentioned literature to obtain polyethersulfone with sulfonic acid groups. However, there are problems with high raw material costs and complex preparation methods. Guan R et al., in the paper "Polyethersulfonesulfonated by chlorosulfonic acid and its membrane characteristics" (European Polymer Journal, 2005, 41, 1554-1560), dissolved linear polyethersulfone in concentrated sulfuric acid and then sulfonated the polyethersulfone with chlorosulfonic acid to obtain sulfonated polyethersulfone. However, the use of concentrated sulfuric acid and chlorosulfonic acid can cause environmental pollution. In "Direct catalytic conversion of glucose and cellulose" (Green Chemistry, 2018, 20:863-872), Li ZH et al. synthesized linear polyphenylene sulfide using Na2S and 1,4-dichlorobenzene. The linear polyphenylene sulfide was subsequently sulfonated using 10% SO3 in H2SO4 to produce a polymer containing sulfone and sulfonic acid groups. However, the polymer suffered from low specific surface area and poor stability.

[0005] According to the aforementioned literature, the current synthesis of polymers containing sulfone and sulfonic acid groups is plagued by a series of problems, including expensive raw materials, complex processes, and environmental pollution. Furthermore, polymers containing sulfone and sulfonic acid groups also suffer from small specific surface areas and poor stability. Therefore, it is necessary to develop a more environmentally friendly method for preparing polymers containing sulfone and sulfonic acid groups, which has a rich pore structure and high stability. Summary of the invention:

[0006] The object of the present invention is to provide a method for preparing a polymer containing sulfone groups and sulfonic acid groups, which can effectively reduce costs and shorten the process flow. The polymer has a rich pore structure and surface oxygen-containing functional groups.

[0007] To achieve the above objectives, in-depth research has revealed that a polymer containing sulfone and sulfonic acid groups can be obtained using the following method, which features low-cost raw materials, a simple synthesis method, and high yields: First, a sulfide-containing aromatic monomer, dimethoxymethane, and a catalyst are uniformly mixed in a molar ratio of 1:1:1 to 1:5:5, then added to an organic solvent. The mixture is reacted at 45-80°C for 5-25 hours to obtain a sulfide-containing polymer. Second, concentrated sulfuric acid and the sulfide-containing polymer are mixed at a liquid-to-solid ratio of 5 mL:1 g to 50 mL:1 g, and sulfonated at 40-150°C for 2-20 hours. The resulting solid, which is the polymer containing sulfonic acid and sulfide groups, is filtered, washed, and dried. Third, an oxidizing solution is mixed with the polymer containing sulfonic acid and sulfide groups at a liquid-to-solid ratio of 5 mL:1 g to 100 mL:1 g, and the reaction is carried out at room temperature for 1-24 hours. The solid is then washed with deionized water until the filtrate is neutral. The solid obtained after drying, grinding and sieving is a polymer containing sulfone groups and sulfonic acid groups.

[0008] The present invention provides a method for preparing the above-mentioned polymer containing sulfone groups and sulfonic acid groups, characterized in that the aromatic monomer containing a sulfide group can be one of 4-methyldiphenyl sulfide, diphenyl sulfide, 4,4-diaminodiphenyl sulfide, 4,4-dihydroxydiphenyl sulfide, phenothiazine, 2-chlorophenothiazine, 9-thioxanthone, thianthrene, phenoxathiol, 4-phenylthioaniline and 4-phenylthiobenzyl chloride.

[0009] The present invention provides a method for preparing the above-mentioned polymer containing sulfone groups and sulfonic acid groups, characterized in that the organic solvent can be one of chloroform, 1,2-dichloroethane and dichloromethane.

[0010] The present invention provides a method for preparing the above-mentioned polymer containing sulfone groups and sulfonic acid groups, characterized in that the catalyst is one of AlCl3, FeCl3, SnCl4, TiCl4, ZnCl2, HF, H2SO4 and H3PO4.

[0011] The present invention provides a method for preparing the above-mentioned polymer containing sulfone groups and sulfonic acid groups, characterized in that the polymer containing sulfone groups and sulfonic acid groups can be used for one of cellulose catalytic hydrolysis reaction and esterification reaction.

[0012] This method uses aromatic monomers containing thioether groups as raw materials. The resulting polymers containing sulfone and sulfonic acid groups exhibit a three-dimensional network structure and high stability. Compared to other polymers containing sulfone and sulfonic acid groups, this method also introduces a large number of phenolic hydroxyl and carboxyl groups, significantly enhancing the polymer's catalytic activity. Compared to other synthesis methods, this method offers the advantages of inexpensive raw materials and a simple process.

[0013] The above preparation method uses inexpensive and readily available materials. The polymer containing sulfone groups and sulfonic acid groups prepared by this method has the following advantages:

[0014] 1. Compared with other polymers containing sulfone and sulfonic acid groups, the polymer has rich pore structure and large specific surface area.

[0015] 2. Compared with other polymers containing sulfone and sulfonic acid groups, the polymer surface also contains abundant oxygen-containing functional groups, such as phenolic hydroxyl and carboxyl groups.

[0016] 3. Compared with other polymers containing sulfone and sulfonic acid groups, the polymer has higher catalytic activity.

[0017] 4. Compared with other synthesis methods of polymers containing sulfone groups and sulfonic acid groups, this synthesis method uses low-cost raw materials and has a simple process flow. Description of the drawings:

[0018] Figure 1 This is the XPS S2p narrow scan spectrum of the sulfide group-containing polymer of the present invention, which shows the existence form of sulfur in the polymer.

[0019] Figure 2 This is the xPS S2p narrow scan spectrum of the polymer containing sulfone groups and sulfonic acid groups of the present invention, which shows the existence form of sulfur in the polymer.

[0020] Figure 3 This is the infrared spectrum of the polymer containing sulfone groups and sulfonic acid groups of the present invention, which shows the types of groups contained in the polymer. Specific implementation method:

[0021] To help those skilled in the art better understand the technical solutions of the present invention, the technical solutions in the embodiments of the present invention are clearly and completely described below. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of them. All other embodiments obtained by those skilled in the art based on the embodiments of the present invention without creative work should fall within the scope of protection of the present invention.

[0022] Example 1

[0023] First, 4-methyldiphenyl sulfide, dimethoxymethane, and AlCl3 were mixed in a molar ratio of 1:1:3 and then added to 1,2-dichloroethane. The mixture was reacted at 45°C for 10 hours to obtain a polymer containing sulfide groups. Secondly, concentrated sulfuric acid and the polymer containing sulfide groups were mixed at a liquid-solid ratio of 10 mL:1 g, and sulfonated at 60°C for 5 hours. The solid obtained after filtration, washing, and drying was a polymer containing sulfonic acid groups and sulfide groups. Finally, hydrogen peroxide was mixed with the polymer containing sulfonic acid groups and sulfide groups at a liquid-solid ratio of 20 mL:1 g and reacted at room temperature for 7 hours. The solid was then washed with deionized water until the filtrate was neutral. The solid obtained after drying, grinding, and sieving was a polymer containing sulfone groups and sulfonic acid groups. Analysis showed that the specific surface area of ​​the polymer containing sulfone groups and sulfonic acid groups was 301 m 2 / g. The phenolic hydroxyl and carboxyl group densities of the polymer containing sulfone and sulfonic acid groups were determined by titration to be 1.02 mmol / g and 0.62 mmol / g, respectively. In a reactor equipped with a reflux system, the polymer containing sulfone and sulfonic acid groups, oleic acid, and methanol were added to a round-bottom flask and reacted in a heating unit with a constant magnetic stirring device at 70°C for 2 hours. The calculated oleic acid conversion was 71%. Under the same experimental conditions, the oleic acid conversion rate of the polymer containing sulfone and sulfonic acid groups was still 62% after four uses. A certain amount of cellulose, the polymer containing sulfone and sulfonic acid groups, and the mixture were placed in a reactor, and a certain amount of distilled water was added. The mixture was reacted at 150°C for 4 hours, and the glucose yield was 63%. Under the same experimental conditions, the glucose yield of the polymer containing sulfone and sulfonic acid groups was still 51% after five uses.

[0024] Example 2

[0025] First, diphenyl sulfide, dimethoxymethane and FeCl3 are mixed evenly in a molar ratio of 1:4:2 and then added to dichloromethane. The mixture is reacted at 60°C for 20 hours to obtain a polymer containing sulfide groups. Secondly, concentrated sulfuric acid and the polymer containing sulfide groups are mixed at a liquid-solid ratio of 30mL:1g, sulfonated at 100°C for 10 hours, and the solid obtained after filtration, washing and drying is a polymer containing sulfonic acid groups and sulfide groups. Finally, hydrogen peroxide is mixed with the polymer containing sulfonic acid groups and sulfide groups at a liquid-solid ratio of 50mL:1g and reacted at room temperature for 2 hours. The solid is then washed with deionized water until the filtrate is neutral. The solid obtained after drying, grinding and sieving is a polymer containing sulfone groups and sulfonic acid groups. Analysis and detection show that the specific surface area of ​​the polymer containing sulfone groups and sulfonic acid groups is 259m 2 / g. The phenolic hydroxyl and carboxyl group densities of the polymer containing sulfone and sulfonic acid groups were determined by titration to be 1.23 mmol / g and 0.72 mmol / g, respectively. In a reactor equipped with a reflux system, the polymer containing sulfone and sulfonic acid groups, oleic acid, and methanol were added to a round-bottom flask and reacted in a heating unit with a constant magnetic stirrer at 70°C for 2 hours. The calculated oleic acid conversion was 76%. Under the same experimental conditions, the oleic acid conversion of the polymer containing sulfone and sulfonic acid groups remained at 65% after four uses. A certain amount of cellulose, the polymer containing sulfone and sulfonic acid groups, and the mixture were placed in a reactor. A certain amount of distilled water was added and the mixture was reacted at 150°C for 4 hours. The glucose yield was 66%. Under the same experimental conditions, the glucose yield of the polymer containing sulfone and sulfonic acid groups remained at 54% after five uses.

[0026] Example 3

[0027] First, 4,4-diaminodiphenyl sulfide, dimethoxymethane and SnCl4 were mixed in a molar ratio of 1:2:3 and then added to chloroform. The mixture was reacted at 80°C for 25 hours to obtain a polymer containing sulfide groups. Secondly, concentrated sulfuric acid and the polymer containing sulfide groups were mixed at a liquid-solid ratio of 50mL:1g, sulfonated at 150°C for 7 hours, and the solid obtained after filtration, washing and drying was a polymer containing sulfonic acid groups and sulfide groups. Finally, peracetic acid was mixed with the polymer containing sulfonic acid groups and sulfide groups at a liquid-solid ratio of 60mL:1g and reacted at room temperature for 7 hours. The solid was then washed with deionized water until the filtrate was neutral. The solid obtained after drying, grinding and sieving was a polymer containing sulfone groups and sulfonic acid groups. Analysis showed that the specific surface area of ​​the polymer containing sulfone groups and sulfonic acid groups was 263m 2 / g. The phenolic hydroxyl and carboxyl group densities of the polymer containing sulfone and sulfonic acid groups were determined by titration to be 1.41 mmol / g and 0.47 mmol / g, respectively. In a reactor equipped with a reflux system, the polymer containing sulfone and sulfonic acid groups, oleic acid, and methanol were added to a round-bottom flask and reacted in a heating unit with a constant magnetic stirrer at 70°C for 2 hours. The calculated oleic acid conversion was 69%. Under the same experimental conditions, the oleic acid conversion of the polymer containing sulfone and sulfonic acid groups remained at 58% after four uses. A certain amount of cellulose, the polymer containing sulfone and sulfonic acid groups, and the mixture were placed in a reactor, and a certain amount of distilled water was added. The mixture was reacted at 150°C for 4 hours, and the glucose yield was 59%. Under the same experimental conditions, the glucose yield of the polymer containing sulfone and sulfonic acid groups remained at 52% after five uses.

[0028] Example 4

[0029] First, 4.4-dihydroxydiphenyl sulfide, dimethoxymethane, and TiCl4 were mixed in a molar ratio of 1:3:1 and then added to 1,2-dichloroethane. The mixture was reacted at 60°C for 20 hours to obtain a polymer containing sulfide groups. Secondly, concentrated sulfuric acid and the polymer containing sulfide groups were mixed at a liquid-to-solid ratio of 30 mL:1 g, and sulfonated at 120°C for 8 hours. The solid obtained after filtration, washing, and drying was the polymer containing sulfonic acid groups and sulfide groups. Finally, hydrogen peroxide was mixed with the polymer containing sulfonic acid groups and sulfide groups at a liquid-to-solid ratio of 60 mL:1 g and reacted at room temperature for 14 hours. The solid was then washed with deionized water until the filtrate was neutral. The solid obtained after drying, grinding, and sieving was the polymer containing sulfone groups and sulfonic acid groups. Analysis showed that the specific surface area of ​​the polymer containing sulfone groups and sulfonic acid groups was 361 m 2 / g. The phenolic hydroxyl and carboxyl group densities of the polymer containing sulfone and sulfonic acid groups were determined by titration to be 0.99 mmol / g and 0.51 mmol / g, respectively. In a reactor equipped with a reflux system, the polymer containing sulfone and sulfonic acid groups, oleic acid, and methanol were added to a round-bottom flask and reacted in a heating unit with a constant magnetic stirrer at 70°C for 2 hours. The calculated oleic acid conversion was 80%. Under the same experimental conditions, the oleic acid conversion rate of the polymer containing sulfone and sulfonic acid groups remained at 71% after four uses. A certain amount of cellulose, the polymer containing sulfone and sulfonic acid groups, and the mixture were placed in a reactor, and a certain amount of distilled water was added. The mixture was reacted at 150°C for 4 hours, and the glucose yield was 66%. Under the same experimental conditions, the glucose yield of the polymer containing sulfone and sulfonic acid groups remained at 53% after five uses.

[0030] Example 5

[0031] First, thiophene, dimethoxymethane and ZnCl2 are mixed in a molar ratio of 1:3:5 and then added to dichloromethane. The mixture is reacted at 80°C for 25 hours to obtain a polymer containing sulfide groups. Secondly, concentrated sulfuric acid and the polymer containing sulfide groups are mixed at a liquid-solid ratio of 20mL:1g, sulfonated at 50°C for 10 hours, and the solid obtained after filtration, washing and drying is a polymer containing sulfonic acid groups and sulfide groups. Finally, peracetic acid is mixed with the polymer containing sulfonic acid groups and sulfide groups at a liquid-solid ratio of 25mL:1g and reacted at room temperature for 10 hours. The solid is then washed with deionized water until the filtrate is neutral. The solid obtained after drying, grinding and sieving is a polymer containing sulfone groups and sulfonic acid groups. Analysis and detection show that the specific surface area of ​​the polymer containing sulfone groups and sulfonic acid groups is 306m 2 / g. The phenolic hydroxyl and carboxyl group densities of the polymer containing sulfone and sulfonic acid groups were determined by titration to be 1.11 mmol / g and 0.42 mmol / g, respectively. In a reactor equipped with a reflux system, the polymer containing sulfone and sulfonic acid groups, oleic acid, and methanol were added to a round-bottom flask and reacted in a heating unit with a constant magnetic stirrer at 70°C for 2 hours. The calculated oleic acid conversion was 76%. Under the same experimental conditions, the oleic acid conversion rate of the polymer containing sulfone and sulfonic acid groups remained at 64% after four uses. A certain amount of cellulose, the polymer containing sulfone and sulfonic acid groups, and the mixture were placed in a reactor, and a certain amount of distilled water was added. The mixture was reacted at 150°C for 4 hours, and the glucose yield was 71%. Under the same experimental conditions, the glucose yield of the polymer containing sulfone and sulfonic acid groups remained at 56% after five uses.

[0032] Example 6

[0033] First, thianthrene, dimethoxymethane and HF were mixed evenly in a molar ratio of 1:5:4 and then added to 1,2-dichloroethane. The mixture was reacted at 60°C for 20 hours to obtain a polymer containing sulfide groups. Secondly, concentrated sulfuric acid and the polymer containing sulfide groups were mixed at a liquid-solid ratio of 20 mL:1 g, sulfonated at 60°C for 15 hours, and the solid obtained after filtration, washing and drying was a polymer containing sulfonic acid groups and sulfide groups. Finally, peracetic acid was reacted with a polymer containing sulfonic acid groups and sulfide groups at a liquid-solid ratio of 50 mL:1 g at room temperature for 10 hours. The solid was then washed with deionized water until the filtrate was neutral. The solid obtained after drying, grinding and sieving was a polymer containing sulfone groups and sulfonic acid groups. Analysis showed that the specific surface area of ​​the polymer containing sulfone groups and sulfonic acid groups was 369 m 2 / g. The phenolic hydroxyl and carboxyl group densities of the polymer containing sulfone and sulfonic acid groups were determined by titration to be 1.44 mmol / g and 0.77 mmol / g, respectively. In a reactor equipped with a reflux system, the polymer containing sulfone and sulfonic acid groups, oleic acid, and methanol were added to a round-bottom flask and reacted in a heating unit with a constant magnetic stirrer at 70°C for 2 hours. The calculated oleic acid conversion was 82%. Under the same experimental conditions, the oleic acid conversion of the polymer containing sulfone and sulfonic acid groups remained at 65% after four uses. A certain amount of cellulose, the polymer containing sulfone and sulfonic acid groups, and the mixture were placed in a reactor, and a certain amount of distilled water was added. The mixture was reacted at 150°C for 4 hours, and the glucose yield was 73%. Under the same experimental conditions, the glucose yield of the polymer containing sulfone and sulfonic acid groups remained at 62% after five uses.

[0034] Example 7

[0035] First, 4-phenylthioaniline, dimethoxymethane and FeCl3 were mixed in a molar ratio of 1:5:2 and then added to dichloromethane. The mixture was reacted at 45°C for 25 hours to obtain a polymer containing sulfide groups. Secondly, concentrated sulfuric acid and the polymer containing sulfide groups were mixed at a liquid-solid ratio of 35mL:1g, sulfonated at 65°C for 10 hours, and the solid obtained after filtration, washing and drying was a polymer containing sulfonic acid groups and sulfide groups. Finally, hydrogen peroxide was mixed with the polymer containing sulfonic acid groups and sulfide groups at a liquid-solid ratio of 30mL:1g and reacted at room temperature for 6 hours. The solid was then washed with deionized water until the filtrate was neutral. The solid obtained after drying, grinding and sieving was a polymer containing sulfone groups and sulfonic acid groups. Analysis and detection showed that the specific surface area of ​​the polymer containing sulfone groups and sulfonic acid groups was 402m 2 / g. The phenolic hydroxyl and carboxyl group densities of the polymer containing sulfone and sulfonic acid groups were determined by titration to be 1.33 mmol / g and 0.52 mmol / g, respectively. In a reactor equipped with a reflux system, the polymer containing sulfone and sulfonic acid groups, oleic acid, and methanol were added to a round-bottom flask and reacted in a heating unit with a constant magnetic stirrer at 70°C for 2 hours. The calculated oleic acid conversion was 67%. Under the same experimental conditions, the oleic acid conversion of the polymer containing sulfone and sulfonic acid groups remained at 59% after four uses. A certain amount of cellulose, the polymer containing sulfone and sulfonic acid groups, and the mixture were placed in a reactor, and a certain amount of distilled water was added. The mixture was reacted at 150°C for 4 hours, and the glucose yield was 61%. Under the same experimental conditions, the glucose yield of the polymer containing sulfone and sulfonic acid groups remained at 52% after five uses.

[0036] Example 8

[0037] First, 9-thioxanthone, dimethoxymethane and AlCl3 were mixed in a molar ratio of 1:1:5 and then added to chloroform. The mixture was reacted at 65°C for 25 hours to obtain a polymer containing sulfide groups. Secondly, concentrated sulfuric acid and the polymer containing sulfide groups were mixed at a liquid-solid ratio of 15mL:1g, sulfonated at 45°C for 20 hours, and the solid obtained after filtration, washing and drying was a polymer containing sulfonic acid groups and sulfide groups. Finally, peracetic acid was mixed with the polymer containing sulfonic acid groups and sulfide groups at a liquid-solid ratio of 10mL:1g and reacted at room temperature for 14 hours. The solid was then washed with deionized water until the filtrate was neutral. The solid obtained after drying, grinding and sieving was a polymer containing sulfone groups and sulfonic acid groups. Analysis showed that the specific surface area of ​​the polymer containing sulfone groups and sulfonic acid groups was 334m 2 / g. The phenolic hydroxyl and carboxyl group densities of the polymer containing sulfone and sulfonic acid groups were determined by titration to be 1.31 mmol / g and 0.70 mmol / g, respectively. In a reactor equipped with a condenser reflux system, the polymer containing sulfone and sulfonic acid groups, oleic acid, and methanol were added to a round-bottom flask and reacted in a heating unit with a constant magnetic stirrer at 70°C for 2 hours. The calculated oleic acid conversion was 75%. Under the same experimental conditions, the oleic acid conversion rate of the polymer containing sulfone and sulfonic acid groups remained at 63% after four uses. A certain amount of cellulose, a polymer containing sulfone and sulfonic acid groups, and a mixture were placed in a reactor, and a certain amount of distilled water was added. The mixture was reacted at 150°C for 4 hours, and the glucose yield was 66%. Under the same experimental conditions, the glucose yield of the polymer containing sulfone and sulfonic acid groups remained at 52% after five uses.

[0038] Example 9

[0039] First, phenothiazine, dimethoxymethane and FeCl3 were mixed in a molar ratio of 1:2:5 and then added to chloroform. The mixture was reacted at 60°C for 20 hours to obtain a polymer containing sulfide groups. Secondly, concentrated sulfuric acid and the polymer containing sulfide groups were mixed at a liquid-solid ratio of 35mL:1g, sulfonated at 65°C for 20 hours, and the solid obtained after filtration, washing and drying was a polymer containing sulfonic acid groups and sulfide groups. Finally, peracetic acid was mixed with the polymer containing sulfonic acid groups and sulfide groups at a liquid-solid ratio of 30mL:1g and reacted at room temperature for 12 hours. The solid was then washed with deionized water until the filtrate was neutral. The solid obtained after drying, grinding and sieving was a polymer containing sulfone groups and sulfonic acid groups. Analysis showed that the specific surface area of ​​the polymer containing sulfone groups and sulfonic acid groups was 255m 2 / g. The phenolic hydroxyl and carboxyl group densities of the polymer containing sulfone and sulfonic acid groups were determined by titration to be 0.89 mmol / g and 0.55 mmol / g, respectively. In a reactor equipped with a reflux system, the polymer containing sulfone and sulfonic acid groups, oleic acid, and methanol were added to a round-bottom flask and reacted in a heating unit with a constant magnetic stirrer at 70°C for 2 hours. The calculated oleic acid conversion was 65%. Under the same experimental conditions, the oleic acid conversion rate of the polymer containing sulfone and sulfonic acid groups remained at 49% after four uses. A certain amount of cellulose, the polymer containing sulfone and sulfonic acid groups, and the mixture were placed in a reactor, and a certain amount of distilled water was added. The mixture was reacted at 150°C for 4 hours, and the glucose yield was 60%. Under the same experimental conditions, the glucose yield of the polymer containing sulfone and sulfonic acid groups remained at 50% after five uses.

Claims

1. A method for preparing a polymer containing sulfone groups and sulfonic acid groups, characterized in that: The preparation method is carried out according to the following steps: (1) mixing an aromatic monomer containing a thioether group, dimethoxymethane, and a catalyst in a molar ratio of 1:1:1 to 1:5:5, and then adding the mixture to an organic solvent, reacting the mixture at 45 to 80° C. for 5 to 25 hours to obtain a thioether group-containing polymer; (2) Concentrated sulfuric acid and a polymer containing sulfide groups are mixed at a liquid-solid ratio of 5 mL: 1 g to 50 mL: 1 g, and sulfonated at 40 to 150° C. for 2 to 20 h. The solid obtained after filtration, washing, and drying is the polymer containing sulfonic acid groups and sulfide groups; (3) The oxidizing solution is mixed with the polymer containing sulfonic acid groups and sulfide groups at a liquid-solid ratio of 5 mL: 1 g to 100 mL: 1 g, and the mixture is reacted at room temperature for 1 to 24 hours. The solid is then washed with deionized water until the filtrate is neutral. The solid obtained after drying, grinding, and sieving is the polymer containing sulfone groups and sulfonic acid groups.

2. The method for preparing a polymer containing sulfone groups and sulfonic acid groups according to claim 1, wherein: The aromatic monomer containing a sulfide group is one of 4-methyl diphenyl sulfide, diphenyl sulfide, 4,4-diaminodiphenyl sulfide, 4,4-dihydroxydiphenyl sulfide, phenothiazine, 2-chlorophenothiazine, 9-thioxanthone, thianthrene, thiophene, 4-phenylthioaniline and 4-phenylthiobenzyl chloride.

3. The method for preparing a polymer containing sulfone groups and sulfonic acid groups according to claim 1, wherein: The organic solvent is one of chloroform, 1,2-dichloroethane and dichloromethane.

4. The method for preparing a polymer containing sulfone groups and sulfonic acid groups according to claim 1, wherein: The catalyst is one of AlCl3, FeCl3, SnCl4, TiCl4, ZnCl2, HF, H2SO4 and H3PO4.

5. The method for preparing a polymer containing sulfone groups and sulfonic acid groups according to claim 1, wherein: The polymer containing sulfone groups and sulfonic acid groups can be used for one of cellulose catalytic hydrolysis reaction and esterification reaction.

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