A kind of synthetic method of vinyl sulfate

Abstract

The present invention relates to the field of ester synthesis, and in particular to a method for synthesizing vinyl sulfate, comprising the following steps: (1) vinyl sulfite, a catalyst and a solvent are mixed in a flask, magnetic stirring is turned on, and after being stirred evenly, a pre-reaction liquid is formed; (2) at room temperature and pressure, cumene hydroperoxide is dropwise added to the pre-reaction liquid, and after stirring for 1 4 hours, the reaction is stopped, and vinyl sulfate is obtained through purification and separation. The present invention designs a novel synthesis method of vinyl sulfate, which can be directly synthesized by vinyl sulfite at room temperature and pressure, not only has less solid waste generated by the reaction, but also has high yield and high efficiency, which is very consistent with the concept of green chemistry.

Description

Technical Field

[0001] The invention relates to the field of ester synthesis, and in particular to a method for synthesizing vinyl sulfate. Background Art

[0002] As an important substance, vinyl sulfate (DTD) is a new type of lithium-ion battery electrolyte additive with excellent performance. Adding vinyl sulfate to lithium battery electrolyte can effectively solve the problems of lithium battery in the recycling process and also take into account the high and low temperature performance of lithium battery. At the same time, vinyl sulfate also plays an important role in the process of drug synthesis intermediates. It can also be used as a heterocyclic compound to synthesize gelatinization reagents. Therefore, it is of great significance to study the synthesis method of vinyl sulfate.

[0003] Vinyl sulfate has been developed in my country for a relatively short time. The currently disclosed preparation methods are: (1) using vinyl sulfite and sodium hypochlorite as preparation raw materials, and synthesizing vinyl sulfate under the catalytic action of ruthenium trichloride. (2) using vinyl sulfite and sodium periodate as preparation raw materials, and synthesizing vinyl sulfate under the catalytic action of ruthenium trichloride. (3) using vinyl sulfite and sodium percarbonate as preparation raw materials, and synthesizing vinyl sulfate under the catalytic action of ferric sulfate. Therefore, the synthesis of vinyl sulfate by catalytic oxidation is currently the most ideal method. In the process of synthesizing vinyl sulfate, most traditional methods require the addition of highly corrosive and environmentally unfriendly sodium hypochlorite, which generates a lot of solid waste and has a great impact on the environment. Summary of the invention

[0004] In view of the problems existing in the prior art, the object of the present invention is to provide a method for synthesizing vinyl sulfate.

[0005] The purpose of the present invention is achieved by adopting the following technical solutions:

[0006] A method for synthesizing vinyl sulfate comprises the following steps:

[0007] (1) mixing ethylene sulfite, a catalyst and a solvent in a flask, turning on magnetic stirring, and stirring until uniform to form a pre-reaction liquid;

[0008] (2) Adding cumene hydroperoxide solution dropwise to the pre-reaction solution at room temperature and pressure for 0.5-3 hours, stirring is continued for 0.5-1 hour, stopping the reaction, and obtaining vinyl sulfate through purification and separation.

[0009] Preferably, in step (1), the purity of vinyl sulfite is greater than 99%, and the solvent comprises one of dichloromethane, dichloroethane, carbon tetrachloride, dimethyl carbonate and diethyl carbonate.

[0010] Preferably, in step (1), the mass-to-liquid ratio of vinyl sulfite to solvent is 1 g: (10-20) mL.

[0011] Preferably, step (1) is carried out at room temperature, and the stirring speed is 200-300 rpm.

[0012] Preferably, in step (2), the catalyst is a porous coated microsphere with a particle size of 300-600 nm, and the added amount is 0.1%-0.5% of the mass of the vinyl sulfite.

[0013] Preferably, in step (2), the cumene hydroperoxide solution is obtained by combining cumene hydroperoxide with dichloromethane, and the mass concentration of cumene hydroperoxide in the cumene hydroperoxide solution is 10%-50%.

[0014] Preferably, in step (2), the molar ratio of cumene hydroperoxide to vinyl sulfite in the cumene hydroperoxide solution is 2:1.

[0015] Preferably, in step (2), the purification and separation comprises washing and drying. The washing step is to filter out the catalyst and then wash it at least three times with distilled water. The drying step is to dry it under vacuum conditions for 3-8 hours.

[0016] Preferably, the catalyst is prepared by:

[0017] S1. Preparation of polyvinylpyridine:

[0018] Weigh 4-vinyl pyridine and dissolve it in a reaction bottle containing hexafluoroisopropanol, then add copper and ethyl α-chlorophenylacetate in sequence, mix thoroughly, introduce inert gas into the reaction bottle to replace the air, and then place the reaction bottle at 25-30° C. for stirring reaction. After reacting for 4-6 hours, dissolve the product in isopropanol and pour it into cyclohexane. After sealing overnight, filter out the solid and dry it to obtain polyvinyl pyridine;

[0019] S2. Prepare ammonium perrhenate solution:

[0020] Weigh ammonium perrhenate and mix with deionized water, raise the temperature to 50-60°C, and stir thoroughly until completely dissolved to obtain an ammonium perrhenate solution;

[0021] S3. Preparation of porous coated microspheres:

[0022] Weigh nanometer-scale cerium dioxide, dodecyltrimethylammonium chloride, ethanol and deionized water, mix them, and stir them thoroughly at 50-60°C to form a uniform mixed solution, i.e., cerium dioxide mixed solution; then, under stirring, first add polyvinyl pyridine and mix evenly, then continuously drop the ammonium perrhenate solution, and after all the additions, continue to keep warm and stir for 3-6 hours, then cool to room temperature, stop stirring, remove the solvent under reduced pressure, and obtain porous coated microspheres after washing and drying.

[0023] Preferably, in step S1, the molar ratio of 4-vinylpyridine, elemental copper and ethyl α-chlorophenylacetate is 256:1:1, and the volume ratio of 4-vinylpyridine to hexafluoroisopropanol is 1:0.5-1.5.

[0024] Preferably, in step S2, the mass-liquid ratio of ammonium perrhenate NH4ReO4 and deionized water is 1 g: (10-20) mL.

[0025] Preferably, in step S3, the particle size of the nano-scale cerium dioxide is 200-300 nm.

[0026] Preferably, in step S3, in the cerium dioxide mixed liquid, the mass ratio of cerium dioxide, dodecyltrimethylammonium chloride, ethanol and deionized water is 1:0.1-0.3:10-20:10-20.

[0027] Preferably, in step S3, the mass ratio of polyvinyl pyridine, ammonium perrhenate solution and cerium dioxide mixed solution is 1:10-20:30-60.

[0028] The beneficial effects of the present invention are:

[0029] 1. The present invention designs a novel synthesis method of vinyl sulfate, which can be directly synthesized through vinyl sulfite at room temperature and pressure. Not only does the reaction produce less solid waste, but it also has high yield and efficiency, which is very consistent with the concept of green chemistry.

[0030] 2. The present invention prepares a core-shell coated catalyst, which uses cerium dioxide as the core and a cross-linked product of polyvinyl pyridine and ammonium perrhenate as the shell structure. First, cerium dioxide as the core not only plays a bearing role, but also has a catalytic effect, and this structural feature allows the active center to be more evenly dispersed; secondly, the rhenium atoms in ammonium perrhenate can form a coordination complex with the nitrogen atoms in polyvinyl pyridine, and the rhenium element forms irregular cross-links with polyvinyl pyridine, so that the surface of the microspheres forms a porous structure in the subsequent drying process, so that the contact area between the catalyst and the reaction liquid is larger, thereby also promoting the reaction.

[0031] 3. The catalyst prepared by the present invention can realize the rapid oxidation of vinyl sulfite to vinyl sulfate under normal temperature and pressure conditions. Not only are the experimental conditions simpler, no heating or cooling is required, thus reducing consumption, but the reaction is also more rapid. The reaction yield is as high as 94.3% in 3 hours. Even if the reaction time is shortened to 1 hour, the yield can reach more than 85%.

[0032] 4. The oxidant used in the present invention abandons the traditional highly corrosive and environmentally unfriendly sodium hypochlorite and is replaced by more environmentally friendly and safe isopropylbenzene hydroperoxide. However, under normal conditions, hydrogen peroxide needs to be rapidly decomposed under elevated temperature conditions, and the catalyst added in the present invention not only has a catalytic effect on the oxidation of vinyl sulfite, but also has a certain catalytic effect on the decomposition of hydrogen peroxide, thereby accelerating its oxygen production rate and further enhancing the synthesis rate of vinyl sulfate.

[0033] 5. In the preparation process of the catalyst of the present invention, the addition of dodecyltrimethylammonium chloride can reduce the particle size of the generated microspheres, so that the particle size of the microspheres is controlled within the nanometer range, thereby having a larger specific surface area.

[0034] 6. In addition, the catalyst of the present invention has strong reusability, and the catalytic performance is basically not reduced after being reused for at least 5 times. BRIEF DESCRIPTION OF THE DRAWINGS

[0035] The present invention is further described using the accompanying drawings, but the embodiments in the accompanying drawings do not constitute any limitation to the present invention. A person skilled in the art can obtain other drawings based on the following drawings without creative work.

[0036] Figure 1 This is a scanning electron microscope (SEM) image of the catalyst prepared in Example 1 of the present invention. DETAILED DESCRIPTION

[0037] In order to more clearly illustrate the present invention and have a clearer understanding of the technical features, purposes and beneficial effects of the present invention, the technical solution of the present invention is now described in detail below, but it should not be construed as limiting the applicable scope of the present invention.

[0038] The present invention will be further described below in conjunction with the following examples.

[0039] Example 1

[0040] A method for synthesizing vinyl sulfate comprises the following steps:

[0041] (1) Vinyl sulfite with a purity of more than 99%, a catalyst and a solvent of dichloromethane are mixed in a flask, and magnetic stirring is started at room temperature at a stirring speed of 250 rpm. After stirring evenly, a pre-reaction liquid is formed; the mass-liquid ratio of vinyl sulfite to solvent is 1 g:15 mL; the catalyst is a porous coated microsphere with a particle size of 300-600 nm, and the added amount is 0.3% of the mass of vinyl sulfite.

[0042] (2) isopropylbenzene hydroperoxide is combined with dichloromethane to obtain isopropylbenzene hydroperoxide solution, wherein the mass concentration of isopropylbenzene hydroperoxide in the isopropylbenzene hydroperoxide solution is 30%. At room temperature and pressure, the isopropylbenzene hydroperoxide solution is added dropwise to the pre-reaction solution, and the addition is completed after the addition is continued for 2 hours, and the stirring is continued for 1 hour, and the reaction is stopped. After washing and drying, the washing is to filter out the catalyst and then wash it with distilled water for at least three times, and the drying is to dry it under vacuum conditions for 5 hours, and finally vinyl sulfate is obtained; wherein the molar ratio of isopropylbenzene hydroperoxide to vinyl sulfite in the isopropylbenzene hydroperoxide solution is 2:1.

[0043] Wherein, the preparation method of the catalyst is:

[0044] S1. Preparation of polyvinylpyridine:

[0045] Weigh 4-vinyl pyridine and dissolve it in a reaction bottle containing hexafluoroisopropanol, then add copper and ethyl α-chlorophenylacetate in sequence, mix thoroughly, introduce inert gas into the reaction bottle to replace the air, then place the reaction bottle at 25-30° C. for stirring reaction, react for 5 hours, dissolve the product in isopropanol and pour it into cyclohexane, seal overnight, filter out the solid and dry it to obtain polyvinyl pyridine; wherein the molar ratio of 4-vinyl pyridine, copper and ethyl α-chlorophenylacetate is 256:1:1, and the volume ratio of 4-vinyl pyridine to hexafluoroisopropanol is 1:1.

[0046] S2. Prepare ammonium perrhenate solution:

[0047] Weigh ammonium perrhenate and mix with deionized water, heat to 50-60°C, stir thoroughly until completely dissolved, and obtain an ammonium perrhenate solution; wherein the mass-to-liquid ratio of ammonium perrhenate NH4ReO4 to deionized water is 1g:15mL.

[0048] S3. Preparation of porous coated microspheres:

[0049] Weigh nanometer-scale cerium dioxide, dodecyltrimethylammonium chloride, ethanol and deionized water, mix them, and stir them thoroughly at 50-60° C. to form a uniform mixed solution, i.e., cerium dioxide mixed solution; then, under stirring, first add polyvinyl pyridine and mix them evenly, then continuously drop the ammonium perrhenate solution, and after all the additions, continue to keep warm and stir for 3-6 hours, then cool to room temperature, stop stirring, remove the solvent under reduced pressure, and obtain porous coated microspheres after washing and drying; wherein, in the cerium dioxide mixed solution, the mass ratio of cerium dioxide, dodecyltrimethylammonium chloride, ethanol and deionized water is 1:0.2:15:15; the mass ratio of polyvinyl pyridine, ammonium perrhenate solution and cerium dioxide mixed solution is 1:15:45.

[0050] Example 2

[0051] A method for synthesizing vinyl sulfate comprises the following steps:

[0052] (1) Vinyl sulfite with a purity of more than 99%, a catalyst and a solvent of dichloromethane are mixed in a flask, and magnetic stirring is started at room temperature at a stirring speed of 200 rpm. After stirring evenly, a pre-reaction liquid is formed; the mass-liquid ratio of vinyl sulfite to solvent is 1 g:10 mL; the catalyst is a porous coated microsphere with a particle size of 300-600 nm, and the added amount is 0.3% of the mass of vinyl sulfite.

[0053] (2) isopropylbenzene hydroperoxide is combined with dichloromethane to obtain isopropylbenzene hydroperoxide solution, wherein the mass concentration of isopropylbenzene hydroperoxide in the isopropylbenzene hydroperoxide solution is 10%. At room temperature and pressure, the isopropylbenzene hydroperoxide solution is added dropwise to the pre-reaction solution, and the addition is completed after the addition is continued for 0.5 hours, and the stirring is continued for 0.5 hours, and the reaction is stopped. After washing and drying, the washing is to filter out the catalyst and then wash it with distilled water for at least three times, and the drying is to dry it under vacuum conditions for 3 hours, and finally vinyl sulfate is obtained; wherein the molar ratio of isopropylbenzene hydroperoxide to vinyl sulfite in the isopropylbenzene hydroperoxide solution is 2:1.

[0054] The preparation method of the catalyst is the same as that in Example 1.

[0055] Example 3

[0056] A method for synthesizing vinyl sulfate comprises the following steps:

[0057] (1) Vinyl sulfite with a purity of more than 99%, a catalyst and a solvent of dichloromethane are mixed in a flask, and magnetic stirring is started at room temperature at a stirring speed of 300 rpm. After stirring evenly, a pre-reaction liquid is formed; the mass-liquid ratio of vinyl sulfite to solvent is 1 g:20 mL; the catalyst is a porous coated microsphere with a particle size of 300-600 nm, and the added amount is 0.3% of the mass of vinyl sulfite.

[0058] (2) isopropylbenzene hydroperoxide is combined with dichloromethane to obtain isopropylbenzene hydroperoxide solution, wherein the mass concentration of isopropylbenzene hydroperoxide in the isopropylbenzene hydroperoxide solution is 50%. At room temperature and pressure, the isopropylbenzene hydroperoxide solution is added dropwise to the pre-reaction solution, and the addition is completed after the addition is continued for 3 hours, and the stirring is continued for 1 hour, and the reaction is stopped. After washing and drying, the washing is to filter out the catalyst and then wash it with distilled water for at least three times, and the drying is to dry it under vacuum conditions for 8 hours, and finally vinyl sulfate is obtained; wherein the molar ratio of isopropylbenzene hydroperoxide to vinyl sulfite in the isopropylbenzene hydroperoxide solution is 2:1.

[0059] The preparation method of the catalyst is the same as that in Example 1.

[0060] Example 4

[0061] A method for synthesizing vinyl sulfate, the preparation process is the same as that of Example 1, except that the preparation conditions of the catalyst are partially different.

[0062] Wherein, the preparation method of the catalyst is:

[0063] S1. Preparation of polyvinylpyridine:

[0064] 4-vinyl pyridine is weighed and dissolved in a reaction bottle containing hexafluoroisopropanol, and then copper and ethyl α-chlorophenylacetate are added in sequence. After being fully mixed, an inert gas is introduced into the reaction bottle to replace the air, and then the reaction bottle is placed at 25-30° C. for stirring reaction. After reacting for 4 hours, the product is dissolved in isopropanol and poured into cyclohexane. After sealing overnight, the solid is filtered out and dried to obtain polyvinyl pyridine; wherein the molar ratio of 4-vinyl pyridine, copper and ethyl α-chlorophenylacetate is 256:1:1, and the volume ratio of 4-vinyl pyridine to hexafluoroisopropanol is 1:0.5.

[0065] S2. Prepare ammonium perrhenate solution:

[0066] Weigh ammonium perrhenate and mix with deionized water, raise the temperature to 50°C, and stir thoroughly until completely dissolved to obtain an ammonium perrhenate solution; wherein the mass-to-liquid ratio of ammonium perrhenate NH4ReO4 to deionized water is 1g:10mL.

[0067] S3. Preparation of porous coated microspheres:

[0068] Weigh nanometer-scale cerium dioxide, dodecyltrimethylammonium chloride, ethanol and deionized water, mix them, and stir them thoroughly at 50°C to form a uniform mixed solution, i.e., the cerium dioxide mixed solution; then, under stirring, first add polyvinyl pyridine and mix them evenly, then continuously drop the ammonium perrhenate solution, and after all the additions, continue to keep warm and stir for 3 hours, then cool to room temperature, stop stirring, remove the solvent under reduced pressure, and obtain porous coated microspheres after washing and drying; wherein, in the cerium dioxide mixed solution, the mass ratio of cerium dioxide, dodecyltrimethylammonium chloride, ethanol and deionized water is 1:0.1:10:10; the mass ratio of polyvinyl pyridine, ammonium perrhenate solution and the cerium dioxide mixed solution is 1:10:30.

[0069] Example 5

[0070] A method for synthesizing vinyl sulfate, the preparation process is the same as that of Example 1, except that the preparation conditions of the catalyst are partially different.

[0071] Wherein, the preparation method of the catalyst is:

[0072] S1. Preparation of polyvinylpyridine:

[0073] 4-vinyl pyridine is weighed and dissolved in a reaction bottle containing hexafluoroisopropanol, and then copper and ethyl α-chlorophenylacetate are added in sequence. After being fully mixed, an inert gas is introduced into the reaction bottle to replace the air, and then the reaction bottle is placed at 25-30° C. for stirring reaction. After reacting for 6 hours, the product is dissolved in isopropanol and poured into cyclohexane. After sealing overnight, the solid is filtered out and dried to obtain polyvinyl pyridine; wherein the molar ratio of 4-vinyl pyridine, copper and ethyl α-chlorophenylacetate is 256:1:1, and the volume ratio of 4-vinyl pyridine to hexafluoroisopropanol is 1:1.5.

[0074] S2. Prepare ammonium perrhenate solution:

[0075] Weigh ammonium perrhenate and mix with deionized water, raise the temperature to 60°C, and stir thoroughly until completely dissolved to obtain an ammonium perrhenate solution; wherein the mass-to-liquid ratio of ammonium perrhenate NH4ReO4 to deionized water is 1g:20mL.

[0076] S3. Preparation of porous coated microspheres:

[0077] Weigh nanometer-scale cerium dioxide, dodecyltrimethylammonium chloride, ethanol and deionized water, mix them, and stir them thoroughly at 60°C to form a uniform mixed solution, i.e., the cerium dioxide mixed solution; then, under stirring, first add polyvinyl pyridine and mix them evenly, then continuously drop the ammonium perrhenate solution, and after all the additions, continue to keep warm and stir for 6 hours, then cool to room temperature, stop stirring, remove the solvent under reduced pressure, and obtain porous coated microspheres after washing and drying; wherein, in the cerium dioxide mixed solution, the mass ratio of cerium dioxide, dodecyltrimethylammonium chloride, ethanol and deionized water is 1:0.3:20:20; the mass ratio of polyvinyl pyridine, ammonium perrhenate solution and the cerium dioxide mixed solution is 1:20:60.

[0078] Example 6

[0079] A method for synthesizing vinyl sulfate is the same as that of Example 1, except that the amount of catalyst added is 0.1% of the mass of vinyl sulfite.

[0080] Example 7

[0081] A method for synthesizing vinyl sulfate is the same as that of Example 1, except that the amount of catalyst added is 0.5% of the mass of vinyl sulfite.

[0082] Comparative Example 1

[0083] A method for synthesizing vinyl sulfate, the preparation process is the same as that of Example 1, the difference is that the catalyst is different from that of Example 1, and the catalyst is cerium dioxide of the same mass and size.

[0084] Comparative Example 3

[0085] A method for synthesizing vinyl sulfate, wherein the preparation process is the same as that of Example 1, except that the catalyst is different from that of Example 1, and the catalyst is ammonium perrhenate of the same mass and size.

[0086] Comparative Example 3

[0087] A method for synthesizing vinyl sulfate, wherein the preparation process is the same as that of Example 1, except that the catalyst is different from that of Example 1; the mass and size of the catalyst are the same as those of Example 1.

[0088] Wherein, the preparation method of the catalyst is:

[0089] S1. Preparation of polyvinylpyridine:

[0090] Weigh 4-vinyl pyridine and dissolve it in a reaction bottle containing hexafluoroisopropanol, then add copper and ethyl α-chlorophenylacetate in sequence, mix thoroughly, introduce inert gas into the reaction bottle to replace the air, then place the reaction bottle at 25-30° C. for stirring reaction, react for 5 hours, dissolve the product in isopropanol and pour it into cyclohexane, seal overnight, filter out the solid and dry it to obtain polyvinyl pyridine; wherein the molar ratio of 4-vinyl pyridine, copper and ethyl α-chlorophenylacetate is 256:1:1, and the volume ratio of 4-vinyl pyridine to hexafluoroisopropanol is 1:1.

[0091] S2. Prepare ammonium perrhenate solution:

[0092] Weigh ammonium perrhenate and mix with deionized water, heat to 50-60°C, stir thoroughly until completely dissolved, and obtain an ammonium perrhenate solution; wherein the mass-to-liquid ratio of ammonium perrhenate NH4ReO4 to deionized water is 1g:15mL.

[0093] S3. Preparation of porous coated microspheres:

[0094] Under stirring at 50-60° C., polyvinyl pyridine and deionized water are mixed evenly, and then ammonium perrhenate solution is continuously added dropwise. After all the addition is completed, the mixture is kept warm and stirred for 3-6 hours, then cooled to room temperature, stirring is stopped, the solvent is removed under reduced pressure, and porous coated microspheres are obtained after washing and drying; wherein the mass ratio of polyvinyl pyridine, ammonium perrhenate solution and deionized water is 1:15:45.

[0095] Experimental Example 1

[0096] The yield and purity of the vinyl sulfate synthesized in Examples 1-3 and Comparative Examples 1-3 were tested. The purity was tested by subjecting the prepared vinyl sulfate to recrystallization treatment with dichloromethane and then testing. The test results are shown in Table 1.

[0097] Table 1 Yield of vinyl sulfate

[0098] Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Comparative Example 3 Yield (%) 94.3 86.5 95.1 87.2 83.9 90.2 purity(%) 99.7 98.3 99.2 97.6 98.1 99.1

[0099] Experimental Example 2

[0100] The catalysts synthesized in Example 1 and Comparative Examples 1-3 were tested after being reused 5 times. The results are shown in Table 2.

[0101] Table 2 Catalyst reusability

[0102] Example 1 Comparative Example 1 Comparative Example 2 Comparative Example 3 Yield after repeated use for 5 times (%) 94.0 82.5 79.6 88.7

[0103] It can be seen from Table 1 and Table 2 that the catalyst prepared by the present invention not only has higher catalytic efficiency and purity for the synthesis of vinyl sulfate, but also has stronger reusability and can be reused many times.

[0104] Finally, it should be noted that the above embodiments are only used to illustrate the technical solution of the present invention, rather than to limit the scope of protection of the present invention. Although the present invention has been described in detail with reference to the preferred embodiments, those skilled in the art should understand that the technical solution of the present invention can be modified or replaced by equivalents without departing from the essence and scope of the technical solution of the present invention.

Claims

1. A method for synthesizing vinyl sulfate, characterized in that: The following steps are involved: (1) Mixing ethylene sulfite, a catalyst and a solvent in a flask, turning on magnetic stirring, and stirring until the mixture is uniform to form a pre-reaction liquid; (2) Add cumene hydroperoxide dropwise to the pre-reaction solution at room temperature and pressure, stir for 1-4 hours, stop the reaction, and obtain vinyl sulfate through purification and separation; The preparation method of the catalyst is: S1. Preparation of polyvinylpyridine: Weigh 4-vinyl pyridine and dissolve it in a reaction bottle containing hexafluoroisopropanol, then add copper and ethyl α-chlorophenylacetate in sequence, mix thoroughly, introduce inert gas into the reaction bottle to replace the air, and then place the reaction bottle at 25-30° C. for stirring reaction. After reacting for 4-6 hours, dissolve the product in isopropanol and pour it into cyclohexane. After sealing overnight, filter out the solid and dry it to obtain polyvinyl pyridine; S2. Prepare ammonium perrhenate solution: Weigh ammonium perrhenate and mix with deionized water, raise the temperature to 50-60°C, and stir thoroughly until completely dissolved to obtain an ammonium perrhenate solution; S3. Preparation of porous coated microspheres: Weigh nanometer-scale cerium dioxide, dodecyltrimethylammonium chloride, ethanol and deionized water, mix them, and stir them thoroughly at 50-60°C to form a uniform mixed solution, i.e., cerium dioxide mixed solution; then, under stirring, first add polyvinyl pyridine and mix evenly, then continuously drop the ammonium perrhenate solution, and after all the additions, continue to keep warm and stir for 3-6 hours, then cool to room temperature, stop stirring, remove the solvent under reduced pressure, and obtain porous coated microspheres after washing and drying.

2. The method for synthesizing vinyl sulfate according to claim 1, characterized in that: In step (1), the purity of vinyl sulfite is greater than 99%, and the solvent includes one of dichloromethane, dichloroethane, carbon tetrachloride, dimethyl carbonate, and diethyl carbonate.

3. The method for synthesizing vinyl sulfate according to claim 1, characterized in that: In step (1), the mass-to-liquid ratio of vinyl sulfite to solvent is 1 g: (10-20) mL.

4. The method for synthesizing vinyl sulfate according to claim 1, characterized in that: Step (1) is carried out at room temperature, and the stirring speed is 200-300 rpm.

5. The method for synthesizing vinyl sulfate according to claim 1, characterized in that: In step (2), the catalyst is a porous coated microsphere with a particle size of 300-600 nm, and the added amount is 0.1%-0.5% of the mass of vinyl sulfite.

6. The method for synthesizing vinyl sulfate according to claim 1, characterized in that: In step (2), the cumene hydroperoxide solution is obtained by combining cumene hydroperoxide with dichloromethane, and the mass concentration of cumene hydroperoxide in the cumene hydroperoxide solution is 10%-50%.

7. The method for synthesizing vinyl sulfate according to claim 1, characterized in that: In step (2), the molar ratio of cumene hydroperoxide to vinyl sulfite in the cumene hydroperoxide solution is 2:

1.

8. The method for synthesizing vinyl sulfate according to claim 1, characterized in that: In step (2), the purification and separation includes washing and drying. The washing is performed by washing with dichloromethane at least three times, and the drying is performed under vacuum conditions for 3-8 hours.

9. The method for synthesizing vinyl sulfate according to claim 1, characterized in that: In step S1, the molar ratio of 4-vinylpyridine, elemental copper and ethyl α-chlorophenylacetate is 256:1:1, and the volume ratio of 4-vinylpyridine to hexafluoroisopropanol is 1:0.5-1.5; in step S2, the mass-liquid ratio of ammonium perrhenate NH4ReO4 and deionized water is 1g:(10-20)mL; in step S3, the particle size of nano-scale cerium dioxide is 200-300nm; in step S3, in the cerium dioxide mixed liquid, the mass ratio of cerium dioxide, dodecyltrimethylammonium chloride, ethanol and deionized water is 1:0.1-0.3:10-20:10-20; in step S3, the mass ratio of polyvinylpyridine, ammonium perrhenate solution and cerium dioxide mixed liquid is 1:10-20:30-60.

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