A method for preparing a cyclic sulfate by direct oxidation of hydrogen peroxide

Abstract

The application discloses a method for preparing cyclic sulfate by directly oxidizing hydrogen peroxide; the method comprises the following steps: adding hydrogen peroxide dropwise into a mixture of cyclic sulfite, an organic solvent and a solid catalyst to perform a catalytic oxidation reaction; filtering out the solid catalyst after the reaction is completed; and standing and layering the filtrate, taking the organic layer, and distilling and concentrating the organic layer to obtain a cyclic sulfate product. The method uses cheap hydrogen peroxide to directly catalyze and oxidize cyclic sulfite to prepare cyclic sulfate; on the one hand, the reaction is mild and easy to control, and the reaction conversion rate is high; on the other hand, no waste salt is generated, the water evaporation amount is small, the energy consumption is low, the generated waste water is less, and the production process is more green and environmentally-friendly; the used solid catalyst contains an active component, an active additive and an oxide carrier, can be recycled and repeatedly used, and the consumption of noble metal is reduced, so that the production cost is greatly reduced; the cyclic sulfate prepared by the method has less impurities, high purity and wide market prospect.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of new energy material synthesis, in particular to a method for preparing cyclic sulfate by direct oxidation of hydrogen peroxide, and cyclic sulfate prepared by the method can be used as an additive of lithium ion battery electrolyte and also can be used as an intermediate for drug synthesis. BACKGROUND

[0002] With the enhancement of people's environmental protection consciousness and the progress of science and technology, new green energy technology is increasingly valued by people, especially lithium ion secondary battery, because it has advantages such as high working voltage, small size, light weight, high energy density, small environmental pollution, small self-discharge, long cycle life and no memory effect, it has attracted the attention of the battery industry and has been widely used. As an additive of lithium ion battery electrolyte, cyclic sulfate can effectively avoid the decrease of initial capacity of lithium ion battery, increase the initial discharge capacity, improve the charge-discharge performance and cycle number of the battery, and improve the high-low temperature cycle performance, which is a kind of electrolyte additive especially suitable for high-power lithium ion battery of ternary system positive electrode material.

[0003] There are four kinds of new production processes of cyclic sulfate reported at present, which are acylation method, substitution method, addition method and oxidation method.

[0004] Acylation method is to prepare cyclic sulfate by the reaction of sulfuryl chloride or sulfuryl fluoride with o-diol (Vanhessche K.P.M., Sharpless K.B., Chem. Eur. J. 1997, 3, 517-522 and CN107629032A), although the raw material is cheap, the reaction yield is low, the corrosion is strong, the environmental pollution is large, and it is not suitable for industrial production.

[0005] Substitution method is to generate cyclic sulfate and silver bromide by substitution reaction of dihaloethane, typically dibromoethane, with silver sulfate (Baker, Wilson and Field, Frederick B., Journal of the Chemical Society, 86-91, 1932), the yield of this method is only 23%, and expensive silver salt is used, the cost is too high.

[0006] There are two process routes for the addition method. One is that the addition reaction of ethylene oxide and sulfur trioxide directly generates cyclic sulfate (Deruelle, Roger et al, Fr. Demande, 2664274, 10, Jan., 1992); the other is that the oxidative addition reaction of ethylene and sulfur trioxide in the presence of iodine benzene generates cyclic sulfate (Zefirov N.S. et al, Zhurnal Organicheskoi Khimii, 22(2), 450-2, 1986). However, both of the two process routes use ethylene oxide or ethylene and sulfur trioxide, which are highly dangerous and corrosive.

[0007] The oxidation method is relatively feasible for industrial production. There are five reported methods.

[0008] The first method is to oxidize cyclic sulfite with sodium hypochlorite to obtain the corresponding cyclic sulfate (Wang P., Chun B; Rachakonda S. et al., J. Org. Chem. 2009, 74, 6819-6824; KR102080198B1). Although sodium (calcium) hypochlorite has strong oxidizing properties, it is extremely unstable, especially with low active oxygen content, large amount of wastewater, and the by-product sodium chloride or calcium chloride is difficult to recycle and use, which increases the environmental pressure and the corrosion of equipment. On the other hand, the introduction of chlorine-containing oxidants has the potential risk of increasing impurities, which also increases the difficulty of product purification and downstream use.

[0009] The second method is to oxidize cyclic sulfite with sodium periodate to obtain the corresponding cyclic sulfate (Paddon-Jones G.C., Mcerulean C.S.P., Hayes P. et al, J. Org. Chem., 2001, 66, 7487-7695; Shao H., Rueter J.k., Goodman M., J. Org. Chem., 1998, 63, 5240-5244; Zhang L. Luo S., Mi X. et al., Orangic & Biomolecular Chemistry, 2009, 74, 6819-6824). This method has the following problems: on the one hand, sodium periodate is extremely expensive and has high cost, which can only be used as a reagent in the laboratory and cannot be industrialized; on the other hand, there are many iodine impurities in the product, which affects the later application.

[0010] The third is to oxidize the cyclic sulfite with potassium permanganate to obtain the corresponding cyclic sulfate (Berridge M.S, Franceschini M.P., Rosenfeld E. et al, J. Org. Chem., 1990, 55, 1211-1217). This method has many side reactions, low yield, and difficult product purification.

[0011] The fourth is to use potassium hydrogen sulfate composite salt to oxidize the cyclic sulfate (CN103012386A, CN104744427A). This method is mild and easy to control, but the cost of the oxidant is high, and a large amount of sulfate by-product is produced.

[0012] The fifth is to use hydrogen peroxide and concentrated sulfuric acid or oleum to form peroxy sulfuric acid to oxidize the cyclic sulfite (CN110386916A). This method is also mild and easy to control, but a large amount of sulfate by-product is still produced. Compared with the hypochlorite oxidation method, the sulfate by-product can be recovered and sold as a by-product, reducing the salt treatment cost. Although this method can reduce the treatment cost of the sulfate by-product, the use of sulfuric acid has a great corrosive effect on the equipment, and the amount of wastewater evaporated from the brine is also large, which has a high wastewater treatment cost. In addition, the above-mentioned reaction still uses noble metal as a catalyst, and the catalyst cannot be recycled and reused, resulting in a large consumption of noble metal and high production cost. SUMMARY

[0013] The technical problem solved by the present application is to provide a method for directly preparing a cyclic sulfate by hydrogen peroxide oxidation, which does not produce waste salt, reduces the amount of wastewater, and is clean, green and environmentally friendly.

[0014] To solve the above technical problems, one technical solution of the present application is to provide a method for directly preparing a cyclic sulfate by hydrogen peroxide oxidation, which drops hydrogen peroxide into a mixture of cyclic sulfite, organic solvent and solid catalyst for catalytic oxidation reaction, filters out the solid catalyst after the reaction, and separates the filtrate by layering, and then distills and concentrates the organic layer to obtain the cyclic sulfate product.

[0015] In a preferred embodiment of the present application, the conditions of the catalytic oxidation reaction are as follows: reaction temperature -10-150℃, reaction time 5-500min.

[0016] In a preferred embodiment of the present application, the molar ratio of sulfur atoms in the cyclic sulfite to hydrogen peroxide in the hydrogen peroxide is S:H2O2=1:0.5-5.

[0017] In a preferred embodiment of the present application, the mass concentration of the hydrogen peroxide is greater than or equal to 1%.

[0018] In a preferred embodiment of the present application, the mass of the organic solvent is 1-50 times the mass of the cyclic sulfite; the amount of the solid catalyst is 0.5-100% of the mass of the cyclic vinyl sulfite.

[0019] In a preferred embodiment of the present application, the solid catalyst comprises an active component, an active adjuvant, and an oxide carrier; the active component and the active adjuvant are loaded on the surface of the oxide carrier or embedded in the structure of the oxide; wherein the mass fraction of the active component in the solid catalyst is 0.1-1.5%; the mass fraction of the active adjuvant in the solid catalyst is 0-5%.

[0020] In a preferred embodiment of the present application, the active component is one or more than two transition metal elements; the active adjuvant is one or a combination of more than two of oxides, hydroxides, chlorides, sulfates, carbonates, phosphates, borates, carboxylates, or sulfonates of alkali metals or alkaline earth metals; the oxide carrier is one or a combination of more than two oxides of elements in the main groups III, IV, and V.

[0021] In a preferred embodiment of the present application, the transition metal elements are selected from Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Zr, Mo, Ru, Rh, Pd, Ag, Cd, W, Re, Os, Ir, Pt, Au, Hg, La, Ce, Pr, Nd, Sm, or Eu; the alkali metals or alkaline earth metals are selected from Li, Na, K, Mg, Ca, Sr, or Ba; the elements in the main groups III, IV, and V are selected from B, Si, Al, Ge, Sn, Bi, or Sb.

[0022] In a preferred embodiment of the present application, the cyclic sulfite comprises a five-membered ring monocyclic structure, a six-membered ring monocyclic structure, a polycyclic structure, or a spirocyclic structure compound:

[0023] In a preferred embodiment of the present application, the five-membered ring monocyclic structure compound has the following structure: In the formula, R1 and R2 are the same or different H, F, hydrocarbyl, hydrocarbyloxy, acyloxy;

[0024] The six-membered ring monocyclic structure compound has the following structure: In the formula, R3, R4, and R5 are the same or different H, F, hydrocarbyl, hydrocarbyloxy, acyloxy;

[0025] The polycyclic structure compound has the following structure: In the formula, R6 and R7 are the same or different H, F, hydrocarbyl, hydrocarbyloxy, acyloxy;

[0026] The spirocyclic structure compound has the following structure: or

[0027] In a preferred embodiment of the present application, the organic solvent is one or a combination of two or more of ketone, nitrile, ether, ester, amide, imidazolinone, alkane, halogenated hydrocarbon or aromatic hydrocarbon; wherein the ketone is acetone, butanone, methyl isobutyl ketone or cyclohexanone; the nitrile is acetonitrile or propionitrile; the ether is methyl tert-butyl ether, tetrahydrofuran, 1,3-dioxolane, 1,4-dioxane, ethylene glycol dimethyl ether, propylene glycol dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether or dipropylene glycol dimethyl ether; the ester is methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate, isopentyl acetate, methyl propionate, ethyl propionate, propyl propionate, dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, methyl propyl carbonate or trifluoroethyl methyl carbonate; the amide is dimethylformamide, dimethylacetamide, diethylformamide or hexamethylphosphoric triamide; the imidazolinone is N,N-dimethylimidazolinone; the alkane is n-pentane, n-hexane, n-heptane, cyclohexane, petroleum ether or solvent naphtha; the halogenated hydrocarbon is dichloromethane, dichloroethane or dichloropropane; and the aromatic hydrocarbon is benzene, toluene, xylene, fluorobenzene, chlorobenzene, o-difluorobenzene, m-difluorobenzene, p-difluorobenzene, o-dichlorobenzene, m-dichlorobenzene or p-dichlorobenzene.

[0028] The present application has the following advantages: the method for preparing cyclic sulfate by hydrogen peroxide oxidation of the present application directly catalyzes the oxidation of cyclic sulfite with cheap hydrogen peroxide to obtain cyclic sulfate, which has the advantages of no waste salt, less wastewater, low energy consumption, clean, green and environmentally friendly production process, mild reaction, easy control, high reaction conversion rate, less impurities and high purity of the prepared cyclic sulfate, recyclable solid catalyst, less consumption of noble metal, significant advantages, greatly reduced production cost and broad market prospect. DETAILED DESCRIPTION

[0029] The preferred embodiments of the present application are described in detail below to make the advantages and features of the present application more easily understood by those skilled in the art, so as to define the protection scope of the present application more clearly and explicitly.

[0030] The embodiments of the present application include:

[0031] The application discloses a solid catalyst, which comprises an active component, an active assistant and an oxide carrier; the active component and the active assistant are loaded on the surface of the oxide carrier or inlaid in the crystal structure or porous skeleton structure of the oxide carrier; wherein the active component accounts for 0.1-1.5% of the mass fraction of the solid catalyst; the active assistant accounts for 0-5% of the mass fraction of the solid catalyst; and the active component is selected from one or more than two of transition metals such as Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Zr, Mo, Ru, Rh, Pd, Ag, Cd, W, Re, Os, Ir, Pt, Au, Hg, La, Ce, Pr, Nd, Sm or Eu.

[0032] The active assistant is selected from one or more than two combinations of oxides, hydroxides, chlorides, sulfates, carbonates, phosphates, borates, carboxylates or sulfonates of alkali metals or alkaline earth metals such as Li, Na, K, Mg, Ca, Sr or Ba; and the oxide carrier is selected from one or more than two combinations of oxides of elements in the main groups III, IV and V such as B, Si, Al, Ge, Sn, Bi or Sb.

[0033] The solid catalyst can be recycled and repeatedly used, and the catalytic efficiency is stable, thereby reducing the consumption of noble metals and saving production cost.

[0034] The application further discloses a method for preparing a cyclic sulfate by catalyzing hydrogen peroxide oxidation by using the above solid catalyst; hydrogen peroxide with a mass concentration of greater than or equal to 1% is added dropwise into a mixture of cyclic sulfite, an organic solvent and the solid catalyst to perform catalytic oxidation reaction; after the reaction is completed, the solid catalyst is filtered out; the filtrate is layered by standing; and the organic layer is distilled and concentrated to obtain a cyclic sulfate product. The catalytic oxidation reaction is performed under the following conditions: the reaction temperature is-10-150 DEG C, and the reaction time is 5-500 min; the molar ratio of sulfur atoms in the cyclic sulfite to hydrogen peroxide in the hydrogen peroxide is S:H2O2=1:0.5-5; the amount of the solid catalyst is 0.5-100% of the mass of the cyclic sulfite; and the mass of the organic solvent is 1-50 times of the mass of the cyclic sulfite.

[0035] The cyclic sulfite comprises but is not limited to the following five-membered ring monocyclic structure, six-membered ring monocyclic structure, polycyclic structure or spiro ring structure compounds:

[0036] The five-membered ring monocyclic structure compound has the following structural formula: The cyclic sulfate generated after the reaction has the following structure: In the formula, R1 and R2 are the same or different H, F, a hydrocarbon group, a hydrocarbon oxy group or an acyloxy group.

[0037] The structural formula of the six-membered ring monocyclic compound is: The structure of the corresponding generated cyclic sulfate after the reaction is: In the formula, R3, R4 and R5 are the same or different H, F, hydrocarbyl, hydrocarbyloxy, acyloxy;

[0038] The structural formula of the polycyclic compound is: The structure of the corresponding generated cyclic sulfate after the reaction is: In the formula, R6 and R7 are the same or different H, F, hydrocarbyl, hydrocarbyloxy, acyloxy;

[0039] The structural formula of the spiro ring compound is The structural formula of the cyclic sulfite is The structural formula of the cyclic sulfite is The structural formula of the cyclic sulfite is

[0040] The organic solvent is one or a combination of two or more of ketone, nitrile, ether, ester, amide, imidazolinone, alkane, halogenated hydrocarbon solvent or aromatic hydrocarbon solvent; wherein the ketone organic solvent is acetone, butanone, methyl isobutyl ketone or cyclohexanone; the nitrile organic solvent is acetonitrile or propionitrile; the ether organic solvent is methyl tert-butyl ether, tetrahydrofuran, 1,3-dioxolane, 1,4-dioxane, ethylene glycol dimethyl ether, propylene glycol dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether or dipropylene glycol dimethyl ether; the ester organic solvent is methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate, isopentyl acetate, methyl propionate, ethyl propionate, propyl propionate, dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, methyl propyl carbonate or trifluoroethyl methyl carbonate; the amide organic solvent is dimethylformamide, dimethylacetamide, diethylformamide or hexamethylphosphoric triamide; the imidazolinone organic solvent is N,N-dimethylimidazolinone; the alkane organic solvent is n-pentane, n-hexane, n-heptane, cyclohexane, petroleum ether or solvent naphtha; the halogenated hydrocarbon organic solvent is dichloromethane, dichloroethane or dichloropropane; and the aromatic hydrocarbon organic solvent is benzene, toluene, xylene, fluorobenzene, chlorobenzene, o-difluorobenzene, m-difluorobenzene, p-difluorobenzene, o-dichlorobenzene, m-dichlorobenzene or p-dichlorobenzene.

[0041] Example 1

[0042] Preparation of solid catalyst

[0043] A commercially available neutral silica sol and a neutral alumina sol were diluted with pure water to a 10% mass solids content solution, respectively, 2000 g of the 10% mass solids content silica sol and 850 g of the 10% mass solids content alumina sol were mixed, then 43.3 g of bismuth nitrate was added, and 10% mass concentration sodium hydroxide was added dropwise into the mixture of the silica sol and the alumina sol under stirring until all the solids were precipitated, the solids were filtered, the filter cake was washed with pure water until it was neutral, the filter cake was dried in an oven at 120°C, then it was pulverized to obtain an oxide carrier.

[0044] 250 g of the oxide carrier was added with 32.37 g of ruthenium trichloride trihydrate and 7.75 g of cerium nitrate hexahydrate, and 8.42 g of strontium carbonate, and pure water was added under high-speed stirring to form a slurry. The slurry was vacuum filtered and washed with pure water until the water phase was neutral, then the filter cake was dried in an oven at 105°C, and then it was calcined in an oven at 450°C for 3 hours, and then it was pulverized at high speed after being cooled to room temperature to obtain a powder solid catalyst.

[0045] Example 2

[0046] Synthesis of vinyl sulfite

[0047] A reaction bottle was sequentially added with 972 g of dichloromethane, 324 g of methyl tert-butyl ether, 56 g of the solid catalyst prepared in Example 1, 108 g of vinyl sulfite with the structural formula , stirring was performed, and the reaction system was heated to 40°C with a water bath, then 85 g of hydrogen peroxide with a mass concentration of 60% (the molar ratio of S:H2O2 in the reaction was 1.5) was added dropwise into the reaction system within two hours, and the temperature was kept at about 40°C during the dropwise addition. After the dropwise addition was completed, the reaction was continued for 3 hours under stirring and reflux, and then the reaction was cooled to 5-10°C with an ice water bath, the solid catalyst was filtered out, and the filter cake was washed with a small amount of dichloromethane, and the recovered solid catalyst was collected. The filtrate was allowed to stand to separate the organic layer, and the mass percentage content of the main product was calculated to be 99.93% according to the area normalization method after the solvent peak was deducted by GC analysis. The filtrate was rotary evaporated to dryness to remove the solvent, and 102.2 g of vinyl sulfite with the structural formula was obtained, the product purity was 99.83%, and the yield was 82.4%.

[0048] Example 3

[0049] Synthesis of ethylene dithionate

[0050] A reaction bottle was sequentially added with 856 g of acetonitrile, 2140 g of dimethyl carbonate, and 1284 g of fluorobenzene, and 108 g of ethylene dithionate with the structural formula Ethylene hyposulfite 214 g, solid catalyst prepared in Example 1 90 g, the reactants were heated to 80°C with stirring in a water bath, then hydrogen peroxide with a mass concentration of 30% 294.7 g (the molar ratio of S:H202in the reactants was 1:1.3) was added dropwise into the reaction system in 4 hours, the temperature was kept at about 80°C during the dropwise addition. After the dropwise addition was completed, the reaction was continued for 3 hours with stirring and heat preservation, then the temperature was cooled to room temperature, the solid catalyst was filtered off, and the filter cake was washed with a small amount of dichloromethane to collect and recover the solid catalyst. The filtrate was allowed to stand at 5-10°C to separate the organic layer, GC analysis showed that, after deducting the solvent peak, the mass percentage of the main product calculated by the area normalization method was 99.86%. The organic layer was first dehydrated and dried over anhydrous magnesium sulfate, then rotary evaporated to dryness under reduced pressure to remove the organic solvent, to obtain ethylene hyposulfite product 192.62 g with a purity of 99.67% and a yield of 78.30%, the structural formula of which is .

[0051] Example 4

[0052] Synthesis of 2,4,8,10-tetraoxa-3,9-dithiabicyclo[5.5]undecane-3,3,9,9-tetraoxide

[0053] Into a reaction bottle were sequentially added 1,4-dioxane 684 g, ethyl propionate 4104 g, methyl isobutyl ketone 2052 g, 2,4,8,10-tetraoxa-3,9-dithiabicyclo[5.5]undecane 3,9-dioxide 228 g with a structural formula of , solid catalyst prepared in Example 1 71 g, the temperature of the reactants was maintained at 100°C with stirring in an oil bath, then hydrogen peroxide with a mass concentration of 10% 1360 g (the molar ratio of S:H202in the reactants was 1:2) was added dropwise into the reaction system in 3 hours, the temperature was kept at about 100°C during the dropwise addition. After the dropwise addition was completed, the reaction was continued for 3 hours with stirring and reflux, then the temperature was cooled to 15-20°C, the solid catalyst was filtered off, and the filtrate was allowed to stand to separate the organic layer, GC detection showed that, after deducting the solvent peak, the mass percentage of the main product calculated by the area normalization method was 99.77%. The organic layer was first dehydrated over molecular sieves, then rotary evaporated to dryness under reduced pressure to remove the organic solvent, to obtain 2,4,8,10-tetraoxa-3,9-dithiabicyclo[5.5]undecane-3,3,9,9-tetraoxide product 198.1 g with a purity of 99.57% and a yield of 76.2%, the structural formula of which is .

[0054] Example 5

[0055] Repetition of the synthesis of ethylene sulfate with the recovered solid catalyst

[0056] Using the solid catalyst recovered and dried in Example 2, the preparation experiment of vinyl sulfate was repeated according to the feeding amount and process of Example 2, and the solid catalyst was continuously recovered and recycled, and was used for 5 times in total. The experimental results of 5 times are as follows:

[0057]

[0058] Compared with the prior art, the present application has the following advantages:

[0059] 1. Using cheap hydrogen peroxide as an oxidant, the cyclic sulfite is directly oxidized into cyclic sulfate under the catalysis of the solid catalyst. The hydrogen peroxide directly participates in the reaction as an oxidant, no sulfate by-product is generated, the amount of reaction wastewater is small, the corrosion of equipment is small, the energy consumption of salt water evaporation is avoided, and the synthesis process is cleaner and more environmentally friendly.

[0060] 2. No other substances are introduced in the reaction process, no by-products are generated, the reaction conversion rate is high, the yield of the prepared cyclic sulfate product is high, the impurities are few, the purity is high, and the market prospect is broad.

[0061] 3. The reaction conditions are mild and easy to control.

[0062] 4. The solid catalyst used contains active components, active aids and oxide carriers, can be recycled and reused, and has stable catalytic efficiency, reduces the consumption of noble metal catalysts, and greatly reduces the raw material cost.

[0063] The above only describes the preferred embodiments of the present application and is not used to limit the present application. For those skilled in the art, the present application can have various modifications and changes. Any modification, equivalent replacement, improvement, etc. within the spirit and principle of the present application shall be included in the protection scope of the present application.

Claims

1. A process for the direct oxidation of hydrogen peroxide to produce cyclic sulfate esters, characterized in that, The catalytic oxidation reaction is carried out by adding hydrogen peroxide dropwise into a mixture of cyclic sulfite, organic solvent and solid catalyst, and after the reaction, the solid catalyst is filtered out, the filtrate is layered by standing, and the organic layer is distilled and concentrated to obtain the cyclic sulfate product; The cyclic sulfite is selected from , , , or wherein R1and R2are the same or different H, F, hydrocarbyl, hydrocarbyloxy, acyloxy, R3, R4and R5are the same or different H, F, hydrocarbyl, hydrocarbyloxy, acyloxy, R6and R7are the same or different H, F, hydrocarbyl, hydrocarbyloxy, acyloxy. The solid catalyst comprises an active component, an active assistant and an oxide carrier; the active component and the active assistant are loaded on the surface of the oxide carrier or inlaid in the structure of the oxide carrier; wherein the active component accounts for 0.1-1.5% of the mass fraction of the solid catalyst; the active assistant accounts for 0-5% of the mass fraction of the solid catalyst; The active component is two transition metal elements, and the transition metal is selected from Ru and Ce; The active assistant is selected from strontium carbonate; The oxide carrier is selected from a combination of oxides of Si, Al and Bi.

2. The process for the direct oxidation of hydrogen peroxide to produce cyclic sulfate esters according to claim 1, characterized in that, The catalytic oxidation reaction is carried out under the following conditions: reaction temperature -10-150℃, reaction time 5-500min.

3. The process for the direct oxidation of hydrogen peroxide to produce cyclic sulfate esters according to claim 1, characterized in that, The molar ratio of sulfur atoms in the cyclic sulfite to hydrogen peroxide in the hydrogen peroxide is S:H2O2=1:0.5-5.

4. The process for the direct oxidation of hydrogen peroxide to produce cyclic sulfate esters according to claim 1, characterized in that, The mass concentration of the hydrogen peroxide is greater than or equal to 1%.

5. The process for the direct oxidation of hydrogen peroxide to produce cyclic sulfate esters according to claim 1, characterized in that, The mass of the organic solvent is 1-50 times the mass of the cyclic sulfite; the amount of the solid catalyst is 0.5-100% of the mass of the cyclic vinyl sulfite.

6. The process for the direct oxidation of hydrogen peroxide to produce cyclic sulfate esters according to claim 1, wherein, The organic solvent is selected from one or a combination of two or more of nitrile, ether, ester, halogenated hydrocarbon or aromatic hydrocarbon; wherein the nitrile organic solvent is acetonitrile or propionitrile; the ether organic solvent is selected from methyl tert-butyl ether, tetrahydrofuran, 1,3-dioxolane, 1,4-dioxane, ethylene glycol dimethyl ether, propylene glycol dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether or dipropylene glycol dimethyl ether; the ester organic solvent is selected from methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate, isoamyl acetate, methyl propionate, ethyl propionate, propyl propionate; the halogenated hydrocarbon organic solvent is selected from dichloromethane, dichloroethane or dichloropropane; and the aromatic hydrocarbon organic solvent is selected from benzene, toluene, xylene, fluorobenzene, chlorobenzene, o-difluorobenzene, m-difluorobenzene, p-difluorobenzene, o-dichlorobenzene, m-dichlorobenzene or p-dichlorobenzene.

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