A method for preparing vinyl sulfate

Abstract

The invention discloses a method for preparing vinyl sulfate. The method comprises: under stirring conditions, ethylene sulfite is subjected to oxidation reaction in a halogenated hydrocarbon solvent in the presence of (1,1,1-triacetoxy)-1,1-dihydro-1,2-benzidoyl-3(1H)-ketone to generate vinyl sulfate. The method can achieve an ideal yield and has the advantages of relatively reasonable cost, simple and safe operation, low equipment requirements, less three wastes, and the like.

Description

[0001] The present invention is a divisional application of a Chinese invention patent application with an application date of August 29, 2022, application number 2022110404078, and name “A method for preparing vinyl sulfate”. Technical Field

[0002] The invention relates to the technical field of chemical synthesis, and in particular to a method for preparing vinyl sulfate. Background Art

[0003] Vinyl sulfate (1,3,2-Dioxathiolane 2,2-dioxide), melting point: 99°C, colorless crystals or crystalline powder at room temperature, sensitive to water and high temperature. Vinyl sulfate can be used as an additive for lithium-ion battery electrolytes. Adding vinyl sulfate to lithium-ion battery electrolytes can effectively inhibit the initial capacity decline of lithium-ion batteries, increase the initial discharge capacity, reduce the expansion of batteries after high-temperature storage, improve the battery's charge and discharge performance, and extend the battery cycle life. In addition to being used in lithium-ion batteries, it is also widely used in the fields of medicine and material intermediates, and has broad market prospects. Its structural formula is:

[0004]

[0005] The current method for preparing vinyl sulfate is mainly to obtain the product vinyl sulfate by catalytic oxidation of vinyl sulfite.

[0006] For example, Chinese invention patent CN109988145A discloses a method for preparing vinyl sulfate, comprising the following steps: 1) adding ethylene glycol and dripping thionyl chloride in a reaction bottle to react, and after the reaction is completed, purifying and separating to obtain vinyl sulfite; the molar ratio of the added ethylene glycol and thionyl chloride is 1:1-1.05; 2) adding solvent, vinyl sulfite, palladium chloride complex catalyst, copper chloride catalyst in a closed reactor, and then introducing an oxidant, controlling the pressure in the reactor to 0.1MPa-0.3MPa, heating the reactor to a temperature of 75-90°C for reaction; 3) after the reaction is completed, cooling to 30-35°C, opening the reactor, filtering and recovering the solid catalyst, washing the reaction solution with water, concentrating, crystallizing and drying to obtain a finished vinyl sulfate product. This patent uses a relatively expensive rare metal palladium catalyst, and also requires the use of a copper chloride catalyst in combination, which makes the production cost high, and the reaction temperature is high, and a pressurized reaction is required, the operation is relatively cumbersome and demanding, and the equipment requirements are high.

[0007] Chinese invention patent CN105481826A discloses a method for preparing vinyl sulfate, which comprises: adding sodium bicarbonate aqueous solution to ethylene sulfite at a temperature of about 10°C to adjust the pH value of the system to 7-8, then adding ruthenium trichloride as a catalyst, and dripping sodium hypochlorite solution with a mass concentration of 13% at a temperature of 0-10°C to oxidize and prepare vinyl sulfate. This patent also uses a relatively expensive rare metal ruthenium catalyst, which makes the production cost high, and the use of sodium hypochlorite will result in a lot of three wastes, which is not conducive to environmental protection and does not meet the development requirements of green chemistry. Summary of the invention

[0008] The purpose of the present invention is to overcome one or more deficiencies in the prior art and to provide an improved method for preparing vinyl sulfate, which can achieve an ideal yield while having the advantages of relatively reasonable cost, simple and safe operation, low equipment requirements, less waste, etc.

[0009] To achieve the above object, the technical solution adopted by the present invention is: a method for preparing vinyl sulfate, the preparation method uses ethylene sulfite as a raw material, and the preparation method comprises:

[0010] Ethylene sulfite is subjected to oxidation reaction in a halogenated hydrocarbon solvent in the presence of (1,1,1-triacetoxy)-1,1-dihydro-1,2-benzidoyl-3(1H)-one to generate vinyl sulfate. The oxidation reaction temperature is 10-50°C.

[0011] According to some preferred aspects of the present invention, the molar ratio of the (1,1,1-triacetoxy)-1,1-dihydro-1,2-benzidoyl-3(1H)-one to the ethylene sulfite is 1.05-3:1, more preferably 1.05-1.5:1.

[0012] According to some preferred aspects of the present invention, the temperature of the oxidation reaction is 20-40°C, further 20-30°C.

[0013] According to the present invention, the oxidation reaction of the present invention can also be carried out at 20-25°C, which is basically in the range of room temperature or normal temperature or with a slight fluctuation. The reaction temperature is low, the energy consumption is low, and the equipment requirements are low.

[0014] In some embodiments of the present invention, the reaction time of the oxidation reaction is 1-6 hours, preferably 2-4 hours.

[0015] According to some preferred aspects of the present invention, the halogenated hydrocarbon solvent is a combination of one or more selected from 1,2-dichloroethane, 1-chloropropane, dichloromethane, chloroform, carbon tetrachloride, trichloroethane, tetrachloroethane, bromoethane, dibromoethane and chlorobenzene.

[0016] In some preferred embodiments of the present invention, the halogenated hydrocarbon solvent is a combination of one or more selected from 1,2-dichloroethane, chloroform, trichloroethane, ethyl bromide, and chlorobenzene.

[0017] According to some preferred aspects of the present invention, the preparation method comprises:

[0018] Dissolving (1,1,1-triacetoxy)-1,1-dihydro-1,2-benzimidoyl-3(1H)-one in a partially halogenated hydrocarbon solvent to obtain a (1,1,1-triacetoxy)-1,1-dihydro-1,2-benzimidoyl-3(1H)-one solution;

[0019] dissolving ethylene sulfite in the remaining halogenated hydrocarbon solvent to obtain an ethylene sulfite solution;

[0020] The (1,1,1-triacetoxy)-1,1-dihydro-1,2-benzidoyl-3(1H)-one solution is added dropwise to the ethylene sulfite solution, and after the addition is completed, an oxidation reaction is continued to generate vinyl sulfate.

[0021] Furthermore, the preparation method also includes: after the oxidation reaction is completed, quenching the reaction, separating and concentrating under reduced pressure to obtain a vinyl sulfate concentrate, then adding a low-polarity aprotic solvent for crystallization, and vacuum drying to obtain purified vinyl sulfate;

[0022] Wherein, the low polar aprotic solvent is one or more combinations selected from petroleum ether, n-hexane, cyclohexane, n-pentane, cyclopentane, isopentane, isooctane, toluene, o-xylene, and p-xylene.

[0023] According to some preferred aspects of the present invention, the reduced pressure concentration is carried out at a vacuum degree of 5-10 Torr and a temperature of 30-90°C.

[0024] In some preferred embodiments of the present invention, the reduced pressure concentration is carried out at a temperature of 60-80° C. and can be concentrated to 1 / 8-1 / 5 of the original volume.

[0025] According to some preferred aspects of the present invention, the crystallization temperature of the crystallization is -15°C to -5°C, and the crystallization time is 12-48h; more preferably, the crystallization temperature of the crystallization is -12°C to -8°C, and the crystallization time is 16-24h.

[0026] According to some preferred aspects of the present invention, the vacuum degree of the vacuum drying is 8-10 Torr and the temperature is 10-90°C.

[0027] In some preferred embodiments of the present invention, the vacuum drying temperature is 50-80°C.

[0028] Due to the application of the above technical solution, the present invention has the following advantages compared with the prior art:

[0029] After a large number of experimental studies, the inventor of the present invention accidentally discovered that (1,1,1-triacetoxy)-1,1-dihydro-1,2-benzidoyl-3(1H)-one can be used to oxidize ethylene sulfite to vinyl sulfate, which not only obtains excellent yield and purity, but also has a mild reaction, less wastewater, reduced three wastes, and good environmental protection. At the same time, the operation steps are simple, the production cost is reasonable, and the raw materials are easily available. BRIEF DESCRIPTION OF THE DRAWINGS

[0030] Figure 1 This is the H-NMR spectrum of the vinyl sulfate prepared in Example 1 of the present invention. DETAILED DESCRIPTION

[0031] The above scheme is further described below in conjunction with specific embodiments; it should be understood that these embodiments are used to illustrate the basic principles, main features and advantages of the present invention, and the present invention is not limited to the scope of the following embodiments; the implementation conditions adopted in the embodiments can be further adjusted according to specific requirements, and the implementation conditions not specified are usually the conditions in conventional experiments.

[0032] Unless otherwise specified in the following examples, all raw materials are commercially available or prepared by conventional methods in the art.

[0033] Example 1

[0034] This example provides a method for preparing vinyl sulfate, which comprises the following steps:

[0035] (1) Preparation of (1,1,1-triacetoxy)-1,1-dihydro-1,2-benzimidoyl-3(1H)-one solution: Add a stirring bar to a 250 mL reaction bottle, add 200 mL of ethyl bromide to the reaction bottle, and then cool it to about 10°C in a cold water bath and start stirring. Then slowly add 89.1 g (0.21 mol) of (1,1,1-triacetoxy)-1,1-dihydro-1,2-benzimidoyl-3(1H)-one. Then return to room temperature naturally. After returning to room temperature, continue stirring for 5 minutes to obtain (1,1,1-triacetoxy)-1,1-dihydro-1,2-benzimidoyl-3(1H)-one solution.

[0036] (2) Synthesis of vinyl sulfate: Add a stirring bar, a dropping funnel and a condenser to a 500 mL reaction flask, add 100 mL of ethyl bromide and 21.63 g (0.20 mol) of ethyl sulfite to the reaction flask. Control the temperature at 20°C, slowly add the pre-prepared (1,1,1-triacetoxy)-1,1-dihydro-1,2-benzidoyl-3(1H)-one solution under stirring, and add for about 1 hour. After the addition is complete, continue the reaction for 3 hours, and monitor whether the reaction of ethyl sulfite is complete by GC. After the reaction is complete, quench the reaction with 50 mL of saturated sodium carbonate solution, transfer to a separatory funnel for static separation, and wash the aqueous phase with 2×20 mL of ethyl bromide. After the organic phases were combined, the mixture was concentrated under reduced pressure at a vacuum degree of 10 Torr until it became a slurry. Then, 200 mL of petroleum ether was added to crystallize at -10°C. A white solid product precipitated. After filtration, the solid was dried at a temperature of 65°C and a vacuum degree of 10 Torr to obtain 22.49 g of vinyl sulfate. The GC-MS purity was 99.91% and the yield was 90.61%.

[0037] The NMR hydrogen spectrum of the prepared vinyl sulfate is as follows Figure 1 shown.

[0038] Test results: ICP-OES (ppm): Na + =8.94ppm, K + =0.65ppm,Fe 2+ =1.19ppm, Ca 2+ =3.12ppm, Mg 2+ =0.31ppm. IC: F-=18.34ppm, Cl-=10.95ppm, SO 4 2- =10.72ppm, NO 3 -=2.59ppm. KF:H 2 O=83.5ppm.

[0039] Example 2

[0040] This example provides a method for preparing vinyl sulfate, which comprises the following steps:

[0041] (1) Preparation of (1,1,1-triacetoxy)-1,1-dihydro-1,2-benzimidoyl-3(1H)-one solution: Add a stirring bar to a 250 mL reaction flask, add 200 mL of chloroform to the reaction flask, and then cool it to about 10°C in a cold water bath and start stirring. Then slowly add 89.1 g (0.21 mol) of (1,1,1-triacetoxy)-1,1-dihydro-1,2-benzimidoyl-3(1H)-one. Then return to room temperature naturally. After returning to room temperature, continue stirring for 5 minutes to obtain (1,1,1-triacetoxy)-1,1-dihydro-1,2-benzimidoyl-3(1H)-one solution.

[0042] (2) Synthesis of vinyl sulfate: Add a stirring bar, a dropping funnel and a condenser to a 500 mL reaction flask, add 100 mL of chloroform and 21.63 g (0.20 mol) of ethylene sulfite to the reaction flask. Control the temperature at 25°C, slowly add the prepared (1,1,1-triacetoxy)-1,1-dihydro-1,2-benzidoyl-3(1H)-one solution under stirring, and add for about 1 hour. After the addition is complete, continue the reaction for 3 hours, and monitor whether the ethylene sulfite has reacted completely by GC. After the reaction is complete, quench the reaction with 50 mL of saturated sodium carbonate solution, transfer to a separatory funnel for static separation, and wash the aqueous phase with 2×30 ml of chloroform. After the organic phases were combined, the mixture was concentrated under reduced pressure at a vacuum degree of 10 Torr until it became a slurry. Then, 200 mL of n-hexane was added to crystallize at -10°C. A white solid product precipitated. After filtration, the solid was dried at a temperature of 60°C and a vacuum degree of 8 Torr to obtain 22.82 g of vinyl sulfate. The GC-MS purity was 99.96% and the yield was 91.94%.

[0043] Test results: ICP-OES (ppm): Na + =6.37ppm, K + =0.41ppm,Fe 2+ =0.53ppm, Ca 2+ =1.79ppm,Mg 2+ =0.26ppm. IC: F-=11.89ppm, Cl-=13.01ppm, SO 4 2- =13.11ppm, NO 3 -=1.37ppm. KF:H 2 O=91.8ppm.

[0044] Example 3

[0045] This example provides a method for preparing vinyl sulfate, which comprises the following steps:

[0046] (1) Preparation of (1,1,1-triacetoxy)-1,1-dihydro-1,2-benzimidoyl-3(1H)-one solution: Add a stirring bar to a 500 mL reaction bottle, add 250 mL of 1,2-dichloroethane to the reaction bottle, and then cool it to about 10°C in a cold water bath and start stirring. Then slowly add 114.21 g (0.34 mol) of (1,1,1-triacetoxy)-1,1-dihydro-1,2-benzimidoyl-3(1H)-one. Then return to room temperature naturally, and continue stirring for 5 minutes after returning to room temperature to obtain (1,1,1-triacetoxy)-1,1-dihydro-1,2-benzimidoyl-3(1H)-one solution.

[0047] (2) Synthesis of vinyl sulfate: Add a stirring bar, a dropping funnel and a condenser to a 1000 mL reaction flask, add 100 mL of 1,2-dichloroethane and 32.44 g (0.30 mol) of ethylene sulfite. Control the temperature at 20°C, slowly add the prepared (1,1,1-triacetoxy)-1,1-dihydro-1,2-benzidoyl-3(1H)-one solution under stirring, and add for about 1 hour. After the addition is complete, continue the reaction for 4 hours, and monitor whether the ethylene sulfite has reacted completely by GC. After the reaction is complete, quench the reaction with 100 mL of saturated sodium carbonate solution, transfer to a separating funnel for static separation, and wash the aqueous phase with 2×40 ml of 1,2-dichloroethane. After the organic phases were combined, the product was concentrated under reduced pressure at 8 Torr until it became a slurry. Then, 350 mL of cyclopentane was added to crystallize at -10°C. A white solid product precipitated. After filtration, the solid was dried at 70°C and 8 Torr in a vacuum to obtain 34.29 g of vinyl sulfate. The purity of the product according to GC-MS was 99.94% and the yield was 92.1%.

[0048] Test results: ICP-OES (ppm): Na + =9.11ppm, K + =0.89ppm,Fe 2+ =0.22ppm, Ca 2+ =1.12ppm,Mg 2+ =0.19ppm. IC: F-=14.37ppm, Cl-=16.15ppm, SO 4 2 -=18.42ppm,NO 3 -=3.01ppm. KF:H 2 O=97.2ppm.

[0049] Example 4

[0050] This example provides a method for preparing vinyl sulfate, which comprises the following steps:

[0051] (1) Preparation of (1,1,1-triacetoxy)-1,1-dihydro-1,2-benzimidoyl-3(1H)-one solution: Add a stirring bar to a 500 mL reaction bottle, add 300 mL of chlorobenzene to the reaction bottle, and then cool it to about 10°C in a cold water bath and start stirring. Then slowly add 114.21 g (0.34 mol) of (1,1,1-triacetoxy)-1,1-dihydro-1,2-benzimidoyl-3(1H)-one. Then return to room temperature naturally. After returning to room temperature, continue stirring for 5 minutes to obtain (1,1,1-triacetoxy)-1,1-dihydro-1,2-benzimidoyl-3(1H)-one solution.

[0052] (2) Synthesis of vinyl sulfate: Add a stirring bar, a dropping funnel and a condenser to a 1000 mL reaction flask, add 150 mL of chlorobenzene and 21.62 g (0.20 mol) of ethylene sulfite to the reaction flask. Control the temperature at 20°C, slowly add the pre-prepared (1,1,1-triacetoxy)-1,1-dihydro-1,2-benzidoyl-3(1H)-one solution under stirring, and add for about 1 hour. After the addition is complete, continue the reaction for 4 hours, and monitor whether the ethylene sulfite has reacted completely by GC. After the reaction is complete, quench the reaction with 100 mL of saturated sodium carbonate solution, transfer to a separatory funnel for static separation, and wash the aqueous phase with 2×40 mL of chlorobenzene. After the organic phases were combined, they were concentrated under reduced pressure at a vacuum degree of 6 Torr until they became slurry. Then, 250 mL of isopentane was added to crystallize at -10°C. A white solid product precipitated. After filtration, the solid was dried under vacuum at a temperature of 70°C and 8 Torr to obtain 22.62 g of vinyl sulfate. The GC-MS purity was 99.91% and the yield was 91.12%.

[0053] Test results: ICP-OES (ppm): Na + =12.26ppm, K + =0.99ppm,Fe 2+ =0.43ppm, Ca 2+ =2.65ppm, Mg 2+ =0.13ppm. IC: F-=15.28ppm, Cl-=18.94ppm, SO 4 2 -=16.65ppm,NO 3 -=2.56ppm. KF:H 2 O=92.9ppm.

[0054] Example 5

[0055] This example provides a method for preparing vinyl sulfate, which comprises the following steps:

[0056] (1) Preparation of (1,1,1-triacetoxy)-1,1-dihydro-1,2-benzimidoyl-3(1H)-one: Add a stirring bar to a 1000 mL reaction flask, add 500 mL of trichloroethane to the reaction flask, and then cool it to about 10°C in a cold water bath and start stirring. Then slowly add 190.86 g (0.45 mol) of (1,1,1-triacetoxy)-1,1-dihydro-1,2-benzimidoyl-3(1H)-one. Then return to room temperature naturally, and continue stirring for 5 minutes after returning to room temperature to obtain a (1,1,1-triacetoxy)-1,1-dihydro-1,2-benzimidoyl-3(1H)-one solution.

[0057] (2) Synthesis of vinyl sulfate: A stirring bar, a dropping funnel and a condenser were added to a 1000 mL reaction flask. 200 mL of trichloroethane and 43.24 g (0.40 mol) of ethylene sulfite were added to the reaction flask. The temperature was controlled at 25°C. The pre-prepared peroxytrifluoroacetic acid solution was slowly added dropwise under stirring for about 1 hour. After the addition was completed, the reaction was continued for 5 hours. GC was used to monitor whether the reaction of ethylene sulfite was complete. After the reaction was completed, 150 mL of saturated sodium carbonate solution was used to quench the reaction. The mixture was transferred to a separating funnel for static stratification. The aqueous phase was washed with 2×60 mL of trichloroethane. After the organic phases were combined, the mixture was concentrated under reduced pressure at a vacuum degree of 5 Torr to a slurry state. 300 mL of toluene was added to crystallize at -10°C. A white solid product was precipitated. After filtration, the solid was dried under vacuum at a temperature of 70°C and 8 Torr to obtain 45.97 g of vinyl sulfate. The GC-MS purity was 99.95% and the yield was 92.59%.

[0058] Test results: ICP-OES (ppm): Na + =8.83ppm, K + =0.75ppm,Fe 2+ =0.28ppm, Ca 2+ =1.12ppm,Mg 2+ =0.17ppm. IC: F-=14.31ppm, Cl-=15.82ppm, SO 4 2- =14.59ppm, NO 3 -=1.99ppm. KF:H 2 O=86.4ppm.

[0059] The above embodiments are only for illustrating the technical concept and features of the present invention, and their purpose is to enable people familiar with the technology to understand the content of the present invention and implement it accordingly, and they cannot be used to limit the protection scope of the present invention. Any equivalent changes or modifications made according to the spirit of the present invention should be included in the protection scope of the present invention.

[0060] The endpoints and any values ​​of the ranges disclosed in this article are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of each range, the endpoint values ​​of each range and the individual point values, and the individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed in this article.

Claims

1. A method for preparing vinyl sulfate, characterized in that: The method comprises: under stirring conditions, allowing ethylene sulfite to undergo oxidation reaction in a halogenated hydrocarbon solvent in the presence of (1,1,1-triacetoxy)-1,1-dihydro-1,2-benzidoyl-3(1H)-one at a temperature of 10-50°C to generate vinyl sulfate.

2. The method for preparing vinyl sulfate according to claim 1, characterized in that: After the oxidation reaction is completed, the reaction is quenched, separated and concentrated under reduced pressure to obtain a vinyl sulfate concentrate, which is then crystallized by adding a low-polarity aprotic solvent and dried in vacuo to obtain purified vinyl sulfate.

3. The method for preparing vinyl sulfate according to claim 1 or 2, characterized in that: The implementation method of the oxidation reaction includes: dissolving (1,1,1-triacetoxy)-1,1-dihydro-1,2-benzidoyl-3(1H)-one in a part of a halogenated hydrocarbon solvent to obtain a (1,1,1-triacetoxy)-1,1-dihydro-1,2-benzidoyl-3(1H)-one solution; dissolving ethylene sulfite in the remaining halogenated hydrocarbon solvent to obtain an ethylene sulfite solution; The temperature is controlled at 20-50°C, and under stirring, the (1,1,1-triacetoxy)-1,1-dihydro-1,2-benzidoyl-3(1H)-one solution is added dropwise to the ethylene sulfite solution. After the addition is completed, the oxidation reaction is continued. The reaction time of the oxidation reaction is 1-6 hours to generate vinyl sulfate.

4. The method for preparing vinyl sulfate according to claim 1 or 2, characterized in that: The temperature of the oxidation reaction is 20-40°C.

5. The method for preparing vinyl sulfate according to claim 4, characterized in that: The temperature of the oxidation reaction is 20-30°C.

6. The method for preparing vinyl sulfate according to claim 5, characterized in that: The temperature of the oxidation reaction is 20-25°C, and the reaction time of the oxidation reaction is 2-6h.

7. The method for preparing vinyl sulfate according to claim 1 or 2, characterized in that: The molar ratio of the (1,1,1-triacetoxy)-1,1-dihydro-1,2-benzidoyl-3(1H)-one to the ethylene sulfite is 1.05-3:1; the halogenated hydrocarbon solvent is a combination of one or more selected from 1,2-dichloroethane, 1-chloropropane, dichloromethane, chloroform, carbon tetrachloride, trichloroethane, tetrachloroethane, bromoethane, dibromoethane, and chlorobenzene.

8. The method for preparing vinyl sulfate according to claim 2, characterized in that: The halogenated hydrocarbon solvent is a combination of one or more selected from 1,2-dichloroethane, chloroform, trichloroethane, ethyl bromide, and chlorobenzene; The molar ratio of the (1,1,1-triacetoxy)-1,1-dihydro-1,2-benzidoyl-3(1H)-one to the ethylene sulfite is 1.05-1.5:1; The low polar aprotic solvent is one or more combinations selected from petroleum ether, n-hexane, cyclohexane, n-pentane, cyclopentane, isopentane, isooctane, toluene, o-xylene, and p-xylene.

9. The method for preparing vinyl sulfate according to claim 2, characterized in that: The reduced pressure concentration is carried out at a vacuum degree of 5-10 Torr and a temperature of 30-90°C; The crystallization temperature of the crystallization is -15°C to -5°C, and the crystallization time is 12-48h; The vacuum degree of the vacuum drying is 8-10 Torr and the temperature is 10-90°C.

10. The method for preparing vinyl sulfate according to claim 2, characterized in that: The reduced pressure concentration is carried out at a temperature of 60-80°C and can be concentrated to 1 / 8-1 / 5 of the original volume; The crystallization temperature of the crystallization is -12°C to -8°C, and the crystallization time is 16-24h; The vacuum drying temperature is 50-80°C.

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