Preparation method of ethylene sulfate and derivatives thereof

Abstract

The invention relates to the technical field of organic synthesis, in particular to a preparation method of ethylene sulfate and derivatives thereof, which comprises the following steps: S1, taking an aprotic solvent as a reaction solvent, adding urea peroxide, and stirring until the urea peroxide is dissolved; s2, dropwise adding ethylene sulfite or an ethylene sulfite derivative, stirring for reaction, and purifying to obtain ethylene sulfate or an ethylene sulfate derivative; the method has the advantages of reducing the catalyst cost and reducing the wastewater amount.

Description

Technical Field

[0001] The present application relates to the technical field of organic synthesis, and in particular to a method for preparing vinyl sulfate and its derivatives. Background Art

[0002] Vinyl sulfate and its derivatives can be used as additives for lithium-ion battery electrolytes, mainly vinyl sulfate, 4-methyl vinyl sulfate, 4-ethyl vinyl sulfate, 4-propyl vinyl sulfate, propylene sulfate, 1,4-butanediol sulfate, etc. In the current industry, vinyl sulfite derivatives are mainly prepared as intermediates by reacting diol compounds with thionyl chloride, and then oxidized to obtain vinyl sulfate and its derivatives. There are two commonly used oxidation methods in industry: 1. Using sodium hypochlorite as an oxidant, oxidizing vinyl sulfite and its derivatives into vinyl sulfate and its derivatives under the catalysis of ruthenium trichloride and other catalysts. This method will produce a large amount of salt-containing wastewater, and the precious metal catalyst ruthenium trichloride used is difficult to recycle. Ruthenium is an extremely expensive rare precious metal, which also makes the cost of vinyl sulfate synthesis process very high; 2. Using hydrogen peroxide as an oxidant and titanium silicon molecular sieve TS-1 as a catalyst, oxidize vinyl sulfite and its derivatives to generate vinyl sulfate and its derivatives. In this reaction system, hydrogen peroxide, catalyst, vinyl sulfite and its derivatives are not miscible, and it is a heterogeneous reaction. When the content of hydrogen peroxide is generally 27%-30%, a large amount of wastewater will be generated after the reaction. The catalyst needs to be filtered and recovered, and the process is cumbersome. At the same time, the catalyst is expensive and the cost is high. Summary of the invention

[0003] In order to reduce catalyst costs and reduce the amount of wastewater, the present application provides a method for preparing vinyl sulfate and its derivatives.

[0004] In the first aspect, the present application provides a method for preparing vinyl sulfate and its derivatives, using the following technical scheme: A method for preparing vinyl sulfate and its derivatives, comprising the following steps: S1. Using an aprotic solvent as a reaction solvent, add urea peroxide and stir until dissolved; S2. Add vinyl sulfite or a vinyl sulfite derivative dropwise, stir to react, and purify to obtain vinyl sulfate or a vinyl sulfate derivative.

[0005] By adopting the above technical scheme, the carbamide peroxide selected in the present application can be well dissolved in aprotic solvents, overcoming the problems of heterogeneous reactions in the prior art, such as large amount of wastewater generated and difficulty in catalyst recovery; and the present application does not require the addition of additional catalysts, avoiding the high cost problem caused by precious metal catalysts.

[0006] Preferably, the aprotic solvent in S1 is a mixed solution of one or more of dichloromethane, chloroform and 1,2-dichloroethane.

[0007] By adopting the above technical scheme, the aprotic solvent is any one or a mixed solution of dichloromethane, chloroform and 1,2-dichloroethane, which can make urea peroxide dissolve well and maintain good reaction activity, so that the reaction yield and the purity of the target product are both high.

[0008] Preferably, the molar ratio of the urea peroxide to the vinyl sulfite or the vinyl sulfite derivative is (1.01-1.2):1.

[0009] By adopting the above technical scheme, the amount of carbamide peroxide added has a certain influence on the purity and yield of the product. When the amount of carbamide peroxide added is 1.01-1.2 times the molar amount of vinyl sulfite, the purity and yield of the product are relatively high, which meets the needs of actual production. Among them, the amount of carbamide peroxide added is 1.08 times the molar amount of vinyl sulfite, which is a better addition amount.

[0010] Preferably, the mass ratio of the aprotic solvent to vinyl sulfite or vinyl sulfite derivative is (8-15):1.

[0011] By adopting the above technical solution, the aprotic solvent can dissolve urea peroxide well when added in this amount, so that the urea peroxide can maintain its reaction activity, and the reaction can proceed well in the forward direction without causing excessive solvent waste.

[0012] Preferably, the temperature during the dropwise addition of vinyl sulfite or vinyl sulfite derivative and the stirring reaction in S2 is controlled at 20-50°C.

[0013] By adopting the above technical scheme, considering the reaction activity and overheating decomposition temperature of carbamide peroxide, the reaction temperature should not be too high. Within this range, the reaction yield and product purity can be high. When the reaction temperature is too high, due to the high-temperature decomposition or reduced activity of carbamide peroxide, there are more side reactions, and the purity and yield of the obtained product are low.

[0014] Preferably, the purification step in S2 is as follows: The mixed solution after the reaction is completed is filtered, water is added to the filtrate, stirred, allowed to stand for stratification, the aprotic solvent layer is taken, concentrated and crystallized to obtain vinyl sulfate or vinyl sulfate derivatives.

[0015] By adopting the above technical scheme, unreacted urea peroxide is removed by adding water, and then concentrated and crystallized to obtain a high-purity target product. The purification preparation method of the present application is simple to operate, suitable for mass production, and generates less wastewater.

[0016] Preferably, the amount of water added is 1 / 6-1 / 3 times the mass of vinyl sulfite or vinyl sulfite derivative.

[0017] By adopting the above technical solution, the expected technical effect can be achieved by adding water within this range, which saves water usage, reduces the generation of wastewater, and is beneficial to environmental protection.

[0018] Preferably, the purification step further comprises subjecting the obtained vinyl sulfate or vinyl sulfate derivative to secondary concentration and crystallization.

[0019] By adopting the above technical solution, the purity of the target product can be improved through secondary concentration and crystallization, but this also leads to a certain degree of reduction in yield.

[0020] Preferably, the vinyl sulfate derivative is one of 4-methyl vinyl sulfate, 4-ethyl vinyl sulfate, 4-propyl vinyl sulfate, propylene sulfate and 1,4-butanediol sulfate.

[0021] By adopting the above technical scheme, the preparation method of the present application is applicable to the preparation of a variety of vinyl sulfates and their derivatives, and all have stable reaction activity, and the purity and yield of the obtained target products are both high.

[0022] In summary, the present application includes at least one of the following beneficial technical effects: 1. The carbamide peroxide used in the present application can be well dissolved in aprotic solvents, overcoming the problems of heterogeneous reactions in the prior art, such as large amount of wastewater generated and difficulty in catalyst recovery; and the present application does not require the addition of additional catalysts, thus avoiding the high cost problem caused by precious metal catalysts.

[0023] 2. By using carbamide peroxide as an oxidant, acetic acid sulfate and its derivatives can be efficiently prepared, with a yield of 92.7% or above, and a maximum of 94.8%. At the same time, the purity of the obtained products is between 99.74-99.85%. DETAILED DESCRIPTION

[0024] The present application is further described in detail below in conjunction with the specific contents.

[0025] raw material The raw materials used in the examples of this application were all purchased from commercial sources and were of analytical grade. Example

[0026] Example 1 A method for preparing vinyl sulfate and its derivatives, the general reaction formula of which is shown in Formula 1, comprises the following preparation steps: S1. Weigh 3000g of aprotic solvent and add it to a 5000ml four-necked reaction flask. Add 300g of urea peroxide (1.08 times the molar amount of vinyl sulfite, 92.0541, 3.26mol) under stirring to dissolve it; the aprotic solvent is dichloromethane; S2, evenly add 324g of vinyl sulfite (108.116, 3mol, 2.99678), the temperature is controlled at 20-30°C during the addition, the addition takes 2h, and after the addition is completed, continue to keep the temperature at 20-30°C for 1h; S3. After the reaction is completed, the mixture is filtered to obtain a filtrate. 55 g of water is added to the filtrate, and the mixture is stirred for 0.5 h. The mixture is allowed to stand for stratification. The lower layer is a dichloromethane solution of vinyl sulfate. After evaporation, concentration and crystallization, 351.3 g of vinyl sulfate with a purity of 99.82% is obtained, and the yield is 94.4%.

[0027] Example 2 A method for preparing vinyl sulfate and its derivatives, which is different from Example 1 in that dichloromethane is added dropwise to the final product obtained in S3 until it is completely dissolved, and then evaporation, concentration and crystallization are performed again to obtain vinyl sulfate, and the remaining steps are the same as Example 1.

[0028] Example 3 A method for preparing vinyl sulfate and its derivatives, which is different from Example 1 in that the amount of urea peroxide added is 1.01 times the molar amount of vinyl sulfite, and the remaining steps are the same as those in Example 1.

[0029] Example 4 A method for preparing vinyl sulfate and its derivatives, which is different from Example 1 in that the amount of urea peroxide added is 1.2 times the molar amount of vinyl sulfite, and the remaining steps are the same as those in Example 1.

[0030] Example 5 A method for preparing vinyl sulfate and its derivatives, which is different from Example 1 in that the aprotic solvent is chloroform, and the remaining steps are the same as those in Example 1.

[0031] Example 6 A method for preparing vinyl sulfate and its derivatives, comprising the following preparation steps: S1. Weigh 3700 g of 1,2-dichloroethane and add it to a 5000 ml four-necked reaction flask. Add 300 g of urea peroxide (1.08 times the molar amount of 4-methylvinyl sulfite) under stirring to dissolve it. S2, evenly add 366g of 4-methylvinyl sulfite (122.14, 3mol, 2.99678), the temperature is controlled at 20-30°C during the addition, the addition takes 2h, and after the addition is completed, continue to keep the temperature at 20-30°C for 1h; S3. After the reaction is completed, the reaction is filtered to obtain a filtrate, 55 g of water is added to the filtrate, and the mixture is stirred for 0.5 h. The mixture is allowed to stand and the layers are separated. The lower layer is a 1,2-dichloroethane solution of 4-methylvinyl sulfate. After evaporation, concentration and crystallization, 389 g of 4-methylvinyl sulfate with a purity of 99.85% is obtained, and the yield is 93.8%.

[0032] Example 7 A method for preparing vinyl sulfate and its derivatives, which is different from Example 6 in that 4-methylvinyl sulfite is replaced by an equimolar amount of propylene sulfite, and the remaining steps are the same as those in Example 6.

[0033] Comparative Example Comparative Example 1 A method for preparing vinyl sulfate and its derivatives, which is different from Example 1 in that the temperature during the dropwise addition of vinyl sulfite is controlled at 70°C in S2, and after the dropwise addition is completed, the temperature is kept at 70°C for reaction for 1 hour, and the remaining steps are the same as those in Example 1.

[0034] Performance testing Detection method / test method Vinyl sulfate and its derivatives were prepared according to the preparation methods of Examples 1-7 and Comparative Example 1, and the yields and purities of vinyl sulfate and its derivatives are shown in Table 1.

[0035] Table 1 Test results of Examples 1-7 and Comparative Example 1 purity(%) Yield (%) Example 1 99.82 94.4 Example 2 99.96 92.7 Example 3 99.74 93.7 Example 4 99.76 94.8 Example 5 99.83 94.3 Example 6 99.85 93.8 Example 7 99.81 94.3 Comparative Example 1 84.27 42.9 It can be seen from Examples 1-7 and Comparative Example 1, as well as the test data in Table 1, that by using carbamide peroxide as an oxidant, acetic acid sulfate and its derivatives can be efficiently prepared, with a yield of 92.7% or more, and a maximum of 94.8%. At the same time, the purity of the obtained products is between 99.74% and 99.85%. On this basis, the carbamide peroxide selected in the present application can be well dissolved in aprotic solvents, overcoming the problems of heterogeneous reactions in the prior art, such as a large amount of wastewater generated and difficulty in catalyst recovery. In addition, the present application does not require the addition of a catalyst, thereby avoiding the high cost problem caused by precious metal catalysts.

[0036] It can be seen from the detection data of Examples 1-2 that the purity of the target product can be improved by secondary concentration and crystallization, but this also leads to a certain degree of reduction in yield.

[0037] It can be seen from the test data of Example 1 and Examples 3-4 that the amount of carbamide peroxide added has a certain influence on the purity and yield of the product. When the amount of carbamide peroxide added is 1.01-1.2 times the molar amount of vinyl sulfite, the purity and yield of the product are both high, which meets the needs of actual production. Among them, the amount of carbamide peroxide added is 1.08 times the molar amount of vinyl sulfite, which is a better addition amount.

[0038] It can be seen from the test data of Example 1 and Examples 5-6 that the aprotic solvent is any one or a mixed solution of dichloromethane, chloroform and 1,2-dichloroethane, which can dissolve urea peroxide well, thereby increasing the reaction yield and purity of the target product.

[0039] It can be seen from the test data of Example 1 and Examples 6-7 that the preparation method of the present application is applicable to the preparation of a variety of vinyl sulfates and their derivatives, and all have stable reaction activity, and the purity and yield of the obtained target products are both high.

[0040] It can be seen from the test data of Example 1 and Comparative Example 1 that when the reaction temperature reaches 70°C, due to the high-temperature decomposition or reduced activity of urea peroxide, there are many side reactions, and the purity and yield of the obtained product are both low.

[0041] This specific embodiment is merely an explanation of the present invention and is not a limitation of the present invention. After reading this specification, those skilled in the art may make non-creative modifications to the present embodiment as needed. However, as long as they are within the scope of the claims of the present invention, they are protected by the patent law.

Claims

1. A method for preparing vinyl sulfate and its derivatives, characterized in that: It includes the following steps: S1. Using an aprotic solvent as a reaction solvent, add urea peroxide and stir until dissolved; S2. Add vinyl sulfite or a vinyl sulfite derivative dropwise, stir to react, and purify to obtain vinyl sulfate or a vinyl sulfate derivative.

2. The method for preparing vinyl sulfate and its derivatives according to claim 1, characterized in that: The aprotic solvent in S1 is one or a mixed solution of dichloromethane, chloroform and 1,2-dichloroethane.

3. The method for preparing vinyl sulfate and its derivatives according to claim 1, characterized in that: The molar ratio of the urea peroxide to the vinyl sulfite or the vinyl sulfite derivative is (1.01-1.2):

1.

4. The method for preparing vinyl sulfate and its derivatives according to claim 3, characterized in that: The mass ratio of the aprotic solvent to vinyl sulfite or vinyl sulfite derivative is (8-15):

1.

5. The method for preparing vinyl sulfate and its derivatives according to claim 1, characterized in that: The temperature during the dropwise addition of vinyl sulfite or vinyl sulfite derivative and the stirring reaction in S2 is controlled at 20-50°C.

6. The method for preparing vinyl sulfate and its derivatives according to claim 1, characterized in that: The steps of purification in S2 are as follows: The mixed solution after the reaction is completed is filtered, water is added to the filtrate, stirred, allowed to stand for stratification, the aprotic solvent layer is taken, concentrated and crystallized to obtain vinyl sulfate or vinyl sulfate derivatives.

7. The method for preparing vinyl sulfate and its derivatives according to claim 6, characterized in that: The amount of water added is 1 / 6-1 / 3 times the mass of vinyl sulfite or vinyl sulfite derivative.

8. The method for preparing vinyl sulfate and its derivatives according to claim 6, characterized in that: The purification step also includes subjecting the obtained vinyl sulfate or vinyl sulfate derivative to secondary concentration and crystallization.

9. The method for preparing vinyl sulfate and its derivatives according to claim 1, characterized in that: The vinyl sulfate derivative is one of 4-methyl vinyl sulfate, 4-ethyl vinyl sulfate, 4-propyl vinyl sulfate, propylene sulfate and 1,4-butanediol sulfate.

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