A process for the preparation of vinylsulfate and derivatives thereof

Abstract

The application relates to the technical field of organic synthesis, in particular to a preparation method of vinyl sulfate and derivatives thereof, which comprises the following steps: S1, using an aprotic solvent as a reaction solvent, adding urea peroxide, and stirring until the urea peroxide is dissolved; S2, adding vinyl sulfite or a vinyl sulfite derivative dropwise, stirring to react, purifying, and obtaining the vinyl sulfite or the vinyl sulfite derivative; the method has the advantages of reducing the cost of a catalyst and reducing the amount of waste water.

Description

Technical Field

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

[0002] Vinyl sulfate and its derivatives can be used as additives in lithium-ion battery electrolytes. These mainly include vinyl sulfate, 4-methyl vinyl sulfate, 4-ethyl vinyl sulfate, 4-propyl vinyl sulfate, propylene sulfate, and 1,4-butanediol sulfate. Currently, industrially, vinyl sulfite derivatives are first prepared as intermediates by reacting diol compounds with thionyl chloride, and then oxidized to obtain vinyl sulfate and its derivatives. Two commonly used oxidation methods in industry are:

[0003] 1. Using sodium hypochlorite as an oxidant, vinyl sulfite and its derivatives are oxidized to vinyl sulfate and its derivatives under the catalysis of catalysts such as ruthenium trichloride. This method generates a large amount of saline wastewater, and the precious metal catalyst ruthenium trichloride used is difficult to recover and reuse. Ruthenium is an extremely expensive rare precious metal, which makes the cost of vinyl sulfate synthesis process very high.

[0004] 2. Using hydrogen peroxide as the oxidant and TS-1 titanium-silicon molecular sieve as the catalyst, vinyl sulfite and its derivatives are oxidized to vinyl sulfate and its derivatives. In this reaction system, the hydrogen peroxide, catalyst, and vinyl sulfite and its derivatives are all immiscible, making it a heterogeneous reaction. The hydrogen peroxide content is typically 27%-30%. After the reaction, a large amount of wastewater is generated, and the catalyst needs to be filtered and recovered, making the process cumbersome. Furthermore, the catalyst is expensive, resulting in high costs. Summary of the Invention

[0005] To reduce catalyst costs and wastewater volume, this application provides a method for preparing ethylene sulfate and its derivatives.

[0006] In a first aspect, this application provides a method for preparing vinyl sulfate and its derivatives, comprising the following steps:

[0007] S1. Using an aprotic solvent as the reaction solvent, add urea peroxide and stir until dissolved;

[0008] S2. Add vinyl sulfite or a vinyl sulfite derivative dropwise, stir the reaction, purify, and obtain vinyl sulfate or a vinyl sulfate derivative.

[0009] By adopting the above technical solution, the urea peroxide selected in this application can be well dissolved in aprotic solvents, overcoming the problems in heterogeneous reactions in the prior art, such as large amounts of wastewater generated and difficulty in catalyst recovery; and this application does not require the addition of additional catalysts, avoiding the high cost problem caused by precious metal catalysts.

[0010] Preferably, the aprotic solvent in S1 is one or a mixture of several of dichloromethane, trichloromethane, and 1,2-dichloroethane.

[0011] By adopting the above technical solution, any one or a mixture of dichloromethane, trichloromethane and 1,2-dichloroethane, or other aprotic solvents can effectively dissolve urea peroxide, maintaining its good reactivity, thereby resulting in high reaction yield and high purity of the target product.

[0012] Preferably, the molar ratio of urea peroxide to vinyl sulfite or a vinyl sulfite derivative is (1.01-1.2):1.

[0013] By adopting the above technical solution, the amount of urea peroxide added has a certain impact on the purity and yield of the product. When the amount of urea 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 urea peroxide added is 1.08 times the molar amount of vinyl sulfite, which is the optimal amount.

[0014] Preferably, the mass ratio of the aprotic solvent to vinyl sulfite or a vinyl sulfite derivative is (8-15):1.

[0015] By adopting the above technical solution, the aprotic solvent at this addition amount can effectively dissolve urea peroxide, maintain its reactivity, ensure a good forward reaction, and avoid excessive solvent waste.

[0016] Preferably, the temperature during the addition of vinyl sulfite or vinyl sulfite derivatives in S2 and during the stirring reaction are both controlled at 20-50℃.

[0017] By adopting the above technical solution, considering the reactivity and overheating decomposition temperature of urea peroxide, the reaction temperature should not be too high. Within this range, the reaction yield and product purity can be relatively high. When the reaction temperature is too high, due to the high-temperature decomposition or reduced activity of urea peroxide, there are more side reactions, and the purity and yield of the obtained product are relatively low.

[0018] Preferably, the purification steps in S2 are as follows:

[0019] After the reaction is complete, the mixture is filtered, water is added to the filtrate, the mixture is stirred, allowed to stand and separate into layers, the aprotic solvent layer is collected, concentrated and crystallized to obtain vinyl sulfate or vinyl sulfate derivatives.

[0020] By adopting the above technical solution, unreacted urea peroxide is removed by adding water, and then the target product is obtained by concentration and crystallization. The purification preparation method of this application is simple to operate, suitable for mass production, and generates less wastewater.

[0021] Preferably, the amount of water added is 1 / 6 to 1 / 3 times the mass of vinyl sulfite or vinyl sulfite derivative.

[0022] By adopting the above technical solution, the expected technical effect can be achieved with the amount of water added within this range, saving water consumption, reducing wastewater generation, and helping to protect the environment.

[0023] Preferably, the purification step further includes secondary concentration and crystallization of the obtained vinyl sulfate or vinyl sulfate derivative.

[0024] 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.

[0025] 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.

[0026] By adopting the above technical solution, the preparation method of this application is applicable to the preparation of various vinyl sulfates and their derivatives, and all of them have stable reactivity. The purity and yield of the target products obtained are both high.

[0027] In summary, this application includes at least one of the following beneficial technical effects:

[0028] 1. The urea peroxide selected in this application can be well dissolved in aprotic solvents, overcoming the problems in heterogeneous reactions in the prior art, such as large amounts of wastewater generated and difficulty in catalyst recovery; and this application does not require the addition of additional catalysts, avoiding the high cost problem caused by precious metal catalysts.

[0029] 2. By using urea peroxide as an oxidant, acetic acid sulfate and its derivatives can be prepared efficiently with yields of 92.7% and above, with a maximum of 94.8%. Meanwhile, the purity of the obtained products is between 99.74% and 99.85%. Detailed Implementation

[0030] The following provides a more detailed description of this application in conjunction with specific details.

[0031] raw material

[0032] All raw materials used in the embodiments of this application were purchased commercially and were of analytical purity.

[0033] Example

[0034] Example 1

[0035] A method for preparing vinyl sulfate and its derivatives, wherein the general reaction formula is shown in Formula 1, includes the following preparation steps:

[0036] S1. Weigh 3000g of aprotic solvent and add it to a 5000ml four-necked reaction flask. While stirring, add 300g of urea peroxide (1.08 molar amounts of vinyl sulfite, 92.0541, 3.26mol) and dissolve it. The aprotic solvent is dichloromethane.

[0037] S2. Add 324g of vinyl sulfite (108.116, 3mol, 2.99678) dropwise evenly. The temperature is controlled at 20-30℃ during the dropwise addition process. The dropwise addition takes 2 hours. After the dropwise addition is completed, continue to keep the temperature at 20-30℃ for another hour.

[0038] S3. After the reaction is complete, filter to obtain the filtrate. Add 55g of water to the filtrate, stir for 0.5h, and let stand to separate the layers. The lower layer is a dichloromethane solution of vinyl sulfate. After evaporation, concentration and crystallization, 351.3g of vinyl sulfate with a purity of 99.82% is obtained, with a yield of 94.4%.

[0039]

[0040] Example 2

[0041] A method for preparing vinyl sulfate and its derivatives differs from Example 1 in that dichloromethane is added dropwise to the final product obtained in S3 until it is just completely dissolved, and then the product is evaporated, concentrated and crystallized again to obtain vinyl sulfate. The remaining steps are the same as in Example 1.

[0042] Example 3

[0043] A method for preparing vinyl sulfate and its derivatives differs from Example 1 in that the amount of urea peroxide added is 1.01 molar amounts of vinyl sulfite, while the remaining steps are the same as in Example 1.

[0044] Example 4

[0045] A method for preparing vinyl sulfate and its derivatives differs from Example 1 in that the amount of urea peroxide added is 1.2 molar amounts of vinyl sulfite, while the remaining steps are the same as in Example 1.

[0046] Example 5

[0047] A method for preparing vinyl sulfate and its derivatives differs from Example 1 in that the aprotic solvent is chloroform, while the remaining steps are the same as in Example 1.

[0048] Example 6

[0049] A method for preparing vinyl sulfate and its derivatives, comprising the following preparation steps:

[0050] S1. Weigh 3700g of 1,2-dichloroethane and add it to a 5000ml four-necked reaction flask. While stirring, add 300g of urea peroxide (1.08 molar amounts of 4-methyl sulfite) and dissolve it.

[0051] S2. Add 366g of 4-methyl vinyl sulfite (122.14, 3mol, 2.99678) dropwise evenly. The temperature is controlled at 20-30℃ during the dropwise addition process. The dropwise addition takes 2 hours. After the dropwise addition is completed, continue to keep the temperature at 20-30℃ for another hour.

[0052] S3. After the reaction is complete, filter to obtain the filtrate. Add 55g of water to the filtrate, stir for 0.5h, and let stand to separate the layers. The lower layer is a solution of 4-methyl vinyl sulfate in 1,2-dichloroethane. After evaporation, concentration and crystallization, 389g of 4-methyl vinyl sulfate with a purity of 99.85% is obtained, with a yield of 93.8%.

[0053] Example 7

[0054] A method for preparing vinyl sulfate and its derivatives differs from Example 6 in that 4-methylvinyl sulfite is replaced with an equimolar amount of propylene sulfite, while the remaining steps are the same as in Example 6.

[0055] Comparative Example

[0056] Comparative Example 1

[0057] A method for preparing vinyl sulfate and its derivatives differs from Example 1 in that, in step S2, the temperature during the dropwise addition of vinyl sulfite is controlled at 70°C, and after the dropwise addition is completed, the reaction is continued at 70°C for 1 hour. The remaining steps are the same as in Example 1.

[0058] Performance testing

[0059] Detection methods / test methods

[0060] 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.

[0061] Table 1. Detection results of Examples 1-7 and Comparative Example 1

[0062] 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

[0063] As can be seen from Examples 1-7, Comparative Example 1, and the detection data in Table 1, urea peroxide as an oxidant can efficiently prepare acetate sulfate and its derivatives, with yields of 92.7% and above, reaching a maximum of 94.8%. Simultaneously, the purity of the obtained products is between 99.74% and 99.85%. Furthermore, the urea peroxide selected in this application is well soluble in aprotic solvents, overcoming the problems of heterogeneous reactions in the prior art, such as large amounts of wastewater generated and difficulties in catalyst recovery. Moreover, this application does not require the addition of an additional catalyst, avoiding the high cost problem caused by precious metal catalysts.

[0064] The test data from Examples 1-2 show 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.

[0065] The test data from Examples 1 and 3-4 show that the amount of urea peroxide added has a certain impact on the purity and yield of the product. When the amount of urea 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 urea peroxide added is 1.08 times the molar amount of vinyl sulfite, which is the optimal amount.

[0066] The detection data from Examples 1 and 5-6 show that a mixture of one or more of the aprotic solvents, such as dichloromethane, trichloromethane, and 1,2-dichloroethane, can effectively dissolve urea peroxide, resulting in higher reaction yield and higher purity of the target product.

[0067] The detection data from Examples 1 and 6-7 show that the preparation method of this application is suitable for preparing various vinyl sulfates and their derivatives, and all of them have stable reactivity. The purity and yield of the target products obtained are both high.

[0068] The test data from Example 1 and Comparative Example 1 show that when the reaction temperature reaches 70°C, due to the high-temperature decomposition or reduced activity of urea peroxide, there are more side reactions, resulting in lower purity and yield of the product.

[0069] This specific embodiment is merely an explanation of the present invention and is not intended to limit the invention. After reading this specification, those skilled in the art can make modifications to this embodiment without contributing any inventive step, but such modifications are protected by patent law as long as they are within the scope of the claims of the present invention.

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 the reaction solvent, add urea peroxide and stir until dissolved; S2. Add vinyl sulfite or a vinyl sulfite derivative dropwise, stir the reaction, purify, and obtain vinyl sulfate or a vinyl sulfate derivative.

2. The method for preparing ethylene sulfate and its derivatives according to claim 1, characterized in that: The aprotic solvent in S1 is one or a mixture of several of dichloromethane, trichloromethane, and 1,2-dichloroethane.

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

1.

4. The method for preparing ethylene 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 ethylene sulfate and its derivatives according to claim 1, characterized in that: The temperature during the addition of vinyl sulfite or vinyl sulfite derivatives in S2 and during the stirring reaction are both controlled at 20-50℃.

6. The method for preparing ethylene sulfate and its derivatives according to claim 1, characterized in that: The purification steps in S2 are as follows: After the reaction is complete, the mixture is filtered, water is added to the filtrate, the mixture is stirred, allowed to stand and separate into layers, the aprotic solvent layer is collected, concentrated and crystallized to obtain vinyl sulfate or vinyl sulfate derivatives.

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

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

9. The method for preparing ethylene 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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