阅读说明：本技术 一种乙烯基亚硫酸亚乙酯的制备方法 (Preparation method of ethylene-based ethylene sulfite ) 是由 张东全 成勇德 魏范杰 于 2020-12-21 设计创作，主要内容包括：本发明属于添加剂领域,具体涉及一种乙烯基亚硫酸亚乙酯的制备方法。本申请公开栏一种乙烯基亚硫酸亚乙酯的制备方法,包括以下步骤：将3-丁烯-1,2-二醇与氯化亚砜进行反应,即得乙烯基亚硫酸亚乙酯。所述制备方法操作简单,原料易得,绿色环保,具有较大的实施价值和社会经济效益。(The invention belongs to the field of additives, and particularly relates to a preparation method of ethylene-based sulfite. The application discloses a preparation method of ethylene-based ethylene sulfite, which comprises the following steps: 3-butylene-1, 2-diol reacts with thionyl chloride to obtain ethylene-based sulfite. The preparation method is simple to operate, easily available in raw materials, green and environment-friendly, and has a high implementation value and social and economic benefits.)

1. The preparation method of the vinyl ethylene sulfite is characterized by comprising the following steps: 3-butylene-1, 2-diol reacts with thionyl chloride to obtain ethylene-based sulfite.

2. The method of claim 1, wherein the molar ratio of 3-butene-1, 2-diol to thionyl chloride is 1: 1-10.

3. The method of claim 2, wherein the molar ratio of 3-butene-1, 2-diol to thionyl chloride is 1: 1-3.5.

4. The method of preparing vinyl ethylene sulfite according to claim 1, wherein the reaction temperature is from-10 ℃ to 250 ℃.

5. The method of preparing vinyl ethylene sulfite according to claim 4 wherein the reaction temperature is from 0 ℃ to 50 ℃.

6. The method of preparing vinyl ethylene sulfite according to claim 1, wherein the 3-butene-1, 2-diol is reacted with thionyl chloride in the absence of a solvent.

7. The method of preparing vinyl ethylene sulfite according to claim 1, wherein the 3-butene-1, 2-diol is reacted with thionyl chloride in the presence of a solvent.

8. The method according to claim 7, wherein the solvent comprises at least one of ethers, esters, nitriles, aliphatic hydrocarbons, aromatic hydrocarbons, halogenated aliphatic hydrocarbons, and halogenated aromatic hydrocarbons.

9. The method of producing vinyl ethylene sulfite according to claim 8 wherein the mass of the solvent is 1 to 20 times the mass of 3-butene-1, 2-diol.

10. The method of producing vinyl ethylene sulfite according to claim 9 wherein the mass of the solvent is 1 to 5 times the mass of 3-butene-1, 2-diol.

Technical Field

The invention belongs to the field of additives, and particularly relates to a preparation method of ethylene-based sulfite.

Background

In the first charge and discharge process of the liquid lithium ion battery, the electrode material and the electrolyte react on a solid-liquid phase interface to form a passivation layer covering the surface of the electrode material. The passivation layer is an interfacial layer, characterized by a solid electrolyte, which is an electronic insulator but Li⁺Of good electrical conductivity, Li⁺Can be freely inserted and extracted through the passivation layer, so the passivation film is called a solid electrolyte interface film (SEI film) for short. The formation of the SEI film has a crucial influence on the performance of the electrode material. On one hand, the formation of the SEI film consumes part of lithium ions, so that the irreversible capacity of the first charge and discharge is increased, and the charge and discharge efficiency of the electrode material is reduced; on the other hand, the SEI film has organic solvent insolubility, can exist stably in an organic electrolyte solution, and solvent molecules cannot existThrough the passivation film, the co-embedding of solvent molecules can be effectively prevented, the damage to an electrode material caused by the co-embedding of the solvent molecules is avoided, and therefore the cycle performance and the service life of the electrode are greatly improved. Therefore, intensive research on the formation mechanism, composition structure, stability and influence factors thereof of the SEI film and further search for effective ways to improve the performance of the SEI film are always hot spots of research in the world electrochemical world.

The vinyl ethylene sulfite is a sulfite compound, has a vinyl functional group, has low lowest unoccupied orbital (LUMO) energy level, has strong electron obtaining capability, is easy to reduce, generates electrochemical reaction firstly to form an SEI protective film, and is an excellent SEI film forming additive. Journal of the American Chemical Society (1947),69,2955-61, first reported the exchange of 3-butene-1, 2-diol with dimethyl sulfite at elevated temperatures or the exchange of 3-butene-1-chloro-2-hydroxy with dimethyl sulfite to give vinyl ethylene sulfite. The Fujian substance structure research institute of Chinese academy of sciences filed for 2011.10.10, and patent CN 103030626 is applied to obtain vinyl ethylene sulfite by reacting 3, 4-diacetyl-1-butene with dimethyl sulfite in the presence of an acid catalyst. In summary, dimethyl sulfite is used for synthesizing vinyl ethylene sulfite at present, and the dimethyl sulfite is difficult to obtain, so that the method has great defects and problems in industrialization.

The invention aims to provide a production method which is green and environment-friendly, has easily obtained raw materials and is simple to operate.

Disclosure of Invention

In order to solve the above technical problems, a first aspect of the present invention provides a method for preparing vinyl ethylene sulfite, comprising the steps of: 3-butylene-1, 2-diol reacts with thionyl chloride to obtain ethylene-based sulfite.

As a preferable technical scheme, the molar ratio of the 3-butene-1, 2-diol to the thionyl chloride is 1: 1-10.

As a preferable technical scheme, the molar ratio of the 3-butene-1, 2-diol to the thionyl chloride is 1: 1-3.5.

As a preferred technical scheme, the reaction temperature is-10 ℃ to 250 ℃.

As a preferred technical scheme, the reaction temperature is 0 ℃ to 50 ℃.

As a preferable technical scheme, the 3-butene-1, 2-diol is reacted with thionyl chloride under the condition of no solvent.

As a preferable technical scheme, the 3-butene-1, 2-diol is reacted with thionyl chloride in the presence of a solvent.

In a preferred embodiment, the solvent includes at least one of ethers, esters, nitriles, aliphatic hydrocarbons, aromatic hydrocarbons, halogenated aliphatic hydrocarbons, and halogenated aromatic hydrocarbons.

As a preferable technical scheme, the mass of the solvent is 1-20 times of that of the 3-butene-1, 2-diol.

As a preferable technical scheme, the mass of the solvent is 1-5 times of that of the 3-butene-1, 2-diol.

Has the advantages that: the preparation method is simple to operate, easily available in raw materials, green and environment-friendly, and has a high implementation value and social and economic benefits.

Detailed Description

In order to solve the above problems, the present invention provides a method for preparing vinyl ethylene sulfite, comprising the steps of: 3-butylene-1, 2-diol reacts with thionyl chloride to obtain ethylene-based sulfite.

The structural formula of the 3-butene-1, 2-diol is as follows:

the structural formula of the vinyl ethylene sulfite is as follows:

the 3-butene-1, 2-diol may be purchased or manufactured by itself, and preferably, the 3-butene-1, 2-diol of the present application is obtained by itself.

The preparation method of the 3-butene-1, 2-diol comprises the following steps: mixing 1, 4-butylene glycol, mercuric sulfate, sulfuric acid and deionized water, reacting for 4 hours at 90-95 ℃, adjusting the pH value to 7-8 by using 5% saturated sodium bicarbonate water solution, distilling under the negative pressure of 30-40 mmHg to remove water, and distilling under the negative pressure of 2-3 mmHg to obtain 3-butylene-1, 2-glycol.

The weight ratio of the 1, 4-butylene glycol, the mercury sulfate and the sulfuric acid to the deionized water is 85-95: 1: 1: 20-25. Preferably, the weight ratio of the 1, 4-butylene glycol to the mercury sulfate to the deionized water is 88: 1: 1: 22.

the molar ratio of the 3-butene-1, 2-diol to the thionyl chloride is 1: 1-10; preferably, the molar ratio of the 3-butene-1, 2-diol to the thionyl chloride is 1: 1-3.5.

The reaction temperature is-10 ℃ to 250 ℃; preferably, the reaction temperature is from 0 ℃ to 50 ℃.

In one embodiment, the 3-butene-1, 2-diol is reacted with thionyl chloride in the absence of a solvent. In such embodiments, the preferred molar ratio of 3-butene-1, 2-diol to thionyl chloride is 1: 1.5-3.5.

In one embodiment, the 3-butene-1, 2-diol is reacted with thionyl chloride in the presence of a solvent. In such embodiments, the preferred molar ratio of 3-butene-1, 2-diol to thionyl chloride is 1: 1-1.5. The solvent comprises at least one of ethers, esters, nitriles, aliphatic hydrocarbons, aromatic hydrocarbons, halogenated aliphatic hydrocarbons and halogenated aromatic hydrocarbons. As the solvent, tetrahydrofuran, dioxane, ethyl acetate, n-butyl acetate, acetonitrile, n-hexane, toluene, dichloromethane, chlorobenzene and the like can be exemplified. Preferably, the mass of the solvent is 1 to 20 times of the mass of the 3-butene-1, 2-diol. More preferably, the mass of the solvent is 1 to 5 times that of the 3-butene-1, 2-diol.

The preparation method of the vinyl ethylene sulfite under the solvent-free condition comprises the following steps: adding 3-butene-1, 2-diol into a reaction device, dropwise adding thionyl chloride, distilling under reduced pressure by using a water pump after the dropwise adding is finished, and distilling by using an oil pump; or adding thionyl chloride into a reaction device, dropwise adding 3-butene-1, 2-diol, preserving the temperature for a certain time after the dropwise adding is finished, and distilling under reduced pressure by using a water pump and then distilling by using an oil pump.

The preparation method of the vinyl ethylene sulfite in the presence of the solvent comprises the following steps: adding 3-butene-1, 2-diol and a solvent into a reaction device, then dropwise adding thionyl chloride, quenching with water after dropwise adding, adjusting the pH value to 7-8 with saturated sodium bicarbonate, separating an organic phase, concentrating with a water pump, and distilling with an oil pump.

Wherein the reaction is checked for completion by GC throughout.

According to the method, high-purity ethylene vinyl sulfite is obtained by reacting self-made 3-butene-1, 2-diol with thionyl chloride. Theoretically, it is advantageous to increase the amount of the reactant to proceed in the forward reaction, but as the reactant increases, the amount of the product decreases or the purity decreases, and it is presumed that an excessive amount of the reactant reacts with the intermediate product to cause the formation of a by-product. The Applicant has also found that the molar ratio of 3-butene-1, 2-diol to thionyl chloride varies with or without solvent, and that the ratio of the two reactants is also important with or without solvent.

The present invention will be specifically described below by way of examples. It should be noted that the following examples are only for illustrating the present invention and should not be construed as limiting the scope of the present invention, and that the insubstantial modifications and adaptations of the present invention by those skilled in the art based on the above disclosure are still within the scope of the present invention.

In addition, the starting materials used are all commercially available, unless otherwise specified.

Examples

Preparation example: preparation of 3-butene-1, 2-diol

880 g of 1, 4-butylene glycol, 10 g of mercuric sulfate, 10 g of sulfuric acid and 220 g of deionized water are mixed, reacted at 90-95 ℃ for 4 hours, the pH value is adjusted to 7-8 by using 5% saturated sodium bicarbonate aqueous solution, then the water is removed by distillation under the negative pressure of 30-40 mmHg, then the product is distilled under the negative pressure of 2-3 mmHg, and 665 g of the product is obtained, wherein the yield is 75.6%. HNMR data: (cdcl3,400mhz):3.29(s,2H), 3.47(dd, J ═ 6.00Hz,12.00Hz,1H), 3.64(dd, J ═ 4.00Hz,12.00Hz,1H), 4.21(m,1H),5.20(d, J ═ 8.00,1H), 5.34(d, J ═ 20.00Hz,1H), 5.82(m, 1H).

Example 1

A preparation method of vinyl ethylene sulfite comprises the following steps: adding 88.1 g of 3-butene-1, 2-diol into a reaction bottle, dropwise adding 200 g of thionyl chloride at the temperature of below 5 ℃ (the dropwise adding time is 2 hours), distilling under reduced pressure by using a water pump to remove excessive thionyl chloride after the dropwise adding is finished, and distilling by using an oil pump to obtain 125 g of product, wherein the yield is 93.2%. The purity of the product is 99.5 percent, the chloride ion is less than 1ppm, the sulfate radical is less than 1ppm, and the acid value of the product is 12 ppm.

Example 2

A preparation method of vinyl ethylene sulfite comprises the following steps: adding 88.1 g of 3-butene-1, 2-diol and 300 g of dichloromethane, dropwise adding 130 g of thionyl chloride at the temperature of below 25 ℃ (the dropwise adding time is 1 hour), quenching with water after dropwise adding, adjusting the pH value to 7-8 with saturated sodium bicarbonate, separating out an organic phase, concentrating with a water pump, and distilling with an oil pump to obtain 119 g of a product, wherein the yield is 88.9%. The purity of the product is 99.7 percent, the chloride ion is less than 1ppm, the sulfate radical is less than 1ppm, and the acid value of the product is 10 ppm.

Example 3

A preparation method of vinyl ethylene sulfite comprises the following steps: adding 88.1 g of 3-butene-1, 2-diol and 300 g of toluene, heating to 80 ℃, dropwise adding 140 g of thionyl chloride (the dropwise adding time is 1.5 hours), keeping the temperature at 80 ℃ for 2 hours after dropwise adding, then quenching with water, adjusting the pH value to 7-8 with saturated sodium bicarbonate, separating out an organic phase, concentrating with a water pump, and distilling with an oil pump to obtain 117 g of a product, wherein the yield is 87.3%. The purity of the product is 99.5 percent, the chloride ion is less than 1ppm, the sulfate radical is less than 1ppm, and the acid value of the product is 9 ppm.

Example 4

A preparation method of vinyl ethylene sulfite comprises the following steps: adding 400 g of thionyl chloride into a reaction bottle, controlling the temperature below 50 ℃, dropwise adding 88.1 g of 3-butene-1, 2-diol (the dropwise adding time is 1 hour), keeping the temperature at 50 ℃ for 2 hours after dropwise adding, distilling by using a water pump under reduced pressure to remove the redundant thionyl chloride, and distilling by using an oil pump to obtain 121 g of product, wherein the yield is 90.3%. The purity of the product is 99.6 percent, the chloride ion is less than 1ppm, the sulfate radical is less than 1ppm, and the acid value of the product is 13 ppm.

Example 5

A process for producing vinyl ethylene sulfite, the specific embodiment of which is the same as in example 1, except that 95 g of thionyl chloride is added dropwise at 5 ℃ or lower (the addition time is 2 hours). The yield thereof was found to be 61%. The purity of the product was 91%, the chloride ion content was 11ppm, the sulfate radical content was 30ppm, and the acid value of the product was 206 ppm.

Example 6

A process for producing vinyl ethylene sulfite, the specific embodiment of which is the same as in example 1, except that 119 g of thionyl chloride was added dropwise at 5 ℃ or lower (the addition time was 2 hours). The yield thereof was found to be 71%. The purity of the product was 95%, the chloride ion content was 15ppm, the sulfate radical content was 20ppm, and the acid value of the product was 143 ppm.

The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention in other forms, and any person skilled in the art may modify or change the technical content of the above disclosure into equivalent embodiments with equivalent changes, but all those simple modifications, equivalent changes and modifications made to the above embodiments according to the technical spirit of the present invention still belong to the protection scope of the present invention.