阅读说明：本技术 一种硫酸乙烯酯的合成方法 (Method for synthesizing vinyl sulfate ) 是由 姜飞 陈雪君 陈群 孙西船 翟涛 于 2020-12-27 设计创作，主要内容包括：本发明公开了一种硫酸乙烯酯的合成方法包括以下步骤：将亚硫酸乙烯酯、第一有机溶剂、氧化剂次氯酸钙固体和催化剂三氯化钌混合投入到反应釜中,将反应体系降至-15℃～-10℃；剧烈搅拌状态下缓慢滴加一定量的冷水,滴加结束后,继续-10℃～-5℃反应6-10h,反应结束后,抽滤,滤液分液,有机相用少量冰水洗涤两遍,加入分子筛干燥除水,过滤之后,浓缩重结晶,离心干燥,得到硫酸乙烯酯成品；本发明提高了亚硫酸乙烯酯合成收率；由于常用的氧化剂次氯酸钠溶液,常温下保存易分解,本发明使用次氯酸钙固体,保存方便,现配现用,硫酸乙烯酯的氧化过程中催化剂用量少、成本低。(The invention discloses a method for synthesizing vinyl sulfate, which comprises the following steps: mixing and putting ethylene sulfite, a first organic solvent, an oxidant calcium hypochlorite solid and a catalyst ruthenium trichloride into a reaction kettle, and reducing the temperature of a reaction system to-15 to-10 ℃; slowly adding a certain amount of cold water under the condition of violent stirring, continuously reacting for 6-10h at-10 to-5 ℃ after the dropwise adding is finished, performing suction filtration after the reaction is finished, separating filtrate, washing an organic phase twice by using a small amount of ice water, and adding)

1. A method for synthesizing vinyl sulfate is characterized in that: the method comprises the following steps:

s1, putting the ethylene sulfite, a first organic solvent, an oxidant and a catalyst into a reaction kettle according to a certain proportion, wherein the first organic solvent is carboxylic ester, the oxidant is calcium hypochlorite solid, and the catalyst is ruthenium trichloride solid;

s2, controlling the temperature of the mixed liquid in the reaction kettle between-15 ℃ and-10 ℃, and slowly dripping a certain amount of cold water while rapidly stirring;

s3, after the dropwise addition of the cold water is finished, continuously keeping the temperature between minus 10 ℃ and minus 5 ℃ for continuous reaction for 6 to 10 hours;

s4, after the reaction is finished, carrying out suction filtration treatment, separating liquid from the mixed liquid, and washing the obtained organic phase solution with a small amount of ice water;

and S5, adding the organic phase solution washed in the step S4 into a 4A molecular sieve for drying and dewatering, filtering, and then concentrating, recrystallizing and centrifugally drying to obtain a finished product of the vinyl sulfate.

2. The method for synthesizing vinyl sulfate according to claim 1, wherein: the ethylene sulfite in the step S1 is a colorless transparent liquid, and the ethylene sulfite is prepared by adding thionyl chloride into a reaction kettle, cooling the system to 0-5 ℃, then slowly dripping ethylene glycol, controlling the dripping speed, and absorbing hydrogen chloride gas and volatilized thionyl chloride by using a tail gas absorption device; and after the dropwise addition is finished, controlling the reaction temperature to be room temperature, continuously reacting for 6-8 hours, and after the reaction is finished, evaporating redundant thionyl chloride to obtain the obtained liquid.

3. The method for synthesizing vinyl sulfate according to claim 1, wherein: the first organic solvent in step S1 includes, but is not limited to, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, ethyl formate, propyl formate, methyl propionate, ethyl propionate, and propyl propionate.

4. The method for synthesizing vinyl sulfate according to claim 1, wherein: the mass ratio of the ethylene sulfite to the first organic solvent in the step S1 is 1: 5 to 10.

5. The method for synthesizing vinyl sulfate according to claim 1, wherein: the molar ratio of the ethylene sulfite to the calcium hypochlorite solid in the step S1 is 1: 0.5 to 0.55.

6. The method for synthesizing vinyl sulfate according to claim 1, wherein: the dosage of the catalyst ruthenium trichloride in the step S1 is 0.01-0.05 per mill of the dosage of the ethylene sulfite.

7. The method for synthesizing vinyl sulfate according to claim 2, wherein: the molar ratio of the ethylene glycol to the thionyl chloride is 1: 1.0 to 1.05.

8. The method for synthesizing vinyl sulfate according to claim 2, wherein: the temperature is controlled between 0 ℃ and 5 ℃ during the dropwise adding reaction of the ethylene glycol and the thionyl chloride.

9. The method for synthesizing vinyl sulfate according to claim 2, wherein: the temperature of the reaction kettle is controlled to be 0-5 ℃ when the ethylene glycol is dripped.

Technical Field

The invention relates to a method for synthesizing an electrolyte additive of a lithium ion battery, in particular to a method for synthesizing vinyl sulfate.

Background

The cyclic sulfate is used as an additive of the lithium ion battery electrolyte, and has the functions of inhibiting the reduction of the initial capacity of the battery, increasing the initial discharge capacity, reducing the expansion of the battery after high-temperature placement, and improving the charge and discharge performance and the cycle number of the battery.

In the synthetic routes reported in the prior literatures and patents, the vinyl sulfate is mainly synthesized by the following methods:

1) the method uses flammable and explosive ethylene, has serious safety problems in large-scale production and has higher requirements on equipment and personnel operation;

2) the method has the problem that the residue of the ethylene sulfite is difficult to remove;

3) ethylene glycol and sulfonyl chloride or sulfonyl fluoride are directly synthesized into vinyl sulfate, and the method has more byproducts, lower product yield and strong equipment corrosivity;

4) 1, 2-dibromoethane and silver sulfate are refluxed in toluene to prepare vinyl sulfate, and the method has low product yield and high raw material price;

5) ethylene oxide and sulfur trioxide react in dioxane to synthesize vinyl sulfate, and the ethylene oxide is a high-toxicity substance and is gas at normal temperature, so that the requirement on equipment is high.

Disclosure of Invention

The invention aims to overcome the defects of the prior art and provide a preparation method which improves the productivity of the ethylene sulfite, solves the problem of the stability of an oxidant and improves the oxidation yield of the ethylene sulfate by changing a solvent.

In order to achieve the purpose, the invention provides a method for synthesizing vinyl sulfate, which comprises the following steps:

s1, putting the ethylene sulfite, a first organic solvent, an oxidant and a catalyst into a reaction kettle according to a certain proportion, wherein the first organic solvent is carboxylic ester, the oxidant is calcium hypochlorite solid, and the catalyst is ruthenium trichloride solid;

s2, controlling the temperature of the mixed liquid in the reaction kettle between-15 ℃ and-10 ℃, and slowly dripping a certain amount of cold water while rapidly stirring;

s3, after the dropwise addition of the cold water is finished, continuously keeping the temperature between minus 10 ℃ and minus 5 ℃ for continuous reaction for 6 to 10 hours;

s4, after the reaction is finished, carrying out suction filtration treatment, separating liquid from the mixed liquid, and washing the obtained organic phase solution with a small amount of ice water;

and S5, adding the organic phase solution washed in the step S4 into a 4A molecular sieve for drying and dewatering, filtering, and then concentrating, recrystallizing and centrifugally drying to obtain a finished product of the vinyl sulfate.

As a further improvement of the above scheme, the ethylene sulfite in step S1 is a colorless transparent liquid, and the ethylene sulfite is obtained by adding thionyl chloride into a reaction kettle, cooling the system to 0-5 ℃, then slowly adding ethylene glycol dropwise, controlling the dropwise adding speed, absorbing hydrogen chloride gas and volatilized thionyl chloride by using a tail gas absorption device, after the dropwise adding is finished, controlling the reaction temperature to room temperature, continuing to react for 6-8 hours, and after the reaction is finished, evaporating excess thionyl chloride to obtain a liquid.

As a further improvement of the above scheme, the first organic solvent in step S1 includes, but is not limited to, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, ethyl formate, propyl formate, methyl propionate, ethyl propionate, and propyl propionate.

As a further improvement of the above scheme, the mass ratio of the vinyl sulfite to the first organic solvent in step S1 is 1: 5 to 10.

As a further improvement of the above solution, the molar ratio of the ethylene sulfite to the calcium hypochlorite solid in the step S1 is 1: 0.5 to 0.55.

As a further improvement of the scheme, the dosage of the catalyst ruthenium trichloride in the step S1 is 0.01 to 0.05 per mill of the dosage of the ethylene sulfite.

As a further improvement of the above scheme, the molar ratio of the ethylene glycol to the amount of thionyl chloride is 1: 1.0 to 1.05.

As a further improvement of the scheme, the temperature of the dropwise adding reaction of the ethylene glycol and the thionyl chloride is controlled to be 0-5 ℃.

The scheme is further improved, and the temperature of the reaction kettle is controlled to be 0-5 ℃ when the ethylene glycol is dripped.

The invention has the beneficial effects that: the synthetic method of the vinyl sulfate has simple and controllable synthetic process route, and improves the synthetic yield of the vinyl sulfite; because the common oxidant sodium hypochlorite solution is easy to decompose when being stored at normal temperature, the invention uses the calcium hypochlorite solid, is convenient to store and can be prepared for use at present, the dosage of the catalyst is less in the oxidation process of the vinyl sulfate, and the cost is low; the hydrolysis rate of the vinyl sulfate can be reduced by reducing the reaction temperature, the oxidation yield is improved, and a high-purity vinyl sulfate product can be obtained by subsequent recrystallization, has the purity of over 99.5 percent and can be used as an additive of lithium ion battery electrolyte.

Detailed Description

In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. It is to be understood that the embodiments described are only a few embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the described embodiments of the invention, are within the scope of the invention.

The embodiment of the invention provides a preparation method of ethylene sulfite, which comprises the following operation steps: adding thionyl chloride into a reaction kettle, cooling the temperature of the system to 0-5 ℃, then slowly adding ethylene glycol dropwise, controlling the dropwise adding speed, absorbing hydrogen chloride gas and volatile thionyl chloride by using a tail gas absorption device, controlling the reaction temperature to room temperature after dropwise adding, continuously reacting for 6-8 hours, and evaporating redundant thionyl chloride to obtain a liquid which is a finished product of the ethylene sulfite after the reaction is finished.

Example 1

625g of thionyl chloride liquid is added into a reaction kettle once, the temperature of the system is reduced to 5 ℃, 310g of ethylene glycol is dripped, a tail gas absorption device is used for absorbing hydrogen chloride gas and volatile thionyl chloride, after the dripping is finished, the reaction temperature is controlled at room temperature, the reaction is carried out for 7 hours, after the reaction is finished, redundant thionyl chloride is evaporated out under reduced pressure, a finished product of the ethylene sulfite is obtained by suction filtration, the yield is 98%, the purity of the product is characterized by adopting GC (gas chromatography), and the result proves that the purity of the target product, namely the ethylene sulfite, is 99.3%.

Example 2

595g of thionyl chloride liquid is added into a reaction kettle once, the temperature of the system is reduced to 0 ℃, 310g of ethylene glycol is dripped, a tail gas absorption device is used for absorbing hydrogen chloride gas and volatile thionyl chloride, after the dripping is finished, the reaction temperature is controlled at room temperature, the reaction is carried out for 6 hours, after the reaction is finished, redundant thionyl chloride is evaporated out under reduced pressure, a finished product of the ethylene sulfite is obtained by suction filtration, the yield is 96%, a GC gas chromatograph is adopted to characterize the purity of the product, and the result proves that the product is the target product of the ethylene sulfite, and the purity is 99.1%.

Example 3

Adding 610g of thionyl chloride liquid into a reaction kettle at one time, cooling the system to 0 ℃, dropwise adding 310g of ethylene glycol, absorbing hydrogen chloride gas and volatile thionyl chloride by using a tail gas absorption device, controlling the reaction temperature at room temperature after dropwise adding, reacting for 8 hours, reducing pressure after the reaction is finished, evaporating redundant thionyl chloride, and performing suction filtration to obtain a finished product of the ethylene sulfite, wherein the yield is 98%, and the product purity is characterized by adopting a GC (gas chromatography) instrument, and the result proves that the target product of the ethylene sulfite has a purity of 99.2%.

The embodiment of the invention provides a preparation method of vinyl sulfate, which comprises the following operation steps:

s1, putting the ethylene sulfite, a first organic solvent, an oxidant and a catalyst into a reaction kettle according to a certain proportion, wherein the first organic solvent is carboxylic ester, the oxidant is calcium hypochlorite solid, and the catalyst is ruthenium trichloride solid;

s2, controlling the temperature of the mixed liquid in the reaction kettle between-15 ℃ and-10 ℃, and slowly dripping a certain amount of cold water while rapidly stirring;

s3, after the dropwise addition of the cold water is finished, continuously keeping the temperature between minus 10 ℃ and minus 5 ℃ for continuous reaction for 6 to 10 hours;

s4, after the reaction is finished, carrying out suction filtration treatment, separating liquid from the mixed liquid, and washing the obtained organic phase solution with a small amount of ice water;

and S5, adding the organic phase solution washed in the step S4 into a 4A molecular sieve for drying and dewatering, filtering, and then concentrating, recrystallizing and centrifugally drying to obtain a finished product of the vinyl sulfate.

Example 4

Adding 75g of ethylene sulfite, 750g of butyl acetate, 57g of calcium hypochlorite solid and 3mg of ruthenium trichloride solid into a reaction kettle, and reducing the temperature of a reaction system to-15 ℃; and (2) dropwise adding 250g of cold water under vigorous stirring, ensuring that the reaction temperature is-10 ℃, controlling the temperature to react for 10 hours at-10 ℃ after dropwise adding, carrying out suction filtration on reaction liquid after the reaction is finished, collecting and discarding filter residues, separating filtrate, washing an organic phase with cold water, drying and dewatering by using a 4A molecular sieve, filtering, recrystallizing a concentrated organic phase, and carrying out centrifugal drying to obtain a finished product of the vinyl sulfate, wherein the yield is 83%, and the purity of the product is 99.8% by representing the purity by using GC (gas chromatography).

Example 5

Adding 75g of ethylene sulfite, 750g of propyl formate, 49g of calcium hypochlorite solid and 2mg of ruthenium trichloride solid into a reaction kettle, reducing the temperature of a reaction system to-10 ℃, dropwise adding 210g of cold water under vigorous stirring, controlling the reaction temperature to-5 ℃, reacting for 8 hours at-10 ℃ after dropwise adding, carrying out suction filtration on reaction liquid after reaction, collecting and discarding filter residues, separating filtrate, washing an organic phase with cold water, drying and dewatering the organic phase with a 4A molecular sieve, filtering, recrystallizing the concentrated organic phase, and carrying out centrifugal drying to obtain a finished product of the ethylene sulfate, wherein the yield is 78%, and the purity of the product is represented by GC (gas chromatography), and the purity is 99.6%.

Example 6

Adding into a reaction kettle75g of ethylene sulfite, 750g of propyl propionate, 52g of calcium hypochlorite solid and 2mg of ruthenium trichloride solid, the temperature of the reaction system was lowered to-15 ℃, and 225g of cold water was added dropwise with vigorous stirring. Controlling the reaction temperature to be-5 ℃, reacting for 6 hours at-5 ℃ after the dropwise adding is finished, filtering the reaction solution after the reaction is finished, collecting and discarding filter residues, separating the filtrate, washing the organic phase with cold water,drying and dewatering the molecular sieve, filtering, concentrating an organic phase, recrystallizing, and centrifugally drying to obtain a finished product of the vinyl sulfate, wherein the yield is 76%, and the purity of the product is represented by GC (gas chromatography), and is 99.55%.

In a word, the synthesis process route of the vinyl sulfate synthesis method is simple and controllable, and the synthesis yield of the vinyl sulfite is improved; because the common oxidant sodium hypochlorite solution is easy to decompose when being stored at normal temperature, the invention uses the calcium hypochlorite solid, is convenient to store and can be prepared for use at present, the dosage of the catalyst is less in the oxidation process of the vinyl sulfate, and the cost is low; the hydrolysis rate of the vinyl sulfate can be reduced by reducing the reaction temperature, the oxidation yield is improved, and a high-purity vinyl sulfate product can be obtained by subsequent recrystallization, has the purity of over 99.5 percent and can be used as an additive of lithium ion battery electrolyte.

It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof. The present embodiments are therefore to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein.

Furthermore, it should be understood that although the present description refers to embodiments, not every embodiment may contain only a single embodiment, and such description is for clarity only, and those skilled in the art should integrate the description, and the embodiments may be combined as appropriate to form other embodiments understood by those skilled in the art.