CN114591289B - Preparation method of vinyl sulfate - Google Patents
Preparation method of vinyl sulfate Download PDFInfo
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- CN114591289B CN114591289B CN202210314658.4A CN202210314658A CN114591289B CN 114591289 B CN114591289 B CN 114591289B CN 202210314658 A CN202210314658 A CN 202210314658A CN 114591289 B CN114591289 B CN 114591289B
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- vinyl sulfate
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D327/00—Heterocyclic compounds containing rings having oxygen and sulfur atoms as the only ring hetero atoms
- C07D327/10—Heterocyclic compounds containing rings having oxygen and sulfur atoms as the only ring hetero atoms two oxygen atoms and one sulfur atom, e.g. cyclic sulfates
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention provides a preparation method of vinyl sulfate, which comprises the following steps: ethylene glycol and halosulfonic acid are used as raw materials, an azeotropic organic solvent which is insoluble in water is used as a reaction medium, the halosulfonic acid is dropwise added into an azeotropic organic solvent system which is insoluble in water, and the vinyl sulfate is obtained after acylation reaction and azeotropic dehydration reaction, cooling crystallization, solid-liquid separation to remove the solvent, recrystallization of the organic solvent and drying. The method has the advantages of cheap and easily obtained raw materials, no need of catalysts, short reaction route, mild reaction conditions, simple operation, high product purity and yield and small wastewater amount, and adopts a one-pot process for the two-step reaction.
Description
Technical Field
The invention belongs to the technical field of preparation of lithium ion battery electrolyte additives, and particularly relates to a preparation method of vinyl sulfate.
Background
Lithium ion batteries have been widely used in portable electronic devices, energy storage systems, electric vehicles, and hybrid vehicles, and the energy density thereof has been increasingly demanded. The electrolyte additive can effectively improve the dynamic characteristics of the battery, obviously improve the comprehensive performance of the battery and is used as an effective method for solving the problem. The initial discharge capacity of the battery can be increased by adding the vinyl sulfate into the lithium ion battery electrolyte, the initial capacity drop of the battery is restrained, the expansion of the battery placed at high temperature is reduced, and the charge and discharge performance and the cycle times of the battery are improved. As a novel lithium battery electrolyte additive with excellent performance, the method for researching and developing the vinyl sulfate is of great significance.
CN 107629032A discloses a process for preparing vinyl sulfate by reacting ethylene glycol with sulfuryl fluoride in the presence of an acid-binding agent and a catalyst. Although the provided preparation method of vinyl sulfate has short reaction steps and only uses one-step reaction, the product yield is low, the adopted raw material sulfuryl fluoride is gas, the storage and the use are inconvenient, and the crown ether catalyst which is expensive, toxic and difficult to recycle and treat is not suitable for industrial production. In addition, CN 109776487A discloses a purification method for preparing a crude product by nucleophilic substitution reaction with ethylene glycol and sulfonyl chloride as starting materials and chloroform as solvent, and recrystallizing with chloroform as solvent. Although the inconvenient gas raw materials are avoided, the post-treatment process is complex, the generated wastewater is large in quantity and difficult to treat, and the environmental pollution is large.
Disclosure of Invention
Aiming at the defects of the technology, the invention provides the preparation method of the vinyl sulfate, which has the advantages of low-cost and easily-obtained raw materials, simple and convenient operation, high product purity and yield, environmental friendliness and suitability for industrial production.
The technical scheme of the invention is as follows:
ethylene glycol and halosulfonic acid are used as raw materials, an azeotropic organic solvent which is insoluble in water is used as a reaction medium, the halosulfonic acid is dropwise added into an azeotropic organic solvent system which is insoluble in water, and the vinyl sulfate is obtained after acylation reaction and azeotropic dehydration reaction, cooling crystallization, solid-liquid separation to remove the solvent, recrystallization of the organic solvent and drying.
In the technical scheme of the invention, the halosulfonic acid is chlorosulfonic acid or fluorosulfonic acid;
the organic solvent azeotroped with water is selected from dichloromethane, chloroform, dichloroethane, cyclohexane and chlorobenzene;
the mol ratio of the glycol to the halosulfonic acid is 1 (0.9-1.1);
the acylation reaction step is carried out, and the reaction temperature is controlled to be-10-30 ℃ when halosulfonic acid is added dropwise. After the halosulfonic acid is added dropwise, the reaction temperature is-10-120 ℃ and the reaction time is 1-6 h;
the azeotropic dehydration reaction step is carried out at the reaction temperature of the azeotropic point of the organic solvent and water, and the reaction time is until no water is separated.
The organic solvent is recrystallized, and the recrystallization solvent is selected from dichloromethane, chloroform, dichloroethane, n-hexane and cyclohexane.
Compared with the prior art, the invention has the following advantages and effects:
ethylene glycol and halosulfonic acid are used as raw materials, the two steps of reaction of acylation and azeotropic dehydration are carried out in an azeotropic solvent, a catalyst is not needed, the intermediate generated in the first step of acylation reaction is not needed to be separated, and the second step of azeotropic dehydration reaction is directly carried out by adopting a one-pot process to obtain the vinyl sulfate.
Detailed Description
The present invention will be described in further detail with reference to specific examples.
Example 1
400g of methylene dichloride and 12.4g of ethylene glycol are added into a 500mL four-neck flask with a stirrer, a dropping funnel, a thermometer and a reflux condenser, 23.3g of chlorosulfonic acid is added into a reaction bottle through the dropping funnel under stirring and cooling, the reaction temperature is controlled to-10 to-5 ℃ in the process of adding chlorosulfonic acid, and tail gas generated in the reaction process is absorbed by water. After the dripping is finished, stirring and reacting for 6 hours at the temperature of minus 10 ℃ to minus 5 ℃. Then changing the reflux reaction device into a reflux water diversion reaction device, and carrying out reflux water diversion reaction under heating and stirring until no water is discharged. After the reaction is finished, the reaction product is cooled to minus 10 ℃ under the condition of cooling and stirring, solid is separated out, the solid is collected by suction filtration, the recrystallization is carried out by using methylene dichloride, 22.3g of vinyl sulfate is obtained after drying, the content is 99.9% (GC normalization method), and the yield is 88.9%.
Example 2
400g of chloroform and 12.4g of ethylene glycol are added into a 500mL four-neck flask with a stirrer, a dropping funnel, a thermometer and a reflux condenser, 23.3g of chlorosulfonic acid is added into a reaction flask through the dropping funnel under stirring and cooling, the reaction temperature is controlled to be-5-0 ℃ in the process of adding chlorosulfonic acid, and tail gas generated in the reaction process is absorbed by water. After the dripping is finished, stirring and reacting for 4 hours at the temperature of 5-10 ℃. Then changing the reflux reaction device into a reflux water diversion reaction device, and carrying out reflux water diversion reaction under heating and stirring until no water is discharged. After the reaction is finished, the reaction product is cooled to minus 5 ℃ under the condition of cooling and stirring, solid is separated out, the solid is collected by suction filtration, and is recrystallized by methylene dichloride, 21.4g of vinyl sulfate with the content of 99.8 percent is obtained after drying (GC normalization method), and the yield is 86.3 percent.
Example 3
400g of dichloroethane and 12.4g of ethylene glycol are added into a 500mL four-necked flask with a stirrer, a dropping funnel, a thermometer and a reflux condenser, 23.3g of chlorosulfonic acid is added dropwise into a reaction flask through the dropping funnel under stirring and cooling, the reaction temperature is controlled to be 0-5 ℃ in the process of dropwise adding chlorosulfonic acid, and tail gas generated in the reaction process is absorbed by water. After the dripping is finished, stirring and reacting for 3 hours at 15-20 ℃. Then changing the reflux reaction device into a reflux water diversion reaction device, and carrying out reflux water diversion reaction under heating and stirring until no water is discharged. After the reaction is finished, the reaction product is cooled to 0 ℃ under the condition of cooling and stirring to precipitate solid, the solid is collected by suction filtration, recrystallized by chloroform, and dried to obtain 21.8g of vinyl sulfate with the content of 99.9 percent (GC normalization method), and the yield is 87.9 percent
Example 4
Into a 500mL four-necked flask with a stirrer, a dropping funnel, a thermometer and a reflux condenser, 300g of dichloroethane and 12.4g of ethylene glycol are added, 23.3g of chlorosulfonic acid is added dropwise into a reaction flask through the dropping funnel under stirring and cooling, the reaction temperature is controlled to be 10-15 ℃ during the dropwise addition of chlorosulfonic acid, and tail gas generated in the reaction process is absorbed by water. After the dripping is finished, stirring and reacting for 2 hours at 25-30 ℃. Then changing the reflux reaction device into a reflux water diversion reaction device, and carrying out reflux water diversion reaction under heating and stirring until no water is discharged. After the reaction is finished, the reaction product is cooled to 5 ℃ under stirring to precipitate solid, the solid is collected by suction filtration, recrystallized by dichloroethane, and dried to obtain 20.5g of vinyl sulfate with the content of 99.9% (GC normalization method) with the yield of 82.7%.
Example 5
Into a 500mL four-necked flask with a stirrer, a dropping funnel, a thermometer and a reflux condenser, 300g of cyclohexane and 12.4g of ethylene glycol are added, 25.6g of chlorosulfonic acid is added dropwise into a reaction flask through the dropping funnel under stirring and cooling, the reaction temperature is controlled to be 20-25 ℃ in the process of adding chlorosulfonic acid dropwise, and tail gas generated in the reaction process is absorbed by water. After the dripping is finished, stirring and reacting for 2 hours at 75-80 ℃. Then changing the reflux reaction device into a reflux water diversion reaction device, and carrying out reflux water diversion reaction under heating and stirring until no water is discharged. After the reaction is finished, the reaction product is cooled to 15 ℃ under stirring, solid is separated out, the solid is collected by suction filtration, recrystallized by normal hexane, 18.9g of vinyl sulfate is obtained after drying, the content is 99.8% (GC normalization method), and the yield is 76.2%.
Example 6
400g of chlorobenzene and 12.4g of ethylene glycol are added into a 500mL four-necked flask with a stirrer, a dropping funnel, a thermometer and a reflux condenser, 18.0g of fluorosulfonic acid is added dropwise into a reaction flask through the dropping funnel under stirring and cooling, the reaction temperature is controlled to be 25-30 ℃ in the process of adding chlorosulfonic acid dropwise, and tail gas generated in the reaction process is absorbed by water. After the dripping is finished, stirring and reacting for 1h at 115-120 ℃. Then changing the reflux reaction device into a reflux water diversion reaction device, and carrying out reflux water diversion reaction under heating and stirring until no water is discharged. After the reaction is finished, the reaction product is cooled to 0 ℃ under stirring to precipitate solid, the solid is collected by suction filtration, the solid is recrystallized by cyclohexane, 19.9g of vinyl sulfate with the content of 99.9 percent is obtained after drying (GC normalization method), and the yield is 80.3 percent.
Claims (8)
1. A process for preparing vinyl sulfate includes such steps as adding halosulfonic acid to the system of glycol and water-insoluble azeotropic organic solvent, sulfonylating, azeotropic dewatering, cooling, crystallizing, solid-liquid separation to remove solvent, recrystallizing and drying.
2. A process for the preparation of vinyl sulfate as claimed in claim 1, wherein the halosulfonic acid is chlorosulfonic acid or fluorosulfonic acid.
3. A process for the preparation of vinyl sulfate as claimed in claim 1, wherein the organic solvent which azeotropes with water is selected from the group consisting of methylene chloride, chloroform, dichloroethane, cyclohexane and chlorobenzene.
4. A process for producing vinyl sulfate according to claim 1, wherein the molar ratio of ethylene glycol to halosulfonic acid is 1 (0.9-1.1).
5. A process for producing vinyl sulfate as claimed in claim 1, wherein said sulfonylation step is carried out at a controlled reaction temperature of-10 to 30 ℃ when a halosulfonic acid is added dropwise.
6. A method for preparing vinyl sulfate according to claim 1, wherein the sulfonylation reaction step is carried out at-10-120 ℃ for 1-6 h after the halosulfonic acid is added dropwise.
7. A process for producing vinyl sulfate according to claim 1, wherein the azeotropic dehydration reaction step is carried out at a temperature of an azeotropic point of the organic solvent and water, and a reaction time is set until no water is discharged.
8. A process for the preparation of vinyl sulfate as claimed in claim 1, wherein the organic solvent is recrystallized from a solvent selected from the group consisting of methylene chloride, chloroform, ethylene dichloride, n-hexane and cyclohexane.
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| CN202210314658.4A CN114591289B (en) | 2022-03-29 | 2022-03-29 | Preparation method of vinyl sulfate |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108822075A (en) * | 2018-07-13 | 2018-11-16 | 山东贵邦药业有限公司 | A kind of sulfuric acid vinyl ester synthesis technology |
| CN111170985A (en) * | 2019-12-27 | 2020-05-19 | 烟台海川化学制品有限公司 | Preparation method of allyl sulfate |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108822075A (en) * | 2018-07-13 | 2018-11-16 | 山东贵邦药业有限公司 | A kind of sulfuric acid vinyl ester synthesis technology |
| CN111170985A (en) * | 2019-12-27 | 2020-05-19 | 烟台海川化学制品有限公司 | Preparation method of allyl sulfate |
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