CN113549048A - A kind of preparation method of vinyl sulfite - Google Patents
A kind of preparation method of vinyl sulfite Download PDFInfo
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- CN113549048A CN113549048A CN202110823974.XA CN202110823974A CN113549048A CN 113549048 A CN113549048 A CN 113549048A CN 202110823974 A CN202110823974 A CN 202110823974A CN 113549048 A CN113549048 A CN 113549048A
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- ethylene glycol
- vinyl sulfite
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- disodium salt
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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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Abstract
本发明提供了一种亚硫酸乙烯酯的制备方法，包括如下步骤：1）将乙二醇二钠盐加入溶剂中，在氮气保护下，在一定温度下滴加氯化亚砜，加毕，反应一段时间后，用碳酸氢钠水溶液洗至中性，分出有机相；2）有机相用无水硫酸钠干燥，常压回收溶剂，减压得到亚硫酸乙烯酯。本发明的制备方法具有如下有益效果：1）本发明的合成方法通过以乙二醇二钠盐为原料，在溶剂中和氯化亚砜反应，合成亚硫酸乙烯酯，这一合成路线从根本上消除了含酸废水和副产的排放，达到了清洁化生产的要求；同时达到降低了生产成本，具有很大的经济效益和社会效益。The invention provides a preparation method of vinyl sulfite, which comprises the following steps: 1) adding ethylene glycol disodium salt into a solvent, under nitrogen protection, dropwise adding thionyl chloride at a certain temperature, and after the addition, After reacting for a period of time, wash with an aqueous sodium bicarbonate solution until neutral, and separate the organic phase; 2) Dry the organic phase with anhydrous sodium sulfate, recover the solvent under normal pressure, and obtain vinyl sulfite under reduced pressure. The preparation method of the present invention has the following beneficial effects: 1) The synthetic method of the present invention uses ethylene glycol disodium salt as a raw material, reacts with thionyl chloride in a solvent, and synthesizes vinyl sulfite. This synthetic route is fundamentally It eliminates the discharge of acid-containing wastewater and by-products, and meets the requirements of clean production; at the same time, it reduces production costs and has great economic and social benefits.
Description
Technical Field
The invention relates to the field of lithium ion battery electrolyte additives, in particular to a method for synthesizing ethylene sulfite which can be used as a lithium ion battery electrolyte additive.
Background
The ethylene sulfite is a colorless transparent liquid and is stable to heat. The boiling point is 170 ℃.
The Ethylene Sulfite (ES) is an additive which can make the use effect of the lithium ion battery electrolyte more excellent. After the vinyl sulfate is added into the electrolyte of the lithium ion battery, the storage stability of the battery can be greatly improved, and the low-temperature performance of the battery can also be improved.
In the prior art, the synthesis method of the ethylene sulfite is disclosed as follows:
CN109776361A, CN109369609A, CN106187989B and CN112375064A disclose that ethylene glycol and thionyl chloride are used as raw materials, reacted in dichloromethane, and then washed with alkali to synthesize the ethylene sulfite. The methods have the defects of generating a large amount of hydrogen chloride gas, generating a large amount of salt-containing wastewater and having large environmental protection treatment pressure.
CN107987052A discloses a method for preparing ethylene sulfite by using ethylene glycol and dimethyl sulfite as raw materials and carrying out ester exchange in the presence of a catalyst. The dimethyl sulfite used by the method is not easy to obtain, and has high toxicity and high potential safety hazard.
The synthesis process of the ethylene sulfite has many hidden dangers in the aspects of safety, environmental protection and the like. The production costs are also relatively high.
In addition, the method has the advantages of improving the product yield, simplifying reaction steps, avoiding potential safety hazards, reducing emission, and being green and environment-friendly, and is a problem which must be considered in modern chemical production.
Disclosure of Invention
The invention aims to provide a method for preparing ethylene sulfite, aiming at the problems in the prior art.
The technical scheme of the invention is as follows:
a preparation method of ethylene sulfite comprises the following steps:
1) adding ethylene glycol disodium salt into a solvent, dropwise adding thionyl chloride at a certain temperature under the protection of nitrogen, reacting for a period of time after the addition, washing the mixture to be neutral by using a sodium bicarbonate aqueous solution, and separating an organic phase;
2) drying the organic phase by using anhydrous sodium sulfate, recovering the solvent at normal pressure, and decompressing to obtain the ethylene sulfite.
Preferably, the first and second electrodes are formed of a metal,
in step 1), the molar ratio of ethylene glycol disodium salt to thionyl chloride is 1: 0.9-1.2.
In the step 1), the reaction temperature is-5-15 ℃.
In the step 1), the reaction time is 3-9 hours.
In the step 1), the solvent is one of dichloromethane, dichloroethane, benzene and dimethyl carbonate.
In step 1), the synthesis method of ethylene glycol disodium salt is as follows: mixing ethylene glycol and a mesitylene solvent, adding sodium hydroxide under the protection of nitrogen, stirring and heating, refluxing at normal pressure for water separation, starting reduced pressure distillation when no water is separated, evaporating mesitylene to obtain crude ethylene glycol disodium salt, performing suction filtration, washing, and performing vacuum drying to obtain the ethylene glycol disodium salt.
In the synthesis method of the ethylene glycol disodium salt, the molar ratio of the ethylene glycol to the sodium hydroxide is 1: 2.
the preparation method of the invention has the following beneficial effects:
1) the synthesis method of the invention synthesizes the ethylene sulfite by taking ethylene glycol disodium salt as a raw material to react with thionyl chloride in a solvent, and the synthesis route fundamentally eliminates the discharge of acid-containing wastewater and byproducts, thereby meeting the requirement of clean production; meanwhile, the production cost is reduced, and great economic and social benefits are achieved.
2) According to the invention, by selecting specific reaction raw materials, the dosage ratio of the reaction raw materials, specific reaction temperature and specific reaction time, the obtained product has high yield and high purity, the yield reaches more than 92 percent, the purity reaches more than 99 percent, and the method has unexpected technical effects compared with the prior art.
Detailed Description
The following examples are intended to further illustrate the invention and are not intended to limit the application of the invention. The percentages in the examples are uniformly mass fractions.
Example 1
62g of ethylene glycol and 300ml of mesitylene solvent were put into a 500ml four-neck reaction flask with a water-dividing device. Adding 80g of sodium hydroxide under the protection of nitrogen, stirring and heating, refluxing at normal pressure for water separation, starting reduced pressure distillation when no water is separated out, and evaporating mesitylene to obtain crude ethylene glycol disodium salt. Pulping with 300ml methyl ethyl ketone, filtering, washing with 50ml methyl ethyl ketone, and vacuum drying the solid at 50 deg.C to obtain 95g ethylene glycol disodium salt.
Example 2
Into a 250ml four-necked flask equipped with a thermometer, a condenser and a drying tube, 10.6g of ethylene glycol disodium prepared in example 1 was chargedSalt (0.1 mol) and 50g benzene are stirred vigorously under nitrogen protection, 14.3g thionyl chloride is added dropwise at-5 ℃ after the addition is completed, and after 6 hours of reaction, the mixture is washed to neutrality with 5% (by weight) aqueous sodium bicarbonate solution, and the organic phase is separated. The organic phase was dried over 10g of anhydrous sodium sulfate, the solvent was recovered at normal pressure, and 10.5g of vinyl sulfite with a content of 99.2% or more was obtained under reduced pressure (GC, normalization method) with a yield of 97.2%.1HNMR:δ4.276(s,4H), GC-MS，m/z (%)：108(M + , 100%)。
Example 3
In a 250ml four-necked flask equipped with a thermometer, a condenser and a drying tube, 10.6g of ethylene glycol disodium salt (0.1 mol) prepared in example 1 and 50g of methylene chloride were charged, vigorously stirred under nitrogen, 10.8g of thionyl chloride was added dropwise at 15 ℃ after completion of the addition, and after 9 hours of the reaction, the mixture was washed with 5% by weight of an aqueous sodium bicarbonate solution to neutrality, and an organic phase was separated. The organic phase was dried over 10g of anhydrous sodium sulfate, methylene chloride was recovered at normal pressure, and 10.1g of vinyl sulfite having a content of 99.4% or more was obtained under reduced pressure ((HPLC, normalization method), yield 93.5%.1HNMR:δ4.276(s,4H), GC-MS，m/z (%)：108(M + , 100%)。
Example 4
In a 250ml four-necked flask equipped with a thermometer, a condenser and a drying tube, 10.6g of ethylene glycol disodium salt (0.1 mol) prepared in example 1 and 50g of dichloroethane were charged, vigorously stirred under nitrogen protection, 13.1g of thionyl chloride was added dropwise at 7 ℃ after completion of the addition, and after 3 hours of reaction, washed with 5% (by weight) aqueous sodium bicarbonate solution to neutrality, and the organic phase was separated. The organic phase was dried over 10g of anhydrous sodium sulfate, ethylene dichloride was recovered at normal pressure, and 10g of vinyl sulfite with a content of 99.0% or more was obtained under reduced pressure ((HPLC, normalization method), yield 92.6%.1HNMR:δ4.276(s,4H), GC-MS，m/z (%)：108(M + , 100%)。
The above-mentioned embodiments are merely illustrative of the technical ideas and features of the present invention, and are intended to enable those skilled in the art to understand the contents of the present invention, and not to limit the scope of the present invention. All equivalent changes and modifications made according to the spirit of the present invention should be covered within the protection scope of the present invention.
Claims (7)
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| CN202110823974.XA CN113549048B (en) | 2021-07-21 | 2021-07-21 | Preparation method of ethylene sulfite |
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| CN202110823974.XA CN113549048B (en) | 2021-07-21 | 2021-07-21 | Preparation method of ethylene sulfite |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115677652A (en) * | 2022-11-14 | 2023-02-03 | 陕西煤业化工技术研究院有限责任公司 | Method for continuously preparing vinyl sulfate |
| CN115806540A (en) * | 2022-11-18 | 2023-03-17 | 山东兴文工业技术研究院有限公司 | Preparation method of ethylene sulfite |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108373460A (en) * | 2018-03-27 | 2018-08-07 | 上海康鹏科技有限公司 | A kind of preparation method of cyclic sulfates |
| CN112679466A (en) * | 2020-12-27 | 2021-04-20 | 江苏瀚康新材料有限公司 | Method for synthesizing vinyl sulfate |
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2021
- 2021-07-21 CN CN202110823974.XA patent/CN113549048B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108373460A (en) * | 2018-03-27 | 2018-08-07 | 上海康鹏科技有限公司 | A kind of preparation method of cyclic sulfates |
| CN112679466A (en) * | 2020-12-27 | 2021-04-20 | 江苏瀚康新材料有限公司 | Method for synthesizing vinyl sulfate |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115677652A (en) * | 2022-11-14 | 2023-02-03 | 陕西煤业化工技术研究院有限责任公司 | Method for continuously preparing vinyl sulfate |
| CN115806540A (en) * | 2022-11-18 | 2023-03-17 | 山东兴文工业技术研究院有限公司 | Preparation method of ethylene sulfite |
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Denomination of invention: A method for preparing an ethylene sulfite Granted publication date: 20221004 Pledgee: Jiangsu Rudong Rural Commercial Bank Co.,Ltd. Yangkou Branch Pledgor: Jiaerke Biotechnology Nantong Co.,Ltd. Registration number: Y2025980027460 |