CN113549048B - Preparation method of ethylene sulfite - Google Patents
Preparation method of ethylene sulfite Download PDFInfo
- Publication number
- CN113549048B CN113549048B CN202110823974.XA CN202110823974A CN113549048B CN 113549048 B CN113549048 B CN 113549048B CN 202110823974 A CN202110823974 A CN 202110823974A CN 113549048 B CN113549048 B CN 113549048B
- Authority
- CN
- China
- Prior art keywords
- ethylene glycol
- disodium salt
- solvent
- ethylene
- sulfite
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides a preparation method of ethylene sulfite, which 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. The preparation method of the invention has the following beneficial effects: 1) The synthesis method takes ethylene glycol disodium salt as a raw material, and reacts with thionyl chloride in a solvent to synthesize the ethylene sulfite, 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 benefits and social benefits are achieved.
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 the synthesis of vinyl sulfite by reaction of ethylene glycol and thionyl chloride in dichloromethane, followed by alkaline washing. The methods have the disadvantages 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 the preparation of ethylene sulfite by transesterification of ethylene glycol with dimethyl sulfite as raw material 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 liquid crystal display panels are,
in the 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, when no water is separated out, carrying out reduced pressure distillation, evaporating out mesitylene to obtain crude ethylene glycol disodium salt, carrying out suction filtration, washing, and carrying out vacuum drying to obtain the ethylene glycol disodium salt.
In the synthesis method of the ethylene glycol disodium salt, the molar ratio of ethylene glycol to 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 its application. 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
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 benzene were charged, vigorously stirred under nitrogen gas, 14.3g of thionyl chloride was added dropwise at-5 ℃ and, after completion of the addition, after 6 hours of the 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, 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%. 1 HNMR: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%. 1 HNMR:δ4.276(s,4H), GC-MS，m/z (%)：108(M + , 100%)。
Example 4
10.6g of ethylene glycol disodium salt (0.1 mol) prepared in example 1 and 50g of dichloroethane were charged into a 250ml four-necked flask equipped with a thermometer, a condenser and a drying tube, vigorously stirred under nitrogen protection, 13.1g of thionyl chloride was added dropwise at 7 ℃ and, after completion of the addition, after 3 hours of reaction, washed to neutrality with 5% by weight of an aqueous solution of sodium hydrogencarbonate, and the organic phase was separated off. 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%. 1 HNMR:δ4.276(s,4H), GC-MS，m/z (%)：108(M + , 100%)。
The above-mentioned embodiments are only for illustrating the technical idea and features of the present invention, and the purpose of the invention is to enable those skilled in the art to understand the content of the present invention, and not to limit the protection 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 (3)
1. The preparation method of the ethylene sulfite is characterized by comprising 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 ethylene sulfite;
in the step 1), the molar ratio of the ethylene glycol disodium salt to the 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.
2. The method for preparing vinyl sulfite according to claim 1, wherein in the step 1), the synthesis method of the 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, when no water is separated out, carrying out reduced pressure distillation, evaporating out mesitylene to obtain crude ethylene glycol disodium salt, carrying out suction filtration, washing, and carrying out vacuum drying to obtain the ethylene glycol disodium salt.
3. The method for preparing ethylene sulfite according to claim 2, wherein in the synthesis of ethylene glycol disodium salt, the molar ratio of ethylene glycol to sodium hydroxide is 1:2.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110823974.XA CN113549048B (en) | 2021-07-21 | 2021-07-21 | Preparation method of ethylene sulfite |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110823974.XA CN113549048B (en) | 2021-07-21 | 2021-07-21 | Preparation method of ethylene sulfite |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113549048A CN113549048A (en) | 2021-10-26 |
| CN113549048B true CN113549048B (en) | 2022-10-04 |
Family
ID=78103725
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110823974.XA Active CN113549048B (en) | 2021-07-21 | 2021-07-21 | Preparation method of ethylene sulfite |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113549048B (en) |
Families Citing this family (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 |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108373460B (en) * | 2018-03-27 | 2019-10-15 | 上海康鹏科技股份有限公司 | 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 |
-
2021
- 2021-07-21 CN CN202110823974.XA patent/CN113549048B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN113549048A (en) | 2021-10-26 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN113549048B (en) | Preparation method of ethylene sulfite | |
| CN108503531B (en) | Preparation method of 3, 3-dimethyl-2-oxobutyric acid | |
| CN108610324B (en) | Preparation method of vinyl sulfate | |
| CN114181191B (en) | Synthesis method of cyclic sulfate | |
| CN112250662A (en) | Preparation method of cyclic sulfate | |
| CN113444066A (en) | Preparation method of vinyl sulfate | |
| KR20010053294A (en) | Method for producing ortho-alkylated benzoic acid derivatives | |
| CN101591328A (en) | The chemical synthesis process of a kind of 2-bromothiophene and derivative thereof | |
| CN101210006B (en) | Method for preparing vinylene carbonate | |
| CN111116336A (en) | Synthetic method of 2, 4-dichloroacetophenone | |
| CN115108912A (en) | Strongly alkaline ionic liquid catalyzed CO 2 Method for synthesizing dimethyl carbonate catalyst | |
| WO2022097115A1 (en) | An improved process for preparation of prohexadione and its calcium salt | |
| CN108164502B (en) | Preparation method of 1, 3-propane sultone | |
| CN112521328A (en) | Preparation method of 3-bromocarbazole | |
| CN114149343B (en) | Preparation method of high-purity 1, 4-dicyano-2-butene | |
| CN110746471B (en) | Preparation method of fondaparinux sodium disaccharide intermediate | |
| CN112645829B (en) | Chiral synthesis method of ephedrine key intermediate (S) -2-methylamino-1-phenyl-1-acetone | |
| CN110467529B (en) | Synthesis method of ester | |
| CN102127061A (en) | Improvement method for preparing 6-fluorin-3,4-dihydro-2H-1-benzopyranyl-2-epoxy ethane | |
| CN106478439B (en) | A kind of preparation method of O- tertiary butyls-L-threonine tert-butyl ester | |
| CN115677491A (en) | Preparation process of ethyl 4- (ethoxycarbonyl) methoxybutyrate | |
| CN108164431B (en) | 2-hydroxy-5- (2,3,5, 6-tetrafluoro-4-trifluoromethyl benzylamino) benzoic acid and preparation method thereof | |
| KR100763770B1 (en) | Process for preparing chiral intermediates useful in synthesis of atorvastatin | |
| CN115536494A (en) | Synthesis method of 1- (4-bromophenyl) -1, 4-butanediol | |
| CN115232103A (en) | Preparation method of cyclic sulfate |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |