CN107501231B - A kind of preparation method of vinylene carbonate - Google Patents
A kind of preparation method of vinylene carbonate Download PDFInfo
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- CN107501231B CN107501231B CN201710610079.3A CN201710610079A CN107501231B CN 107501231 B CN107501231 B CN 107501231B CN 201710610079 A CN201710610079 A CN 201710610079A CN 107501231 B CN107501231 B CN 107501231B
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- vinylene carbonate
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D317/00—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms
- C07D317/08—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3
- C07D317/10—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings
- C07D317/32—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D317/34—Oxygen atoms
- C07D317/40—Vinylene carbonate; Substituted vinylene carbonates
Abstract
The invention discloses a kind of preparation method of vinylene carbonate, the preparation method includes：Make ethylene carbonate and selenium dioxide in a solvent, the vinylene carbonate is obtained by the reaction under protective gas atmosphere, wherein the molar ratio of the selenium dioxide and the ethylene carbonate is 1.1 ~ 4 ︰ 1；The present invention is easy to operate, and reaction is mild, and the by-product polluted the environment without exhaust gas, solid waste etc., has clear advantage.
Description
Technical field
The invention belongs to organic film for additive of lithium-ion battery electrolytes and/or additives for overcharge protection additive agent field,
More particularly to a kind of preparation method of vinylene carbonate.
Background technology
Constantly expand with the use scope of lithium ion battery, the technology of lithium ion battery is also being constantly progressive, in conduct
Some additives are added in the electrolyte of lithium ion battery " blood ", many performances of battery can be improved.Wherein, carbonic acid Asia second
Enester is a kind of organic film for additive in electrolyte and additives for overcharge protection additive, with good high temperature performance and
Anti- inflatable function, can increase the stability of solvent, effectively inhibit the decomposition of solvent, promote graphite cathode to be formed good
SEI films improve the cycle performance of battery.
Vinylene carbonate (VC, Vinylene Carbonate), is at room temperature colourless transparent liquid, and fusing point is 21 DEG C,
Boiling point is 165 DEG C/760mmHg, and (20 DEG C) of density is 1.360 g/cm3, and nineteen fifty-three Newman et al. reports carbonic acid Asia for the first time
The synthetic method of vinyl acetate（J. Am. Chem. Soc., 1953,75 (5), pp1263-1264）, utilize chlorine and carbonic acid Asia second
Free radical substitution synthesis chlorocarbonic acid vinyl acetate occurs for ester, and elimination reaction then occurs under ether solvents with triethylamine and obtains carbonic acid
Vinylene.
The method of synthesized vinylene carbonate follows the synthetic schemes of Newman et al. and is improved substantially at present, still
This method will produce a large amount of hydrogen chloride emission, and a large amount of triethylamine hydrochloride solid wastes and coking kettle are residual, to environment and operation
Aspect produces bigger effect.Such as Chinese invention patent CN106831699A discloses a kind of synthesis side of vinylene carbonate
Method includes the following steps：a）Organic solvent is dried and dehydrated；The organic solvent be methyl tertiary butyl ether(MTBE), tetrahydrofuran,
One or more of chloroform, dichloromethane；b）Under nitrogen protection, organic solvent is added into organic solvent at 30 DEG C ~ 100 DEG C
Gross mass 0.2wt% ~ 3wt% polymerization inhibitors and antioxidant compound, chlorocarbonic acid vinyl acetate in organic solvent with nitrogenous class dechlorination
Change hydrogen agent and dehydrochlorination reaction occurs, reacts 2 ~ 10 hours；Wherein chlorocarbonic acid vinyl acetate and the molar ratio of organic solvent are 1：
0.5 ~ 2, the molar ratio of chlorocarbonic acid vinyl acetate and nitrogenous class dehydrochlorination agent is 1：1.0~1.2；c）Products therefrom is through filtering
Rectifying can be obtained vinylene carbonate twice for desalination, negative pressure；Although this patent reaction gentle degree, reduce side reaction
Etc. be made that improvement, but still inevitably produce a large amount of hydrogen chloride emission, environment damaged, pair set
It is standby to cause the influences such as corrosion, it can indirectly increase production cost.
A kind of method directly preparing vinylene carbonate by ethylene carbonate is also disclosed in the prior art simultaneously, such as
Chinese invention patent CN1789259 discloses a kind of method of synthesized vinylene carbonate, using fixed bed reactors, is added
Catalyst, in nitrogen, argon gas or hydrogen as diluent gas and volume gas, reaction temperature is 200 DEG C ~ 600 DEG C, and Feed space velocities are
1 ~ 100g/hmlcat, under the conditions of reaction pressure is 0.1 ~ 10MPa, ethylene carbonate catalytic dehydrogenation obtains vinylene carbonate.
This patent although avoid usually using the hydrogen chloride and salt solid waste for carrying out after chloro generating during elimination reaction again with
And coking kettle is residual, but it still will produce hydrogen and reaction temperature is very high（200℃~600℃）, can be in actual production process
Equipment requirement and safety prevention measure generate greatly negative effect.
Invention content
The technical problem to be solved by the present invention is to overcome the deficiencies of the prior art and provide a kind of safe, easy to operate, ring
Protect the preparation method of free of contamination vinylene carbonate.
In order to solve the above technical problems, a kind of technical solution that the present invention uses is as follows：
A kind of preparation method of vinylene carbonate, the preparation method include：Ethylene carbonate is set to exist with selenium dioxide
In solvent, the vinylene carbonate is obtained by the reaction under protective gas atmosphere, wherein the selenium dioxide and carbonic acid Asia second
The molar ratio of ester is 1.1 ~ 4 ︰ 1.
According to the present invention, the molar ratio of the selenium dioxide and the ethylene carbonate is preferably 1.3 ~ 1.7:1, into
One step is preferably 1.4 ~ 1.6:1.In a specific preferred embodiment, the selenium dioxide and the ethylene carbonate
Molar ratio is 1.5：1.
In certain specific embodiments of the invention, the solvent is in ethyl alcohol, methanol, the tert-butyl alcohol, benzene and acetone
One or more combinations.
In certain specific embodiments of the invention, it is preferable that the matter that feeds intake of the solvent and the ethylene carbonate
Amount is than being 1 ~ 5 ︰ 1.
It is further preferred that the mass ratio that feeds intake of the solvent and the ethylene carbonate is 1 ~ 3 ︰ 1.
In certain specific embodiments of the invention, it is preferable that the temperature of the reaction is the boiling point of the solvent.
In certain specific embodiments of the invention, it is preferable that the reaction time of the reaction is 10 ~ 48h.
Preferably, the reaction time of the reaction be 20 ~ for 24 hours.
In certain specific embodiments of the invention, it is preferable that so that the reaction is carried out in the presence of a catalyst, it is described
Catalyst is one or more combinations in glacial acetic acid, benzoic acid, salicylic acid and tartaric acid.
Further, the molar ratio of the catalyst and the ethylene carbonate is 0.001 ~ 0.01 ︰ 1.Preferably,
The molar ratio of the catalyst and the ethylene carbonate is 0.001 ~ 0.005 ︰ 1.
In certain specific embodiments of the invention, it is preferable that the preparation method specific implementation is as follows：It will be connected with point
The reaction vessel of hydrophone vacuumizes, and is first replaced with protective gas, and then under the protective gas atmosphere, solvent, carbonic acid is added
Ethyl, selenium dioxide are heated to reflux water-dividing, after reaction, are cooled to room temperature, and decompression filters, a small amount of solvent of filter cake
Washing, merging filtrate and cleaning solution, then steam solvent, rectification under vacuum is to get the vinylene carbonate by its normal pressure.
In the present invention, the protective gas can be the inert gases such as nitrogen, argon gas.
Due to the implementation of above-mentioned technical proposal, the present invention has the following advantages that compared with prior art：
The preparation method of the vinylene carbonate of the present invention participates in reacting, while controlling dioxy by using selenium dioxide
The dosage for changing the dosage and solvent of selenium makes it that the more considerable vinylene carbonate of yield be made with ethylene carbonate single step reaction
Ester overcomes the bad influence that the by-product generated in conventional method brings environment and production equipment, while the present invention is anti-
Answer, separating-purifying it is simple, easy to operate, the vinylene carbonate purity of preparation can reach 99.9% or more, agree with well low
Cost, high yield, environmental protection, the current demand of safety.
Specific implementation mode
With reference to specific preferred embodiment, invention is further explained, but the present invention is not limited to following realities
Apply example.
In the following embodiments, unless otherwise specified, all raw materials are all from commercially available or are prepared with conventional method.
Embodiment 1
The 1L four-hole bottles for being connected with water knockout drum are vacuumized, nitrogen is replaced 3 times, in a nitrogen atmosphere, benzene 352g, carbonic acid is added
Ethyl 176g, selenium dioxide 333g；It is then heated to reflux water-dividing 36 hours, after reaction, is cooled to room temperature, decompression is taken out
Filter, filter cake are washed with a small amount of benzene, and then its normal pressure is steamed benzene by merging filtrate and cleaning solution, rectification under vacuum obtains product carbonic acid
Vinylene, yield 43.4%, purity 99.93%.
Embodiment 2
The 1L four-hole bottles for being connected with water knockout drum are vacuumized, nitrogen is replaced 3 times, in a nitrogen atmosphere, benzene 352g, carbonic acid is added
Ethyl 176g, selenium dioxide 333g and glacial acetic acid 0.24g, are heated to reflux water-dividing 30 hours, after reaction, are cooled to
Room temperature, decompression filter, and filter cake is washed with a small amount of benzene, and then its normal pressure is steamed benzene by merging filtrate and cleaning solution, rectification under vacuum obtains
To product vinylene carbonate, yield 44.1%, purity 99.95%.
Embodiment 3
The 1L four-hole bottles for being connected with water knockout drum are vacuumized, nitrogen is replaced 3 times, in a nitrogen atmosphere, benzene 352g, carbonic acid is added
Ethyl 176g, selenium dioxide 333g and glacial acetic acid 0.3g, are heated to reflux water-dividing 24 hours, after reaction, are cooled to
Room temperature, decompression filter, and filter cake washs merging filtrate and cleaning solution with a small amount of benzene, its normal pressure is then steamed benzene, and rectification under vacuum obtains
To product vinylene carbonate, yield 45.1%, purity 99.95%.
Comparative example
The 1L four-hole bottles for being connected with water knockout drum are vacuumized, nitrogen is replaced 3 times, in a nitrogen atmosphere, acetone 352g, carbon is added
Sour ethyl 176g, selenium dioxide 222g and benzoic acid 1.2g, are heated to reflux water-dividing 20 hours, are cooled to room temperature, decompression
It filters, filter cake is washed with a small amount of acetone, and then its normal pressure is steamed acetone by merging filtrate and cleaning solution, rectification under vacuum is produced
Product vinylene carbonate, yield 12%, purity 99.91%.
The present invention is described in detail above, its object is to allow the personage for being familiar with this field technology that can understand this
The content of invention is simultaneously implemented, and it is not intended to limit the scope of the present invention, and the present invention is not limited to above-mentioned implementations
, equivalent change or modification made by all Spirit Essences according to the present invention should be covered by the protection scope of the present invention.
Claims (7)
1. a kind of preparation method of vinylene carbonate, which is characterized in that the preparation method includes：Make ethylene carbonate and two
Selenium oxide in a solvent, the vinylene carbonate is obtained by the reaction under protective gas atmosphere, wherein the selenium dioxide with it is described
The molar ratio of ethylene carbonate is 1.3 ~ 1.7:1, the solvent is one kind in ethyl alcohol, methanol, the tert-butyl alcohol, benzene and acetone
Or a variety of combinations, the temperature of the reaction are the boiling point of the solvent.
2. the preparation method of vinylene carbonate according to claim 1, which is characterized in that the solvent and the carbonic acid
The mass ratio that feeds intake of ethyl is 1 ~ 5 ︰ 1.
3. the preparation method of vinylene carbonate according to claim 2, which is characterized in that the solvent and the carbonic acid
The mass ratio that feeds intake of ethyl is 1 ~ 3 ︰ 1.
4. the preparation method of vinylene carbonate according to claim 1, which is characterized in that the reaction time of the reaction
For 10 ~ 48h.
5. the preparation method of vinylene carbonate according to claim 1, which is characterized in that make the reaction in catalyst
In the presence of carry out, the catalyst be glacial acetic acid.
6. the preparation method of vinylene carbonate according to claim 5, which is characterized in that the catalyst and the carbon
The molar ratio of sour ethyl is 0.001 ~ 0.01 ︰ 1.
7. the preparation method of vinylene carbonate according to claim 1, which is characterized in that the preparation method is specifically real
It applies as follows：The reaction vessel for being connected with water knockout drum is vacuumized, is first replaced with protective gas, then in the protective gas atmosphere
Under, solvent, ethylene carbonate, selenium dioxide is added, is heated to reflux water-dividing, after reaction, is cooled to room temperature, decompression is taken out
Filter, filter cake are washed with a small amount of solvent, and then its normal pressure is steamed solvent, then carries out rectification under vacuum by merging filtrate and cleaning solution, i.e.,
Obtain the vinylene carbonate.
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Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110981848A (en) * | 2019-12-20 | 2020-04-10 | 泰兴华盛精细化工有限公司 | Production process of vinylene carbonate |
| CN111393403B (en) * | 2020-04-27 | 2021-11-26 | 苏州华一新能源科技有限公司 | Preparation method of vinylene carbonate |
| CN113816937B (en) * | 2021-11-23 | 2022-02-22 | 山东海科创新研究院有限公司 | Method for preparing vinylene carbonate |
| CN114957193B (en) * | 2022-05-11 | 2023-07-28 | 内蒙古源宏精细化工有限公司 | Method for green synthesis of vinylene carbonate |
| CN116693494B (en) * | 2023-05-22 | 2023-12-08 | 大连华一锂电科技有限公司 | Synthesis method of vinylene carbonate |
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Address after: 215433 GCL Middle Road, petrochemical District, taicanggang port, Suzhou City, Jiangsu Province Patentee after: Suzhou Huayi New Energy Technology Co.,Ltd. Address before: 215433 No.8, middle Xiexin Road, petrochemical District, taicanggang port area, Suzhou City, Jiangsu Province Patentee before: SUZHOU HUAYI NEW ENERGY TECHNOLOGY Co.,Ltd. |
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