CN101597275B - Method for purifying fluoroethylene carbonate - Google Patents
Method for purifying fluoroethylene carbonate Download PDFInfo
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- CN101597275B CN101597275B CN2009101157324A CN200910115732A CN101597275B CN 101597275 B CN101597275 B CN 101597275B CN 2009101157324 A CN2009101157324 A CN 2009101157324A CN 200910115732 A CN200910115732 A CN 200910115732A CN 101597275 B CN101597275 B CN 101597275B
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Abstract
The invention relates to a method for purifying fluoroethylene carbonate. The method ensures that fluoroethylene carbonate performs recrystallization in a mixed solvent of toluene and normal hexane at a temperature of between 30 DEG C below zero and 0 DEG C; and in the mixed solvent, the weight ratio of toluene to normal hexane is 1:1-10. After purification by the method, the content of the fluoroethylene carbonate is over 99.5 weight percent, and the acidity is below 0.005 percent, the fluoroethylene carbonate meets the requirement of lithium ion electrolyte additives, and the method has simple operation.
Description
Technical field
The invention belongs to the preparing technical field of fluoroethylene carbonate.
Background technology
Fluoroethylene carbonate, fusing point 17-19 ℃, 200 ℃ of boiling points, structural formula is:
When fluoroethylene carbonate uses as the lithium-ion battery electrolytes additive, require its content more than the 99.5wt% with acidity below 0.005%.At present, distillation method of purification commonly used can't be met the fluoroethylene carbonate that the lithium-ion electrolyte additive requires in the industry.
Summary of the invention
Technical problem to be solved by this invention provides a kind of purification process of fluoroethylene carbonate, and this method refining effect is good.
For solving above technical problem, the present invention takes following technical scheme:
A kind of purification process of fluoroethylene carbonate, this method comprise makes fluoroethylene carbonate in the mixed solvent of toluene and normal hexane, under-30-0 ℃, carries out the step of recrystallization, and in the mixed solvent, the weight ratio of toluene and normal hexane is 1: 1-10.
In the mixed solvent, the weight ratio of methane and normal hexane is preferably 1: 1-4.Behind the recrystallization, remove by filter mixed solvent, can get the crystal of fluoroethylene carbonate, during the temperature of this crystal more than the fusing point of fluoroethylene carbonate, change into liquid state.At this moment, but the fluoroethylene carbonate of liquid towards further purify, preferably, be that fluoroethylene carbonate is carried out underpressure distillation and collects the fluoroethylene carbonate cut, wherein, underpressure distillation is preferably carried out under vacuum tightness 500-1100Pa.
The present invention also will provide a kind of preparation method of fluoroethylene carbonate simultaneously, and this method is raw material with the ethylene carbonate, comprises the steps:
(1), make ethylene carbonate and simple substance fluoride at temperature 30-50 ℃, there is reaction down in nitrogen, obtains the bullion of fluoroethylene carbonate;
(2), adopt above-mentioned purification process that bullion is carried out purifying.
Fluoroethylene carbonate of the present invention also can prepare through following method: with the chlorocarbonic acid ethyl is raw material, at first makes chlorocarbonic acid ethyl and Sodium Fluoride in the presence of methylcarbonate and the Tetrabutyl amonium bromide, in reacting under 60-70 ℃ and after reaction finishes, removing methylcarbonate to obtain the bullion of fluoroethylene carbonate; Adopt above-mentioned purification process that the gained bullion is carried out purifying then.
Because the technique scheme utilization, the present invention compared with prior art has advantage:
Fluoroethylene carbonate after purification process of the present invention is purified, its purity and acidity can satisfy the requirement of lithium-ion electrolyte additive; In addition, purification process of the present invention is simple to operate.
Embodiment
Below in conjunction with concrete embodiment the present invention is done further detailed explanation, but be not limited to these embodiment.
Embodiment 1
According to the preparation method of the fluoroethylene carbonate of present embodiment, detailed process is following:
In 2000ml stainless steel pressure container, add 880 gram ethylene carbonates (content is 99wt%), load onto the uv lamp of 5W, connect stainless steel gas tube and device for absorbing tail gas; Be warmed up to 40 ℃, feeding 660g volume ratio is 1: 1 a delivery of fluorine/nitrogen mixed gas, and gas feeds and finishes; Obtain the bullion of 1011g fluorinated ethylene carbonate; Wherein, fluorinated ethylene carbonate content is 52.30wt%, and the acidity of bullion is 0.23%.
Embodiment 2
According to the preparation method of the fluoroethylene carbonate of present embodiment, detailed process is following:
In the four-hole boiling flask of 5000ml, configuration is stirred, condensing surface, adds Sodium Fluoride, 3000ml methylcarbonate and the 5 gram Tetrabutyl amonium bromides of 1680g; Stir, be warming up to 60 ℃, splash into the 1225g methylcarbonate; Reaction is finished, and methylcarbonate is removed in underpressure distillation, obtains the bullion of 980g fluorinated ethylene carbonate; Wherein the content of fluorinated ethylene carbonate is 75.62wt%, and the acidity of bullion is 1.3%.
Embodiment 3
According to following unified method; Make 50g embodiment 1 gained fluoroethylene carbonate bullion in the mixed solvent of the toluene of different ratios and normal hexane and under the temperature-10 ℃, carry out recrystallization; Underpressure distillation under vacuum tightness 665Pa-1064Pa then; The fluoroethylene carbonate cut of collecting 84-85 ℃ is as product, and the ratio of mixed solvent, consumption and product gas purity and acidity value are specifically seen the table 1 of Instructions Page 3.
Table 1
| Toluene (g) | Normal hexane (g) | Product (g) | Product purity (%) | Product acidity (%) |
| 25 | 25 | 12 | 99.91 | 0.0040 |
| 50 | 50 | 8 | 99.96 | 0.0036 |
| 75 | 75 | 5 | 99.95 | 0.0030 |
| 100 | 100 | 2 | 99.99 | 0.0028 |
| 33 | 66 | 14 | 99.97 | 0.0025 |
| 25 | 75 | 10 | 99.93 | 0.0045 |
| 20 | 80 | 8 | 99.94 | 0.0043 |
Embodiment 4
According to following unified method; Make 50g embodiment 2 gained fluoroethylene carbonate bullions in the mixed solvent of the toluene of different ratios and normal hexane and under 0 ℃ of the temperature, carry out recrystallization; Underpressure distillation under vacuum tightness 665Pa-1064Pa then; The fluoroethylene carbonate cut of collecting 84-85 ℃ is as product, and the ratio of mixed solvent, consumption and product gas purity and acidity value are specifically seen table 2.
| Toluene (g) | Normal hexane (g) | Product (g) | Product purity (%) | Product acidity (%) |
| 25 | 25 | 24 | 99.92 | 0.0048 |
| 50 | 50 | 20 | 99.93 | 0.0040 |
| 75 | 75 | 6 | 99.94 | 0.0042 |
| 100 | 100 | 5 | 99.94 | 0.0038 |
| 33 | 66 | 27 | 99.95 | 0.0036 |
| 25 | 75 | 20 | 99.94 | 0.0040 |
| 20 | 80 | 15 | 99.94 | 0.0042 |
Visible from table 1 and table 2, purification process refining effect of the present invention is good, and in the product after it is purified, fluoroethylene carbonate purity and acidity all can satisfy the requirement of lithium-ion electrolyte additive.
Above-described only is preferred implementation of the present invention.Should be pointed out that for the person of ordinary skill of the art, under the prerequisite that does not break away from patent principle of the present invention; Can also make some distortion and improvement; For example, according to the general knowledge of this area, in order further to improve the effect of purifying; Described re-crystallization step can be carried out once or repeatedly, these also should be regarded as belonging to protection scope of the present invention.
Claims (4)
1. the purification process of a fluoroethylene carbonate; It is characterized in that: this method comprises makes fluoroethylene carbonate in the mixed solvent of toluene and normal hexane; Under-30-0 ℃, carry out the step of recrystallization; In the described mixed solvent, the weight ratio of toluene and normal hexane is 1: 1-4, this method also comprises the step of the fluoroethylene carbonate of re-crystallization step gained being carried out underpressure distillation.
2. purification process according to claim 1 is characterized in that: described underpressure distillation is carried out under vacuum tightness 500-1100Pa.
3. the preparation method of a fluoroethylene carbonate, it is characterized in that: with the ethylene carbonate is raw material, comprises the steps:
(1), make ethylene carbonate and simple substance fluoride at temperature 30-50 ℃, there is reaction down in nitrogen, obtains the bullion of fluoroethylene carbonate;
(2), the described purification process of arbitrary claim carries out purifying to step (1) gained bullion among the employing claim 1-2.
4. the preparation method of a fluoroethylene carbonate, it is characterized in that: with the chlorocarbonic acid ethyl is raw material, comprises the steps:
(1), make chlorocarbonic acid ethyl and Sodium Fluoride in the presence of methylcarbonate and the Tetrabutyl amonium bromide, in reacting under 60-70 ℃ and after reaction finishes, removing methylcarbonate to obtain the bullion of fluoroethylene carbonate;
(2), the described purification process of arbitrary claim carries out purifying to step (1) gained bullion among the employing claim 1-2.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009101157324A CN101597275B (en) | 2009-07-16 | 2009-07-16 | Method for purifying fluoroethylene carbonate |
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| CN2009101157324A CN101597275B (en) | 2009-07-16 | 2009-07-16 | Method for purifying fluoroethylene carbonate |
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| CN101597275A CN101597275A (en) | 2009-12-09 |
| CN101597275B true CN101597275B (en) | 2012-05-30 |
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Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105541783A (en) * | 2015-12-28 | 2016-05-04 | 苏州华一新能源科技有限公司 | Production method of high-purity fluoroethylene carbonate |
| CN107033119B (en) * | 2017-04-06 | 2019-10-11 | 多氟多化工股份有限公司 | A kind of preparation method of high-purity fluorinated ethylene carbonate |
| CN113121491A (en) * | 2020-01-16 | 2021-07-16 | 中国科学院宁波材料技术与工程研究所 | Method for producing fluoroethylene carbonate through micro-channel |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000309583A (en) * | 1999-04-28 | 2000-11-07 | Kanto Denka Kogyo Co Ltd | Production of 4-fluoro-1,3-dioxolan-2-one |
| JP2007008826A (en) * | 2005-06-28 | 2007-01-18 | Central Glass Co Ltd | Method for producing high-purity 4-fluoro-1,3-dioxolan-2-one |
| JP2007008825A (en) * | 2005-06-28 | 2007-01-18 | Central Glass Co Ltd | Method for producing high-purity 4-fluoro-1,3-dioxolan-2-one |
| CN101066965A (en) * | 2007-06-01 | 2007-11-07 | 张家港市华盛化学有限公司 | Prepn process of fluoric cyclic carbonate |
-
2009
- 2009-07-16 CN CN2009101157324A patent/CN101597275B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000309583A (en) * | 1999-04-28 | 2000-11-07 | Kanto Denka Kogyo Co Ltd | Production of 4-fluoro-1,3-dioxolan-2-one |
| JP2007008826A (en) * | 2005-06-28 | 2007-01-18 | Central Glass Co Ltd | Method for producing high-purity 4-fluoro-1,3-dioxolan-2-one |
| JP2007008825A (en) * | 2005-06-28 | 2007-01-18 | Central Glass Co Ltd | Method for producing high-purity 4-fluoro-1,3-dioxolan-2-one |
| CN101066965A (en) * | 2007-06-01 | 2007-11-07 | 张家港市华盛化学有限公司 | Prepn process of fluoric cyclic carbonate |
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Address after: 215433 Jiangsu city of Taicang province Taicang port Petrochemical Zone GCL Road Patentee after: SUZHOU HUAYI NEW ENERGY TECHNOLOGY CO., LTD. Address before: 215433 Jiangsu city of Taicang province Taicang port Petrochemical Zone GCL Road Patentee before: Taichang Huayi Chemical Technology Co., Ltd. |
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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 Jiangsu city of Taicang province Taicang port Petrochemical Zone GCL Road Patentee before: SUZHOU HUAYI NEW ENERGY TECHNOLOGY Co.,Ltd. |
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