CN101210005B - Method for preparing fluoroethylene carbonate - Google Patents
Method for preparing fluoroethylene carbonate Download PDFInfo
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- CN101210005B CN101210005B CN2006101560684A CN200610156068A CN101210005B CN 101210005 B CN101210005 B CN 101210005B CN 2006101560684 A CN2006101560684 A CN 2006101560684A CN 200610156068 A CN200610156068 A CN 200610156068A CN 101210005 B CN101210005 B CN 101210005B
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- vinyl acetate
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- ethylene carbonate
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Abstract
The invention discloses a method for preparing fluoroethylene carbonate with relatively short reaction time, relatively high yield and relatively low cost; the invention essentially comprise the following steps that: 1. fluoride and phase transfer catalyst are added into a reaction vessel; 2. chloroethylenes carbonate is added into the reaction vessel, all the reactants are subject to reaction in the reaction vessel, thus obtaining the mixture containing fluoroethylene carbonate; 3. the fluoroethylene carbonate in the mixture is solid-liquid separated and extracted by distillation, thus acquiring fluoroethylene carbonate with needed purity. By adopting the preparation method of the invention, the fluoroethylene carbonate with high yield can be obtained under a mild reaction condition and in relatively short reaction time. Additionally, the invention is more economical and more environment friendly and can use relatively cheap original materials, thus reducing production cost. The invention can be used for preparing fluoroethylene carbonate.
Description
Technical field
The present invention relates to the ethylene carbonate ester derivative that contains fluorine atom, the preparation method who refers in particular to fluorinated ethylene carbonate.
Background technology
Fluorinated ethylene carbonate (F-EC), English name: Fluoroethylene carbonate, chemical name: 4-Fluoro-1,3-dioxolan-2-one.It can be used as medicine, pesticide intermediate and lithium-ion battery electrolytes additive.
USP Pat.No.6 has introduced a kind of compound method of synthesizing fluoroethylene carbonate in 010,806, and the route of use is dimethyl carbonate and 3,3, and 3-three fluoro-1,2-third rare oxide compound are synthetic under the condition that sodium hydrogencarbonate exists.3,3 of present method use, 3-three fluoro-1, the price of 2-third rare oxide compound is very high, and the reaction times is very long, needs 8-40 hour, and this has just seriously limited the industriallization of present method.
Introduced the method for using chlorocarbonic acid vinyl acetate and Potassium monofluoride prepared in reaction fluorinated ethylene carbonate among the International Patent Application Publication No. WO 98/15024.This method is not used phase-transfer catalyst, causes very high temperature of reaction needed and very long reaction times, and transformation efficiency is also very low, finally causes being difficult to obtain highly purified fluorinated ethylene carbonate product.
Using the fluorine gas and the mixed gas of nitrogen also is an important method of preparation fluorinated ethylene carbonate with the NSC 11801 reaction, and the raw material that this method is used is fluorine gas, and fluorine gas toxicity height not only, and the reactive behavior height, react be easy to out of control.Because the violent heating of reaction is easy to cause the reaction vessel internal pressure higher, occur dangerously, and fluorine gas has severe toxicity, and corrodibility is strong, and is very high for the requirement of conversion unit.
Summary of the invention
The technical problem that the present invention will solve is: the preparation method that the fluorinated ethylene carbonate that a kind of reaction times is short, yield is higher and cost is relatively low is provided.
For solving the problems of the technologies described above, the technical scheme that the present invention adopts is: the preparation method of described a kind of fluorinated ethylene carbonate comprises the steps:
One, fluorochemical and phase-transfer catalyst are joined in the reaction vessel; Two and then add the chlorocarbonic acid vinyl acetate, above-mentioned each reactant is reacted in reaction vessel, finally obtain containing the mixture of fluorinated ethylene carbonate; Three, the fluorinated ethylene carbonate in the said mixture is purified, obtain the fluorinated ethylene carbonate of required purity.
The above-mentioned chlorocarbonic acid vinyl acetate and the mol ratio of fluorochemical are: 1.0: 1.0～1.0: 1.2, the adding quality of phase-transfer catalyst was chlorocarbonic acid vinyl acetate and fluorochemical total mass 0.01～0.5 times.
Above-mentioned fluorochemical representes that with molecular formula MF wherein: M is basic metal or NH4; Described phase-transfer catalyst is crown ether or polyoxyethylene glycol.Wherein, described crown ether is preferably 12-hat-6～18-hat-6, and the polymerization degree of described polyoxyethylene glycol is preferably between 400～2000.
Temperature is controlled between 10 ℃～200 ℃ in the process of dropping chlorocarbonic acid vinyl acetate in above-mentioned steps two; Be preferably 50 ℃～70 ℃.Dropwise the back temperature and be controlled at 10 ℃～200 ℃, be preferably 90 ℃～110 ℃.
Among the present invention, above-mentioned chlorocarbonic acid vinyl acetate can be represented with following structural formula:
Described fluorinated ethylene carbonate can be represented with following chemical structural formula:
Among the present invention, the purity of described chlorocarbonic acid vinyl acetate can select to be not less than 60%, and when actual fabrication, can select purity is about 70～80% chlorocarbonic acid vinyl acetate.
Among the present invention, the method for in the above-mentioned steps three fluorinated ethylene carbonate in the mixture being purified is: earlier mixture is carried out solid-liquid separation, and then the reaction solution that separation obtains is carried out rectification and purification.
Advantage of the present invention is: use preparation method of the present invention, can under the reaction conditions of gentleness, in the short reaction times, obtain the fluorinated ethylene carbonate of high yield.In addition, it is more economical, more friendly to environment, and can utilize relatively cheap parent material, has reduced production cost.
Embodiment
Below in conjunction with specific embodiment the present invention is done further description.
The comparative example one:
Be furnished with tap funnel, adding the 42g Sodium Fluoride in the three neck round-bottomed flasks of condensing surface, whisking appliance and TM and stir, dripping 122.5g chlorocarbonic acid vinyl acetate then; The control dropping temperature is 50-70 ℃; Along with the carrying out that drips, the color of mixture becomes dun, and heat release heats up voluntarily; After dropwising, mixture is thickness very.After 3 hours, cooled materials to 30 ℃ is used centrifugal suction filtration then 100 ℃ of insulations, obtains black filtrating, wherein contains 41% responseless chlorocarbonic acid vinyl acetate, the impurity of bringing in 55% fluorinated ethylene carbonate and other raw materials.
Can find through this comparative example, not use phase-transfer catalyst to react just can not react very thorough.
Embodiment two:
Be furnished with tap funnel, adding the 44g Sodium Fluoride in the three neck round-bottomed flasks of condensing surface, whisking appliance and TM and stir, adding 3.4g polyoxyethylene glycol phase-transfer catalyst (polymerization degree 800); Drip 122.5g chlorocarbonic acid vinyl acetate then, the control dropping temperature is 50-70 ℃, along with the carrying out that drips; The color of mixture becomes dun; Heat release heats up voluntarily, and after dropwising, mixture is thickness very.After 3 hours, cooled materials to 30 ℃ is used centrifugal suction filtration then 100 ℃ of insulations, obtains black filtrating, wherein contains 0.5% responseless chlorocarbonic acid vinyl acetate, the impurity of bringing in 92% fluorinated ethylene carbonate and other raw materials.Black filtrating is carried out rectification under vacuum, finally obtain purity and be 99.9% product 59g.
Contrast through present embodiment and comparative example one can find, uses phase-transfer catalyst, and reaction can be soon, carry out very up hill and dale.
Embodiment three:
This embodiment is an interpolation order of having put upside down material among the embodiment two.That is: will add 2.8g polyoxyethylene glycol phase-transfer catalyst (polymerization degree 800) and 122.5g chlorocarbonic acid vinyl acetate earlier and mix, under 40 ℃, progressively the 42g sodium fluoride powder progressively added in the above-mentioned mixed solution then through funnel; Adding speed is wanted slowly, and control reaction temperature is 50-70 ℃, adds in 2 hours; Other steps are identical with embodiment two situation, at insulation material very thickness that becomes after 3 hours, and cooled materials to 30 ℃; Use centrifugal suction filtration then; Obtain black filtrating, wherein contain 4% responseless chlorocarbonic acid vinyl acetate, the impurity of bringing in 89% fluorinated ethylene carbonate and other raw materials.Black filtrating is carried out rectification under vacuum, finally obtain purity and be 99.5% product 41g.
Compare and can find with embodiment two through present embodiment, in reaction process, the chlorocarbonic acid vinyl acetate is joined in the Sodium Fluoride, effect is better than Sodium Fluoride being added in the chlorocarbonic acid vinyl acetate.
Embodiment four:
In this embodiment; Is being furnished with tap funnel; Add the 42g Sodium Fluoride during three neck round-bottomed flasks of condensing surface, whisking appliance and TM and 1.7g is preced with 18 ethers, drip 122.5g chlorocarbonic acid vinyl acetate then, product has exothermic phenomenon; The control dropping temperature is 50-70 ℃, then 100 ℃ of insulation reaction 3 hours.Insulation is carried out suction filtration after finishing, and gets filtrating and carries out stratographic analysis, and chlorocarbonic acid vinyl acetate content is 1%; 91% fluorinated ethylene carbonate; All the other are the not clear impurity that band is come in the raw material, then filtrating are carried out rectification under vacuum, finally obtain purity and be 99.8% finished product 57g.
Can find to use polyoxyethylene glycol phase-transfer catalyst effect the same through present embodiment with crown ether-like transfer catalyst effect.
Embodiment five:
Be furnished with tap funnel, adding the 44g Sodium Fluoride in the three neck round-bottomed flasks of condensing surface, whisking appliance and TM and stir, adding 2.5g polyoxyethylene glycol phase-transfer catalyst (polymerization degree 800); Drip 122.5g chlorocarbonic acid vinyl acetate then, the control dropping temperature is 50-70 ℃, along with the carrying out that drips; The color of mixture becomes dun; Heat release heats up voluntarily, and after dropwising, mixture is thickness very.After 3 hours, cooled materials to 30 ℃ is used centrifugal suction filtration then 150 ℃ of insulations, obtains black filtrating, wherein contains 0.5% responseless chlorocarbonic acid vinyl acetate, the impurity of bringing in 81% fluorinated ethylene carbonate and other raw materials.Black filtrating is carried out rectification under vacuum, finally obtain purity and be 99.9% product 28g.
Can find that through present embodiment holding temperature is too high, side reaction increases, and product yield reduces.
Embodiment six:
Be furnished with tap funnel, adding the 44g Sodium Fluoride in the three neck round-bottomed flasks of condensing surface, whisking appliance and TM and stir, adding 2.1g polyoxyethylene glycol phase-transfer catalyst (polymerization degree 800); Drip 122.5g chlorocarbonic acid vinyl acetate (purity 68%) then, the control dropping temperature is 50-70 ℃, along with the carrying out that drips; The color of mixture becomes dun, and has a large amount of irritating gases to generate, and material heat release voluntarily heats up; After dropwising, mixture is thickness very.After 3 hours, cooled materials to 30 ℃ is used centrifugal suction filtration then 100 ℃ of insulations, obtains black filtrating, wherein contains 0.5% responseless chlorocarbonic acid vinyl acetate, the impurity of bringing in 64% fluorinated ethylene carbonate and other raw material.Black filtrating is carried out rectification under vacuum, finally obtain purity and be 95% product 41g.
Can find that through present embodiment the purity of chlorocarbonic acid vinyl acetate is too low, product gas purity and yield can receive very big influence.
Embodiment seven:
Be furnished with tap funnel, adding the 44g Sodium Fluoride in the three neck round-bottomed flasks of condensing surface, whisking appliance and TM and stir, adding 2.1g polyoxyethylene glycol phase-transfer catalyst (polymerization degree 800); Drip 122.5g chlorocarbonic acid vinyl acetate (purity 68%) then, do not control dropping temperature, material heat release voluntarily is warmed up to 170 ℃; Urgent cooling along with the rising of temperature, has a large amount of irritating gases to generate in the material; After dropwising, mixture is thickness very.After 3 hours, cooled materials to 30 ℃ is used centrifugal suction filtration then 100 ℃ of insulations, obtains black filtrating, wherein contains 0.5% responseless chlorocarbonic acid vinyl acetate, the impurity of bringing in 84% fluorinated ethylene carbonate and other raw material.Black filtrating is carried out rectification under vacuum, finally obtain purity and be 97% product 31g.
Can find through present embodiment,, be easy to occur the too fast situation of temperature of reaction rising, reduce product yield on the one hand, also can cause danger on the one hand in addition if do not control dropping temperature.
Claims (7)
1. the preparation method of a fluorinated ethylene carbonate comprises the steps:
One, fluorochemical and phase-transfer catalyst are joined in the reaction vessel; Two and then add the chlorocarbonic acid vinyl acetate, above-mentioned each reactant is reacted in reaction vessel, finally obtain containing the mixture of fluorinated ethylene carbonate; Three, the fluorinated ethylene carbonate in the said mixture is purified, obtain the fluorinated ethylene carbonate of required purity;
Described fluorochemical representes that with molecular formula MF wherein: M is a basic metal; Described phase-transfer catalyst is crown ether or polyoxyethylene glycol.
2. preparation method according to claim 1; It is characterized in that: the mol ratio of described chlorocarbonic acid vinyl acetate and fluorochemical is: 1.0: 1.0～1.0: 1.2, the adding quality of phase-transfer catalyst was chlorocarbonic acid vinyl acetate and fluorochemical total mass 0.01～0.5 times.
3. preparation method according to claim 1 and 2 is characterized in that: described crown ether is 12-hat-6 or 18-hat-6, and the polymerization degree of described polyoxyethylene glycol is between 400～2000.
4. preparation method according to claim 1 and 2 is characterized in that: temperature is controlled between 10 ℃～200 ℃ in the process that drips the chlorocarbonic acid vinyl acetate; Dropwise the back temperature and be controlled at 10 ℃～200 ℃.
5. preparation method according to claim 4 is characterized in that: temperature is controlled between 50 ℃～70 ℃ in the process that drips the chlorocarbonic acid vinyl acetate; Dropwise the back temperature and be controlled at 90 ℃～110 ℃.
6. preparation method according to claim 1 and 2 is characterized in that: the purity of described chlorocarbonic acid vinyl acetate is not less than 60%.
7. preparation method according to claim 1 and 2 is characterized in that: the method for in the step 3 fluorinated ethylene carbonate in the mixture being purified is: earlier mixture is carried out solid-liquid separation, and then the reaction solution that separation obtains is carried out rectification and purification.
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| CN2006101560684A CN101210005B (en) | 2006-12-30 | 2006-12-30 | Method for preparing fluoroethylene carbonate |
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| CN2006101560684A CN101210005B (en) | 2006-12-30 | 2006-12-30 | Method for preparing fluoroethylene carbonate |
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| CN101210005B true CN101210005B (en) | 2012-07-25 |
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Families Citing this family (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5358974B2 (en) * | 2008-02-28 | 2013-12-04 | ダイキン工業株式会社 | Method for producing fluorinated 1,3-dioxolan-2-one |
| CN101676282A (en) * | 2008-09-16 | 2010-03-24 | 中国科学院福建物质结构研究所 | Method for synthesizing fluorinated ethylene carbonate |
| CN101717391B (en) * | 2009-11-09 | 2013-09-25 | 中国海洋石油总公司 | Method for preparing fluoroethylene carbonate |
| CN102060838A (en) * | 2010-12-31 | 2011-05-18 | 浙江华晶氟化学科技有限公司 | Method for preparing fluoroethylene carbonate |
| CN102993160B (en) * | 2012-09-26 | 2014-05-07 | 中国海洋石油总公司 | Synthetic method of fluoro ethylene carbonate |
| CN102977070B (en) * | 2012-12-21 | 2014-06-25 | 王学军 | Preparation method of fluoroethylene carbonate |
| CN105481822A (en) * | 2015-12-14 | 2016-04-13 | 苏州华一新能源科技有限公司 | Method for preparing fluoroethylene carbonate |
| CN112321558B (en) * | 2020-11-10 | 2023-03-14 | 湖北省宏源药业科技股份有限公司 | Preparation method of fluoroethylene carbonate |
| CN112500387B (en) * | 2020-12-21 | 2022-04-22 | 苏州华一新能源科技股份有限公司 | Preparation method of fluoroethylene carbonate |
| CN114163412B (en) * | 2021-11-30 | 2023-03-14 | 苏州华一新能源科技股份有限公司 | Preparation process of fluoroethylene carbonate and lithium battery applying fluoroethylene carbonate |
| CN114805281B (en) * | 2022-05-17 | 2023-06-06 | 苏州华一新能源科技股份有限公司 | Preparation method of 1, 2-difluoro ethylene carbonate |
| CN114835671A (en) * | 2022-06-02 | 2022-08-02 | 泰兴华盛精细化工有限公司 | Production process of high-purity fluoroethylene carbonate |
| CN116396264A (en) * | 2023-03-03 | 2023-07-07 | 山东惟普新能源有限公司 | Method for preparing fluoroethylene carbonate by solvent-free one-pot method |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1810764A (en) * | 2005-01-24 | 2006-08-02 | 蔚山化学株式会社 | Manufacturing method and apparatus of 4-fluoroethylene carbonate |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1810764A (en) * | 2005-01-24 | 2006-08-02 | 蔚山化学株式会社 | Manufacturing method and apparatus of 4-fluoroethylene carbonate |
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Address after: 215600 No.35 Nanhai Road, Jiangsu Yangzijiang International Chemical Industrial Park, Zhangjiagang, Suzhou, Jiangsu Province Patentee after: Zhangjiagang Guotai-Huarong New Chemical Materials Co.,Ltd. Address before: 215631 Jiangsu province Zhangjiagang City gold town after Cheng Cheng Road No. 112 Patentee before: Zhangjiagang Guotai-Huarong New Chemical Materials Co.,Ltd. |