CN101870687A - Method for synthesizing fluoroethylene carbonate by phase-transfer catalysis - Google Patents
Method for synthesizing fluoroethylene carbonate by phase-transfer catalysis Download PDFInfo
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- CN101870687A CN101870687A CN200910111559A CN200910111559A CN101870687A CN 101870687 A CN101870687 A CN 101870687A CN 200910111559 A CN200910111559 A CN 200910111559A CN 200910111559 A CN200910111559 A CN 200910111559A CN 101870687 A CN101870687 A CN 101870687A
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Abstract
The invention relates to a method for synthesizing fluoroethylene carbonate by phase-transfer catalysis. The fluoroethylene carbonate is produced by performing halogen exchange reaction on chloroethylene carbonate and potassium fluoride under the catalysis of crown ether serving as a phase-transfer catalyst in aprotic solvent.
Description
Technical field
The present invention relates to a kind of method of synthesizing fluoroethylene carbonate by phase-transfer catalysis.Saying so about the chlorocarbonic acid vinyl acetate in detailed ground, carries out halogen exchange reaction with Potassium monofluoride under the katalysis of phase-transfer catalyst crown ether in aprotic solvent, generates the method for fluorinated ethylene carbonate.This fluorinated ethylene carbonate can be used as the additive of electrolyte of lithium-ion secondary battery, and the ring longevity that is used to improve battery is followed life and improves the safety performance of battery.
Background technology
The fluorinated ethylene carbonate of indication of the present invention is the compound with following structure.
(J.Power Sources 1999,81～82:20) waits fluorinated ethylene carbonate is added to 1mol/L LiPF McMillan R
6Capability retention is 73% behind the/PC+EC electrolyte system, battery circulation 200 times, and battery circuit efficient reaches 100%, battery cycle life is improved, because fluorine had both had the cathode film formation effect, has fire retardation again, so the security of battery is improved.Though do not contain two keys in the fluorinated ethylene carbonate, but it can lose the hydrogen fluoride of a part and form VC, and the film for additive of a kind of excellent property that VC is everybody to generally acknowledge, HF can improve the cyclicity of lithium ion again effectively, so fluorinated ethylene carbonate can play a kind of dual function, thus the safety performance of raising battery.Also just because of this unique effects of fluorinated ethylene carbonate be applied in lithium cell producers such as Korea S, Japan at present.
Mostly the present suitability for industrialized production of fluorinated ethylene carbonate is to adopt fluorine gas directly to fluoridize the method for replacement.As: [J.Fluorine Chemistry 120 (2003) 105～110] F such as Masafumi Kobayashi with 30%
2/ N
2Mixed gas directly carries out the fluorine substitution reaction to NSC 11801 under 50 ℃ condition, and the product fluorinated ethylene carbonate can further carry out the fluorine substitution reaction with this understanding, generates multiple polyfluoride by product.Japanese Patent JP2000-309583 has also adopted similar methods.But this method is difficult to the carrying out of control reaction, and equipment is had special requirement, and is also very high to the requirement that generates technology, and the aftertreatment of excessive fluorine gas is also pretty troublesome, otherwise is easy to take place security incident.
Also mentioned the synthetic method of another in the document, [Tetrahedron57 (2001) 9067～9072] such as Hideki Ishii adopt the partially fluorinated method of electrochemistry, with vinylene carbonate (VC) is starting raw material, synthesized fluorinated ethylene carbonate through two-step reaction, and this method productive rate is low, the cost height is not suitable for suitability for industrialized production.
Summary of the invention
On synthetic, utilize the permutoid reaction of carrying out halogen atom between Organohalogen compounds and the inorganic halides usually, prepare idohydrocarbon or hydrofluoric ether that some directly is difficult to obtain with halogenation method.
Because halogen exchange fluorination is the reaction between inorganic solid phase and the organic liquid phase, fluorizating agent is dissolved in reaction system again hardly, and speed of response is very limited, and adds phase-transfer catalyst, can improve speed of response greatly.
Crown ether is that a class contains organic ring in " hole ", and its hole can hold reactant ion, thereby forms complex compound.This complex compound dissolves in reaction medium, and carries out permutoid reaction between two-phase, and crown ether can be as the phase-transfer catalyst of reaction between the solid-liquid phase.
Crown ether can increase the solubleness of alkaline metal fluoride cpd in non-polar organic solvent, thereby improves F
-Concentration.The solubleness of KF in solvent improves greatly after adding crown ether.
Crown ether can increase F
-The nucleophilicity of (exposed fluorion).This effect of crown ether can make F
-Finish Sn2 smoothly and replace, not only can shorten the reaction times, and can improve reaction yield.
Based on above principle, the present inventor has obtained the operational path of an advantages of simplicity and high efficiency synthesizing fluoroethylene carbonate finally through exploring with keen determination.
The inventive method is a starting raw material with the industrial chlorocarbonic acid vinyl acetate (Cl-EC) that obtains easily, in appropriate solvent, under the catalysis of phase-transfer catalyst crown ether, carries out halogen exchange fluorination with Potassium monofluoride, thereby finishes the present invention.
Further instruction, appropriate solvent of the present invention is meant aprotic solvent, comprises sulfone compound methyl-sulphoxide, tetramethylene sulfone, nitrile compounds acetonitrile, propionitrile, butyronitrile, ketone compounds acetone, butanone.Can use one or more mixed solvent.
In fluorinated ethylene carbonate synthetic, the amount of solvent for use is 1～10 times of chlorocarbonic acid vinyl acetate volume.
Chlorocarbonic acid vinyl acetate and Potassium monofluoride carry out halogen exchange fluorination under the effect of phase-transfer catalyst in aprotic solvent, generate fluorinated ethylene carbonate.Phase-transfer catalyst is meant crown compound among the present invention, preferred 18-hat-6.
In fluorinated ethylene carbonate synthetic, the add-on of phase-transfer catalyst crown ether is 0.001～0.1 times of chlorocarbonic acid vinyl acetate molar weight.
This with the catalytic halogen exchange fluorination of phase-transfer catalyst, chlorocarbonic acid vinyl acetate efficiently high productivity is converted into fluorinated ethylene carbonate.
Embodiment
The invention will be further described below by specific embodiment, but the present invention not only is defined in these examples.
Embodiment 1:
In 1000 milliliters of there-necked flasks of exsiccant, add 245 gram chlorocarbonic acid vinyl acetate, add 400 milliliters of butanone simultaneously, 170 gram Potassium monofluorides, 1 gram 18-hat-6, reacting by heating, reaction is 4 hours under reflux temperature, after reaction finishes, and cooling, filter, filtrate is used gas chromatographic analysis, and analytical results shows has 80.5% chlorocarbonic acid vinyl acetate to react, and the selectivity of fluorinated ethylene carbonate is 85.4%.
Embodiment 2:
In 1000 milliliters of there-necked flasks of exsiccant, add 245 gram chlorocarbonic acid vinyl acetate, add 350 milliliters of butanone simultaneously, 170 gram Potassium monofluorides, 1.5 gram 18-hats-6, reacting by heating, reacted 7 hours down at 80 ℃, after reaction finishes, cooling, filter, filtrate is used gas chromatographic analysis, and analytical results shows has 85.3% chlorocarbonic acid vinyl acetate to react, and the selectivity of fluorinated ethylene carbonate is 82.7%.
Embodiment 3:
In the there-necked flask of 1500 milliliters of exsiccant, add 375 gram chlorocarbonic acid vinyl acetate, add 350 milliliters of acetonitriles simultaneously, 250 gram Potassium monofluorides, 2.0 gram 18-hats-6, reacting by heating was 90 ℃ of following back flow reaction 5 hours.After reaction finished, cooling was filtered, and filtrate is used gas chromatographic analysis, and analytical results shows has 82.6% chlorocarbonic acid vinyl acetate to react, and the selectivity of fluorinated ethylene carbonate is 85.3%.
Embodiment 4:
In 2000 milliliters of there-necked flasks of exsiccant, add 750 and restrain the chlorocarbonic acid vinyl acetate, add 1000 milliliters of methyl-sulphoxides simultaneously, 450 gram Potassium monofluorides, 4.0 gram 18-hats-6, reacting by heating was reacted 4 hours down at 100 ℃.After reaction finished, cooling was filtered, and filtrate is used gas chromatographic analysis, and analytical results shows has 85.8% chlorocarbonic acid vinyl acetate to react, and the selectivity of fluorinated ethylene carbonate is 78.5%.
Embodiment 5:
In 5000 milliliters of there-necked flasks of exsiccant, add 1500 gram chlorocarbonic acid vinyl acetate, add 3000 milliliters of butanone simultaneously, 900 gram Potassium monofluorides, 7.5 gram 18-hats-6, reacting by heating, reaction is 5 hours under reflux temperature.After reaction finished, cooling was filtered, and filtrate is used gas chromatographic analysis, and analytical results shows has 80.4% chlorocarbonic acid vinyl acetate to react, and the selectivity of fluorinated ethylene carbonate is 83.6%.
Claims (6)
1. the method for a synthesizing fluoroethylene carbonate by phase-transfer catalysis comprises the steps: in aprotic solvent, and the chlorocarbonic acid vinyl acetate is carried out halogen exchange reaction with Potassium monofluoride under the catalysis of phase-transfer catalyst crown ether, generates fluorinated ethylene carbonate.
2. the method for synthesizing fluoroethylene carbonate by phase-transfer catalysis as claimed in claim 1 is characterized in that: described aprotic solvent is selected from one or more mixed solvent of ketone, nitrile or sulfone compound.
3. the synthetic method of fluorinated ethylene carbonate as claimed in claim 1 or 2 is characterized in that: described aprotic solvent is selected from one or more the mixed solvent in acetone, butanone, methyl propyl ketone, acetonitrile, propionitrile, butyronitrile, methyl-sulphoxide or the tetramethylene sulfone.
4. the synthetic method of fluorinated ethylene carbonate as claimed in claim 1 or 2, it is characterized in that: the amount of described aprotic solvent is 1～10 times of described chlorocarbonic acid vinyl acetate volume.
5. the synthetic method of fluorinated ethylene carbonate as claimed in claim 1 is characterized in that: described phase-transfer catalyst crown ether is a 18-hat-6.
6. the synthetic method of fluorinated ethylene carbonate as claimed in claim 1, it is characterized in that: the add-on of described phase-transfer catalyst crown ether is 0.001～0.1 times of described chlorocarbonic acid vinyl acetate molar weight.
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| CN200910111559A CN101870687A (en) | 2009-04-24 | 2009-04-24 | Method for synthesizing fluoroethylene carbonate by phase-transfer catalysis |
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102134227A (en) * | 2010-12-31 | 2011-07-27 | 上海康鹏化学有限公司 | Preparation method of fluoroethylene carbonate |
| CN102766130A (en) * | 2012-07-18 | 2012-11-07 | 太仓华一化工科技有限公司 | Preparation method of difluoroethylene carbonate |
| CN102875520A (en) * | 2012-09-25 | 2013-01-16 | 中国海洋石油总公司 | Synthetic method of fluoro carbonic ester |
| CN102875521A (en) * | 2012-09-27 | 2013-01-16 | 中国海洋石油总公司 | Method for preparing fluoro-carbonate ester by means of phase-transfer catalysis |
| CN102993160A (en) * | 2012-09-26 | 2013-03-27 | 中国海洋石油总公司 | Synthetic method of fluoro ethylene carbonate |
| CN103044384A (en) * | 2011-10-17 | 2013-04-17 | 张家港市国泰华荣化工新材料有限公司 | Preparation method of 3-fluorine-1, 3-propane sulfonic acid lactone |
| CN105541789A (en) * | 2015-12-31 | 2016-05-04 | 石家庄圣泰化工有限公司 | Method for preparing ethylene sulfate derivative |
| CN105646632A (en) * | 2016-01-19 | 2016-06-08 | 浙江新和成股份有限公司 | Method for preparing 7-dehydrogenized cholesteryl ester from 7-tosylhydrazones-3-cholesteryl ester |
| CN110775990A (en) * | 2019-10-27 | 2020-02-11 | 淮安瀚康新材料有限公司 | Method for treating fluoroethylene carbonate solid waste |
| CN112500387A (en) * | 2020-12-21 | 2021-03-16 | 苏州华一新能源科技有限公司 | Preparation method of fluoroethylene carbonate |
| CN114621177A (en) * | 2022-02-24 | 2022-06-14 | 浙江诺亚氟化工有限公司 | Preparation method of fluoroethylene carbonate |
-
2009
- 2009-04-24 CN CN200910111559A patent/CN101870687A/en active Pending
Cited By (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102134227A (en) * | 2010-12-31 | 2011-07-27 | 上海康鹏化学有限公司 | Preparation method of fluoroethylene carbonate |
| CN103044384B (en) * | 2011-10-17 | 2014-10-22 | 张家港市国泰华荣化工新材料有限公司 | Preparation method of 3-fluorine-1, 3-propane sulfonic acid lactone |
| CN103044384A (en) * | 2011-10-17 | 2013-04-17 | 张家港市国泰华荣化工新材料有限公司 | Preparation method of 3-fluorine-1, 3-propane sulfonic acid lactone |
| CN102766130A (en) * | 2012-07-18 | 2012-11-07 | 太仓华一化工科技有限公司 | Preparation method of difluoroethylene carbonate |
| CN102875520A (en) * | 2012-09-25 | 2013-01-16 | 中国海洋石油总公司 | Synthetic method of fluoro carbonic ester |
| CN102875520B (en) * | 2012-09-25 | 2014-12-17 | 中国海洋石油总公司 | Synthetic method of fluoro carbonic ester |
| CN102993160A (en) * | 2012-09-26 | 2013-03-27 | 中国海洋石油总公司 | Synthetic method of fluoro ethylene carbonate |
| CN102875521B (en) * | 2012-09-27 | 2014-08-13 | 中国海洋石油总公司 | Method for preparing fluoro-carbonate ester by means of phase-transfer catalysis |
| CN102875521A (en) * | 2012-09-27 | 2013-01-16 | 中国海洋石油总公司 | Method for preparing fluoro-carbonate ester by means of phase-transfer catalysis |
| CN105541789A (en) * | 2015-12-31 | 2016-05-04 | 石家庄圣泰化工有限公司 | Method for preparing ethylene sulfate derivative |
| CN105541789B (en) * | 2015-12-31 | 2018-09-18 | 石家庄圣泰化工有限公司 | The preparation method of sulfuric acid vinyl ester derivative |
| CN105646632A (en) * | 2016-01-19 | 2016-06-08 | 浙江新和成股份有限公司 | Method for preparing 7-dehydrogenized cholesteryl ester from 7-tosylhydrazones-3-cholesteryl ester |
| CN110775990A (en) * | 2019-10-27 | 2020-02-11 | 淮安瀚康新材料有限公司 | Method for treating fluoroethylene carbonate solid waste |
| CN110775990B (en) * | 2019-10-27 | 2022-05-24 | 江苏瀚康新材料有限公司 | Method for treating fluoroethylene carbonate solid waste |
| CN112500387A (en) * | 2020-12-21 | 2021-03-16 | 苏州华一新能源科技有限公司 | 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 |
| CN114621177A (en) * | 2022-02-24 | 2022-06-14 | 浙江诺亚氟化工有限公司 | Preparation method of fluoroethylene carbonate |
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