CN109467507A - A kind of synthetic method of LITHIUM BATTERY two (trifluoroethyl) carbonic ester - Google Patents
A kind of synthetic method of LITHIUM BATTERY two (trifluoroethyl) carbonic ester Download PDFInfo
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- CN109467507A CN109467507A CN201811419195.8A CN201811419195A CN109467507A CN 109467507 A CN109467507 A CN 109467507A CN 201811419195 A CN201811419195 A CN 201811419195A CN 109467507 A CN109467507 A CN 109467507A
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- trifluoroethyl
- carbonic ester
- lithium battery
- hexachloroacetone
- synthetic method
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C68/00—Preparation of esters of carbonic or haloformic acids
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C68/00—Preparation of esters of carbonic or haloformic acids
- C07C68/08—Purification; Separation; Stabilisation
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Abstract
A kind of synthetic method of LITHIUM BATTERY two (trifluoroethyl) carbonic ester, belongs to fluoro carbonic ester synthesis technical field.It is characterized by: hexachloroacetone is added in trifluoroethanol under -15 DEG C ~ 15 DEG C of cryogenic conditions, the molar ratio of trifluoroethanol and hexachloroacetone is 2 ~ 4.5:1, and catalyst is added, and the additional amount of catalyst is the 0.1% ~ 5% of hexachloroacetone quality；Then heating is reacted, and reaction temperature is 60 ~ 120 DEG C, and the reaction time is 1 ~ 10h；By-product chloroform is collected in air-distillation, and then air-distillation collects 116 DEG C ~ 120 DEG C of fraction to get two (trifluoroethyl) carbonic ester crude products, and two (trifluoroethyl) carbonic ester crude product rectifying collect 118 DEG C ~ 119 DEG C of fraction to obtain the final product.High income of the present invention, easy to operate, product purity is high, and energy consumption is few, small to environmental pressure, and reaction process is single, and anhydrous interference meets the requirement of LITHIUM BATTERY additive.
Description
Technical field
A kind of synthetic method of LITHIUM BATTERY two (trifluoroethyl) carbonic ester, belongs to fluoro carbonic ester synthesis technical field.
Background technique
Two (trifluoroethyl) carbonic esters, abbreviation TFEC are a kind of more novel fluoro carbonic esters.With traditional carbonic ester
It compares, after fluorine atom replaces the hydrogen atom on organic solvent, flammable hydrogen content be can decrease, it is suppressed that the burning of solvent
Possibility, so as to improve the thermostabilization and security performance of electrolyte, simultaneously because other correlations can be improved in the presence of F atom
The compatibility of material and electrolyte, and then stablize the chemical property of electrode.The synthesis of fluoro carbonic ester is mainly phosgene at present
Method, direct fluorination, halogenation fluoride process, ester-interchange method, above-mentioned several method, phosgenation toxicity is stronger, and directly or halogenation is fluorinated
Method yield is lower, and ester-interchange method yield is low and higher cost, is very difficult to apply in TFEC industrialized production.
Summary of the invention
The technical problem to be solved by the present invention is a kind of high income is overcome the deficiencies of the prior art and provide, it is easy to operate,
Product purity is high, the synthetic method of LITHIUM BATTERY two (trifluoroethyl) carbonic ester for consuming energy few.
The technical solution adopted by the present invention to solve the technical problems is: the conjunction of LITHIUM BATTERY two (trifluoroethyl) carbonic ester
At method, it is characterised in that: hexachloroacetone is added in trifluoroethanol under -15 DEG C ~ 15 DEG C of cryogenic conditions, trifluoroethanol
Molar ratio with hexachloroacetone is 2 ~ 4.5:1, and catalyst is added, and the additional amount of catalyst is the 0.1% ~ 5% of hexachloroacetone quality；
Then heating is reacted, and reaction temperature is 60 ~ 120 DEG C, and the reaction time is 1 ~ 10h；By-product chloroform is collected in air-distillation,
Then air-distillation collects 116 DEG C ~ 120 DEG C of fraction to get two (trifluoroethyl) carbonic ester crude products, two (trifluoroethyl) carbonic acid
Ester crude product rectifying collects 118 DEG C ~ 119 DEG C of fraction to obtain the final product.
The present invention solves during prior art preparation two (trifluoroethyl) carbonic ester: yield is high, in production process
The three wastes are more, the reaction time long disadvantage that causes energy consumption high high to temperature requirement in production process, provide and a kind of are technically easy control
The method that system, process conditions simply prepare LITHIUM BATTERY two (trifluoroethyl) carbonic ester.Two (trifluoro of LITHIUM BATTERY disclosed by the invention
Ethyl) carbonic ester synthetic method, reacted using hexachloroacetone and trifluoroethanol, obtain two (trifluoroethyl) carbonic esters and chlorine
It is imitative.High income of the present invention, easy to operate, product purity is high, and energy consumption is few, small to environmental pressure, and reaction process is single, anhydrous
Interference, meets the requirement of LITHIUM BATTERY additive.
The temperature of the cryogenic conditions is 0 DEG C ~ 10 DEG C.Under preferred low temperature dropping temperature, it is boring can faster
Even mixing, reaction starting is more stable, and product quality is more stable.
The reaction temperature is 85 DEG C ~ 110 DEG C, and the reaction time is 3 h ~ 5h.Yield is more under preferred reaction temperature
Height, product purity are higher.
The catalyst is benzyltriethylammoinium chloride, 4 bromide, tetrabutylammonium bromide, tetrabutyl chlorination
One or more of ammonium, 18- crown- 6,15- crown- 5, chain polyethylene glycol, chain dialkylethers it is compound
Catalyst.The present invention provides a variety of feasible catalyst, is able to satisfy present invention catalysis and requires.
The catalyst is tetrabutylammonium bromide or 18- crown- 6.Preferred catalyst is to better adaptability of the present invention, instead
Answer rate more suitable, product purity is higher.
The molar ratio of the trifluoroethanol and hexachloroacetone is 3 ~ 3.6:1.Preferred boring proportion can reach better
Yield.
The additional amount of the catalyst is the 0.5 ~ 0.76% of hexachloroacetone quality.The additional amount of preferred catalyst is anti-
Answer rate more suitable, product purity is higher.
Compared with prior art, possessed beneficial effect of the invention is: two (trifluoro second of LITHIUM BATTERY disclosed by the invention
Base) carbonic ester synthetic method, reacted using hexachloroacetone and trifluoroethanol, obtain two (trifluoroethyl) carbonic esters and chloroform.
High income of the present invention, easy to operate, product purity is high, and energy consumption is few, small to environmental pressure, and reaction process is single, anhydrous dry
It disturbs, meets the requirement of LITHIUM BATTERY additive.
Specific embodiment
The present invention will be further described combined with specific embodiments below, and wherein embodiment 1 is best implements.
Embodiment 1
In the flask for being connected to condenser pipe, thermometer, control ice water bath temperature is 0-5 DEG C, and hexachloroacetone 132.37g is added
(0.5mol), trifluoroethanol 150.06g(1.5mol), catalyst tetrabutylammonium bromide 0.66g is added, controls 85 DEG C of reaction temperature
Flow back 5h, carries out air-distillation to system after reaction, and collection obtains by-product chloroform 115g, then proceedes to distill, and collects
116 DEG C ~ 120 DEG C of fraction, last rectifying collect 118 DEG C ~ 119 DEG C of fraction, finally obtain two (trifluoroethyl) carbonic esters
103.99g, reaction yield 92%, products obtained therefrom purity are 99.6%.
Embodiment 2
In the flask for being connected to condenser pipe, thermometer, control ice water bath temperature is 5-10 DEG C, and hexachloroacetone 132.37g is added
(0.5mol), trifluoroethanol 180.07g(1.8mol), catalyst tetrabutylammonium bromide 1.0g is added, controls 100 DEG C of reaction temperature
Flow back 3h, carries out air-distillation to system after reaction, and collection obtains by-product chloroform 112g, then proceedes to distill, and collects
116 DEG C ~ 120 DEG C of fraction, last rectifying collect 118 DEG C ~ 119 DEG C of fraction, finally obtain two (trifluoroethyl) carbonic esters
100.60g, reaction yield 89%, products obtained therefrom purity are 99.5%.
Embodiment 3
In the flask for being connected to condenser pipe, thermometer, control ice water bath temperature is 0-5 DEG C, and hexachloroacetone 132.37g is added
(0.5mol), trifluoroethanol 150.06(1.5mol), 6 0.66g of catalyst 18- crown- is added, controls 110 DEG C of reaction temperature reflux
5h carries out air-distillation to system after reaction, and collection obtains by-product chloroform 110g, then proceedes to distill, and collects 116 DEG C
~ 120 DEG C of fraction, last rectifying collect 118 DEG C ~ 119 DEG C of fraction, finally obtain two (trifluoroethyl) carbonic ester 97.21g,
Reaction yield is 86%, and products obtained therefrom purity is 99.7%.
Embodiment 4
In the flask for being connected to condenser pipe, thermometer, control ice water bath temperature is -15 DEG C ~ 0 DEG C, and hexachloroacetone 132.37g is added
(0.5mol), trifluoroethanol 225.1g(2.25mol), catalyst benzyltriethylammoinium chloride 0.13g is added, controls reaction temperature
120 DEG C of reflux 1h carry out air-distillation to system after reaction, and collection obtains by-product chloroform 114g, then proceedes to distill,
116 DEG C ~ 120 DEG C of fraction is collected, last rectifying collects 118 DEG C ~ 119 DEG C of fraction, finally obtains two (trifluoroethyl) carbonic acid
Ester 94.9g, reaction yield 84%, products obtained therefrom purity are 99.4%.
Embodiment 5
In the flask for being connected to condenser pipe, thermometer, control ice water bath temperature is 10 ~ 15 DEG C, and hexachloroacetone 132.37g is added
(0.5mol), trifluoroethanol 100.04g(1mol), catalyst 4 bromide 6.6g is added, 60 DEG C of reaction temperature of control are returned
10h is flowed, air-distillation is carried out to system after reaction, collection obtains by-product chloroform 107g, then proceedes to distill, and collects
116 DEG C ~ 120 DEG C of fraction, last rectifying collect 118 DEG C ~ 119 DEG C of fraction, finally obtain two (trifluoroethyl) carbonic esters
93.8g, reaction yield 83%, products obtained therefrom purity are 99.4%.
The above described is only a preferred embodiment of the present invention, being not that the invention has other forms of limitations, appoint
What those skilled in the art changed or be modified as possibly also with the technology contents of the disclosure above equivalent variations etc.
Imitate embodiment.But without departing from the technical solutions of the present invention, according to the technical essence of the invention to above embodiments institute
Any simple modification, equivalent variations and the remodeling made, still fall within the protection scope of technical solution of the present invention.
Claims (7)
1. a kind of synthetic method of LITHIUM BATTERY two (trifluoroethyl) carbonic ester, it is characterised in that: in -15 DEG C ~ 15 DEG C of low temperature item
Hexachloroacetone is added in trifluoroethanol under part, the molar ratio of trifluoroethanol and hexachloroacetone is 2 ~ 4.5:1, and catalysis is added
Agent, the additional amount of catalyst are the 0.1% ~ 5% of hexachloroacetone quality；Then heating is reacted, and reaction temperature is 60 ~ 120
DEG C, the reaction time is 1 ~ 10h；By-product chloroform is collected in air-distillation, and then 116 DEG C ~ 120 DEG C of fraction is collected in air-distillation,
Up to two (trifluoroethyl) carbonic ester crude products, the fraction that two (trifluoroethyl) carbonic ester crude product rectifying collect 118 DEG C ~ 119 DEG C is
?.
2. a kind of synthetic method of LITHIUM BATTERY two (trifluoroethyl) carbonic ester according to claim 1, it is characterised in that: institute
The temperature for the cryogenic conditions stated is 0 DEG C ~ 10 DEG C.
3. a kind of synthetic method of LITHIUM BATTERY two (trifluoroethyl) carbonic ester according to claim 1, it is characterised in that: institute
The reaction temperature stated is 85 DEG C ~ 110 DEG C, and the reaction time is 3 h ~ 5h.
4. a kind of synthetic method of LITHIUM BATTERY two (trifluoroethyl) carbonic ester according to claim 1, it is characterised in that: institute
The catalyst stated be benzyltriethylammoinium chloride, 4 bromide, tetrabutylammonium bromide, tetrabutylammonium chloride, 18- crown- 6,
The composite catalyst of one or more of 15- crown- 5, chain polyethylene glycol, chain dialkylethers.
5. a kind of synthetic method of LITHIUM BATTERY two (trifluoroethyl) carbonic ester according to claim 1, it is characterised in that: institute
The catalyst stated is tetrabutylammonium bromide or 18- crown- 6.
6. a kind of synthetic method of LITHIUM BATTERY two (trifluoroethyl) carbonic ester according to claim 1, it is characterised in that: institute
The molar ratio of the trifluoroethanol and hexachloroacetone stated is 3 ~ 3.6:1.
7. a kind of synthetic method of LITHIUM BATTERY two (trifluoroethyl) carbonic ester according to claim 1, it is characterised in that: institute
The additional amount for the catalyst stated is the 0.5 ~ 0.76% of hexachloroacetone quality.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111018709A (en) * | 2019-12-21 | 2020-04-17 | 泰兴华盛精细化工有限公司 | Preparation method of methyl trifluoroethyl carbonate |
| CN112812007A (en) * | 2019-11-18 | 2021-05-18 | 石家庄圣泰化工有限公司 | Preparation method of 2,2, 2-trifluoroethyl hexanoate |
| CN115215747A (en) * | 2021-04-21 | 2022-10-21 | 常州市天华制药有限公司 | Synthesis method of methyl 2,2,2-trifluoroethyl carbonate |
| CN115745768A (en) * | 2022-11-14 | 2023-03-07 | 派瑞科技有限公司 | Method for purifying hexachloroacetone |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101883752A (en) * | 2007-12-03 | 2010-11-10 | 旭硝子株式会社 | Method for producing carbonate compound |
-
2018
- 2018-11-26 CN CN201811419195.8A patent/CN109467507A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101883752A (en) * | 2007-12-03 | 2010-11-10 | 旭硝子株式会社 | Method for producing carbonate compound |
Non-Patent Citations (1)
| Title |
|---|
| 刘鹰翔主编: "《药物合成反应 新世纪第2版》", 31 August 2017, 中国中医药出版社 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112812007A (en) * | 2019-11-18 | 2021-05-18 | 石家庄圣泰化工有限公司 | Preparation method of 2,2, 2-trifluoroethyl hexanoate |
| CN111018709A (en) * | 2019-12-21 | 2020-04-17 | 泰兴华盛精细化工有限公司 | Preparation method of methyl trifluoroethyl carbonate |
| CN115215747A (en) * | 2021-04-21 | 2022-10-21 | 常州市天华制药有限公司 | Synthesis method of methyl 2,2,2-trifluoroethyl carbonate |
| CN115745768A (en) * | 2022-11-14 | 2023-03-07 | 派瑞科技有限公司 | Method for purifying hexachloroacetone |
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