CN102372689B - Preparation method for trifluoromethyl ethylene carbonate - Google Patents

Preparation method for trifluoromethyl ethylene carbonate Download PDF

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CN102372689B
CN102372689B CN201110367546.7A CN201110367546A CN102372689B CN 102372689 B CN102372689 B CN 102372689B CN 201110367546 A CN201110367546 A CN 201110367546A CN 102372689 B CN102372689 B CN 102372689B
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fluoro
tri
ethylene carbonate
carbonate
propylene glycol
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CN102372689A (en
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张翚鹰
田志钢
解承钢
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Xinyuan chemical (Shandong) Co.,Ltd.
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威海新元化工有限公司
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Abstract

The invention relates to a method for trifluoromethyl ethylene carbonate. The method comprises the following steps of: hydrolyzing 2-bromine-3,3,3-trifluoropropanol serving as a raw material with an alkaline liquor to prepare 3,3,3-trifluoro-1,2-propylene glycol; mixing the obtained 3,3,3-trifluoro-1,2-propylene glycol with dialkyl carbonate according to a certain proportion; and reacting by taking methylbenzene, dimethylbenzene and the like as solvents and taking carbonate as a catalyst to prepare trifluoromethyl ethylene carbonate, wherein the product purity is over 99.8 percent. The method has the advantages: expensive 3,3,3-trifluoro-1,2-propylene oxide is not taken as a raw material, the unreacted raw material can be recycled, the solvents can be used repeatedly, the preparation process is simple, and high-purity trifluoromethyl ethylene carbonate can be obtained.

Description

A kind of preparation method of trifluoromethyl ethylene carbonate
Technical field
The present invention relates to organic synthesis field and lithium ion battery electrolytic solution field, particularly, relate to a kind of preparation method of trifluoromethyl ethylene carbonate.
Background technology
Cyclic carbonate comprises ethylene carbonate, Texacar PC and analogue thereof, is the important organic solvent of a class, can fully dissolves various organism and inorganics, have very strong physics, chemical stability and high specific inductivity.Therefore there is very high industrial application value.
Cyclic carbonate is widely used in weaving, printing and dyeing, Polymer Synthesizing and electrochemical field (see JP 08-325258), also occupies critical role in the synthesis of medicine and fine-chemical intermediate simultaneously.
Because cyclic carbonate has stable physicochemical property, and various organism and inorganics and high specific inductivity can be dissolved, be widely used as the non-aqueous electrolytic solvent of battery.In recent years along with the develop rapidly of battery industry, the research of cyclic carbonate also increased gradually, and part has carried out scale operation.But as electrolyte solvent, also there is certain defect, such as: although the low high-melting-point had up to 38 DEG C of its molecular weight of ethylene carbonate, be at room temperature solid-state, must pass through heats liquefied when using as solvent, as the use temperature narrow range of solvent.Texacar PC is widely used as the non-aqueous electrolytic solvent of battery, but be used as with graphite material the solvent of the lithium ion battery being negative pole, or during as the battery solvent being negative material with lithium or lithium alloy, Texacar PC can react with negative material, thus shortens the life-span of battery.
In order to make up above defect, the cyclic carbonate of external proposition fluorine richness replaces existing solvent, mainly contain a fluorine and replace ethylene carbonate, difluoro replacement ethylene carbonate and trifluoro replacement ethylene carbonate, and be applied in electrolytic solution, successful (see JP 07-165750).When particularly trifluoromethyl ethylene carbonate uses as non-aqueous electrolytic solvent, have use temperature wide ranges, physical and chemical stability is good, proof voltage is excellent, charge-discharge cycle is good, and has high flash point and high security, is the ideal solvent of following battery electrolyte.
Less about the research of trifluoromethyl ethylene carbonate at present, roughly there are two kinds of thinkings synthesis aspect: one is with 3,3,3-tri-fluoro-1,2-propylene oxide and carbonic acid gas are raw material, directly synthesize under high temperature, high pressure, catalysts conditions, this method severe reaction conditions, yield is very low, is unfavorable for suitability for industrialized production; Another kind is first hydrolyzed generation 3,3 by the fluoro-1,2 epoxy prapane of 3,3,3-tri-, the fluoro-1,2-PD of 3-tri-, then by fluoro-for 3,3,3-tri-1,2-propylene glycol joins in a large amount of methylcarbonate, and be that catalyzer synthesizes with alkali, this method is simple to operate, but reaction efficiency very low (see US 6010806).In addition, above two kinds of methods also have a common shortcoming, are just the use of expensive 3,3,3-tri-fluoro-1,2 epoxy prapanes and do raw material, directly constrain the application process of trifluoromethyl ethylene carbonate.
In sum, the preparation method of the trifluoromethyl ethylene carbonate of Development of Novel has very important significance.
Summary of the invention
The object of this invention is to provide a kind of preparation method of trifluoromethyl ethylene carbonate, to overcome the problem existing for prior art and cost aspect.
The invention provides a kind of preparation method of trifluoromethyl ethylene carbonate, comprising with bromo-3,3, the 3-trifluoropropanols of 2-is that raw material is prepared the fluoro-1,2-PD of 3,3,3-tri-and is catalyst preparing trifluoromethyl ethylene carbonate with carbonate.
The present invention carries out in two steps, the first step, and bromo-3,3, the 3-trifluoropropanol hydrolysis of 2-generate the fluoro-1,2-PD of intermediate 3,3,3-tri-; Second step, the fluoro-1,2-PD of 3,3,3-tri-and carbonic diester react and generate target product trifluoromethyl ethylene carbonate.
Particularly, the first step reaction joins in alkali lye by bromo-for 2-3,3,3-trifluoropropanols, reacts 6 ~ 8h at a certain temperature.Then be cooled to room temperature, extraction, distillating recovering solvent, obtains the fluoro-1,2-PD of intermediate 3,3,3-tri-.
Described alkali lye does not have particular requirement, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, salt of wormwood, saleratus etc., can be wherein one or more mixing solutionss, preferred sodium carbonate, sodium bicarbonate.
The concentration of described alkali lye between 1% ~ 60%, preferably 5% ~ 45%.
Described temperature of reaction at 30 ~ 100 DEG C, preferably 50 ~ 80 DEG C, more preferably 65 ~ 75 DEG C.
Described extraction liquid does not have particular requirement, ethyl acetate, butylacetate etc., ethyl acetate.
Particularly, second step reaction is mixed by a certain percentage with carbonic diester by 3,3, the 3-tri-fluoro-1,2-PDs obtained, and then joining in solvent, is catalyzer with carbonate, and be heated to certain temperature reaction 10 ~ 14h, rectifying, obtains target product.
Described solvent can not participate in chemical reaction, can control alcohol and carbonic diester azeotropic, with this understanding, and preferred normal hexane, heptane, toluene, o-Xylol, m-xylene, p-Xylol etc., more preferably normal hexane, o-Xylol, toluene, most preferably toluene.
Described carbonic diester does not have particular requirement, methylcarbonate, diethyl carbonate etc., preferred methylcarbonate.
3,3,3-tri-described fluoro-1,2-PDs and the ratio of carbonic diester are 1:1 ~ 1:10 in molar ratio, preferred 1:2 ~ 1:7, more preferably 1:3 ~ 1:5.
Described carbonate catalyst does not have particular requirement, salt of wormwood, sodium carbonate, zinc carbonate, calcium carbonate, lead carbonate etc., preferred zinc carbonate, sodium carbonate.
Described catalyst levels is 0.1 ~ 10% of the fluoro-1,2-PD consumption of 3,3,3-tri-, preferably 0.1 ~ 5%.
Described temperature of reaction at 65 ~ 135 DEG C, along with reaction carrying out progressively raise.
The yield of target product of the present invention is more than 60%, and purity is more than 99.8%, and gained compound is through nmr spectrum and Mass Spectrometric Identification, accurate.
The present invention is compared with the synthetic method of trifluoromethyl ethylene carbonate before this, advantage is that required cost significantly reduces, do not use severe toxicity or have the reagent of environmental protection pressure, reaction conditions is gentle, workable, raw material is easy to get and recoverable, is a kind of method of simple obtained trifluoromethyl ethylene carbonate.
Embodiment
Following examples for illustration of the present invention, but are not used for limiting the scope of the invention.
Embodiment 1:
In 2000mL there-necked flask, add the aqueous sodium carbonate 1000g of 20%, stir and add bromo-3,3, the 3-trifluoropropanols of 164g 2-, be heated to 70 DEG C of reaction 6h.Then be cooled to room temperature, divide three extractions by 1600mL ethyl acetate, extraction liquid is with saturated common salt water washing to neutral, and distillation extraction liquid reclaims ethyl acetate, obtains the fluoro-1,2-PD of 3,3,3-tri-, yield 80%, product purity 94%.
540g toluene is added in 1000mL there-necked flask (with rectifying tower), then stir and add 180g methylcarbonate, 130g3, the fluoro-1,2-PD of 3,3-tri-, 5g zinc carbonate, be heated to 65 DEG C of reactions, along with the carrying out of reaction, improve Heating temperature gradually, in heat-processed, constantly steam methyl alcohol, approximately react 10h.After reaction terminates, unreacted methylcarbonate and solvent toluene are reclaimed in rectifying, and obtain product trifluoromethyl ethylene carbonate.Product yield is 77%, product purity 99.8%.
Embodiment 2:
In 2000mL there-necked flask, add the sodium bicarbonate aqueous solution 1000g of 15%, then add bromo-3,3, the 3-trifluoropropanols of 130g 2-, be heated to 75 DEG C of reaction 6h.Be cooled to room temperature, divide three extractions by 1600mL ethyl acetate, extraction liquid is with saturated common salt water washing to neutral, and distillation extraction liquid, reclaims ethyl acetate, obtain the fluoro-1,2-PD of 3,3,3-tri-, yield 78%, product purity 96%.
In 1000mL there-necked flask (with rectifying tower), add 400g o-Xylol, stir and add 252g diethyl carbonate, 134g3,3, the fluoro-1,2-PD of 3-tri-, 3.2g sodium carbonate, be heated to 80 DEG C of reactions, along with reaction is carried out improving constantly Heating temperature, in reaction process, constantly steam ethanol.After reaction terminates, diethyl carbonate and solvent are reclaimed in rectifying, obtain trifluoromethyl ethylene carbonate.Product yield is 68%, product purity 99.8%.
Embodiment 3:
In 2000mL there-necked flask, add 180g sodium carbonate, 20g sodium hydroxide, be configured to the mixed aqueous solution 1000g of the sodium carbonate-sodium hydroxide of 20%, stir, then bromo-3,3, the 3-trifluoropropanols of 190g2-are added, be heated to 70 DEG C of reaction 6h, be cooled to room temperature, divide three extractions by 1600mL ethyl acetate, extraction liquid is with saturated common salt water washing to neutral, and distillation extraction liquid reclaims ethyl acetate, obtains 3, the fluoro-1,2-PD of 3,3-tri-, yield 83%, product purity 95%.
In 1000mL there-necked flask (with rectifying tower), add 500g toluene, 234g methylcarbonate, stir, then add 113g3, the fluoro-1,2-PD of 3,3-tri-, 2.5g lead carbonate, be heated to 65 DEG C of reactions, along with reaction is carried out improving constantly Heating temperature, in reaction process, constantly steam methyl alcohol.Reaction terminates rear rectifying and reclaims unreacted methylcarbonate and solvent, obtains trifluoromethyl ethylene carbonate.Product yield is 65%, product purity 99.8%.

Claims (2)

1. the preparation method of a trifluoromethyl ethylene carbonate, comprise with 2-bromo-3, 3, 3-trifluoropropanol is that raw material prepares 3, 3, 3-tri-fluoro-1, 2-propylene glycol, and with 3, 3, 3-tri-fluoro-1, 2-propylene glycol is Intermediate Preparation trifluoromethyl ethylene carbonate, the aqueous sodium carbonate 1000g of 20% is it is characterized in that to add in 2000mL there-necked flask, stirring adds 164g 2-bromo-3, 3, 3-trifluoropropanol, be heated to 70 DEG C of reaction 6h, then room temperature is cooled to, three extractions are divided by 1600mL ethyl acetate, extraction liquid is extremely neutral with saturated common salt water washing, distillation extraction liquid, reclaim ethyl acetate, obtain product yield 80%, 3 of product purity 94%, 3, 3-tri-fluoro-1, 2-propylene glycol, then the there-necked flask of 1000mL with rectifying tower is got, 540g toluene is added to it, then stir and add 180g methylcarbonate, 130g be obtained by reacting 3, 3, 3-tri-fluoro-1, 2-propylene glycol, 5g zinc carbonate, be heated to 65 DEG C of reactions, along with the carrying out of reaction, improve Heating temperature gradually, constantly methyl alcohol is steamed in heat-processed, reaction 10h, after reaction terminates, unreacted methylcarbonate and solvent toluene are reclaimed in rectifying, and to obtain product yield be 77%, the product trifluoromethyl ethylene carbonate of product purity 99.8%.
2. the preparation method of a trifluoromethyl ethylene carbonate, comprise with 2-bromo-3, 3, 3-trifluoropropanol is that raw material prepares 3, 3, 3-tri-fluoro-1, 2-propylene glycol, and with 3, 3, 3-tri-fluoro-1, 2-propylene glycol is Intermediate Preparation trifluoromethyl ethylene carbonate, it is characterized in that 180g sodium carbonate, 20g sodium hydroxide, be configured to the mixed aqueous solution 1000g of the sodium carbonate-sodium hydroxide of 20%, add in 2000mL there-necked flask and stir, then 190g2-bromo-3 is added, 3, 3-trifluoropropanol, be heated to 70 DEG C of reaction 6h, then room temperature is cooled to, three extractions are divided by 1600mL ethyl acetate, extraction liquid is extremely neutral with saturated common salt water washing, distillation extraction liquid, reclaim ethyl acetate, obtain product yield 83%, 3 of product purity 95%, 3, 3-tri-fluoro-1, 2-propylene glycol, then the there-necked flask of 1000mL with rectifying tower is got, 500g toluene is added to it, 234g methylcarbonate, stir, then add that 113g is obtained by reacting 3, 3, 3-tri-fluoro-1, 2-propylene glycol, 2.5g lead carbonate, be heated to 65 DEG C of reactions, along with the carrying out of reaction, improve Heating temperature gradually, constantly methyl alcohol is steamed in heat-processed, after reaction terminates, unreacted methylcarbonate and solvent are reclaimed in rectifying, and to obtain product yield be 65%, the product trifluoromethyl ethylene carbonate of product purity 99.8%.
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CN105399607B (en) * 2015-11-06 2017-12-22 西安近代化学研究所 A kind of preparation method of 3,3,3 trifluoropropanol
CN108178752B (en) * 2017-12-19 2021-02-23 西安近代化学研究所 Method for preparing 3,3, 3-trifluoropropene carbonate and 3,3, 3-trifluoro-1, 2-propylene glycol in co-production mode
CN113087695A (en) * 2021-03-31 2021-07-09 武汉大学 Rapid energy-saving integrated method for preparing aliphatic polycarbonate monomer

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Publication number Priority date Publication date Assignee Title
CN1161036A (en) * 1995-06-09 1997-10-01 三井石油化学工业株式会社 Cyclic fluorinated carbonates and electrolyte solution and battery containing the carbonate

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Publication number Priority date Publication date Assignee Title
CN1161036A (en) * 1995-06-09 1997-10-01 三井石油化学工业株式会社 Cyclic fluorinated carbonates and electrolyte solution and battery containing the carbonate

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Title
The Preparation and Properties of 3,3,3-Trifluoro-1,2-epoxypropane;E. T. MCBEEA, et.al.;《Journal of the American Chemical Society》;19520630;第74卷(第12期);第3022-3023页 *

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