CN112299960B - Synthesis method and application of bis (2,2, 2-trifluoroethyl) ether - Google Patents

Synthesis method and application of bis (2,2, 2-trifluoroethyl) ether Download PDF

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CN112299960B
CN112299960B CN202011254512.2A CN202011254512A CN112299960B CN 112299960 B CN112299960 B CN 112299960B CN 202011254512 A CN202011254512 A CN 202011254512A CN 112299960 B CN112299960 B CN 112299960B
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trifluoroethyl
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CN112299960A (en
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徐祥松
高国军
陈建海
李建民
何金峰
刘俊
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Jiangsu Bluestar Green Technology Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
    • C07C41/01—Preparation of ethers
    • C07C41/16—Preparation of ethers by reaction of esters of mineral or organic acids with hydroxy or O-metal groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00—Preparation of halogenated hydrocarbons
    • C07C17/093—Preparation of halogenated hydrocarbons by replacement by halogens
    • C07C17/20—Preparation of halogenated hydrocarbons by replacement by halogens of halogen atoms by other halogen atoms
    • C07C17/21—Preparation of halogenated hydrocarbons by replacement by halogens of halogen atoms by other halogen atoms with simultaneous increase of the number of halogen atoms
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0569—Liquid materials characterised by the solvents
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    • Y02E60/10—Energy storage using batteries

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Abstract

The invention provides a synthesis method of bis (2,2, 2-trifluoroethyl) ether, which comprises the following steps: preparing 1,1, 1-trifluoro-2-chloroethane; adding 550 parts by weight of ethylene glycol 500-1.1 parts by weight, 0.9-1.1 parts by weight of potassium hydroxide and 100 parts by weight of trifluoroethanol into a pressure reaction kettle, sealing the reaction kettle, introducing 130 parts by weight of 1,1, 1-trifluoro-2-chloroethane 110-4 parts by weight, stirring and heating to at least 70-80 ℃ for reaction for 2-4 hours; controlling the system temperature between 70 and 90 ℃, adding a polar solvent into the system, uniformly stirring, and filtering potassium chloride solid precipitate to obtain a filtrate; rectifying the filtrate to obtain a product with the purity of more than 99.98%, and providing the application of the product as a lithium battery electrolyte solution in the field of lithium batteries. The process has the advantages of easily available raw materials, no limitation of supply, simple equipment requirement, no special material requirement, simple process, completely meeting the production requirement, clean production, reduction of equipment cost, increase of the competitive capacity of company products and improvement of economic benefit.

Description

Synthesis method and application of bis (2,2, 2-trifluoroethyl) ether
Technical Field
The invention relates to the field of lithium battery electrolyte solution production, in particular to a production method of fluorinated organic solvent fluorinated ether and application of the fluorinated organic solvent fluorinated ether as a lithium battery electrolyte solution.
Background
Fluorinated organic solvents have long been used in lithium ion batteries, and fluorinated solvents can provide various benefits to the electrolyte compared to conventional electrolytes that are not fluorinated solvents. The bis (2,2, 2-trifluoroethyl) ether is an electrolyte for a lithium battery, which has high oxidation resistance, good flame retardance and good compatibility with a graphite cathode. By adding bis (2,2, 2-trifluoroethyl) ether into the lithium battery electrolyte, the oxidation resistance and flame retardant property of the whole lithium battery system and good compatibility with a graphite cathode can be obviously improved. The bis (2,2, 2-trifluoroethyl) ether is beneficial to forming an excellent solid electrolyte interface film on an electrode interface, improves the compatibility between an electrolyte and an active material, and simultaneously can weaken the viscosity force between molecules, so that the migration resistance of the molecules and ions is reduced, the viscosity is further reduced, the conductivity of the electrolyte is improved, and the cycle stability and the capacity retention rate of a battery are further improved; meanwhile, the bis (2,2, 2-trifluoroethyl) ether has good thermal stability and no flash point, so that the flash point of the lithium battery electrolyte is obviously improved, and the problem of flammability of the electrolyte is effectively solved.
In the conventional method for preparing bis (2,2, 2-trifluoroethyl) ether, such as bis (2,2, 2-trifluoroethyl) ether of U.S. Pat. No. 3,3363006 and the preparation method thereof, 2,2, 2-trifluoroethyl sodium having nucleophilicity is prepared from 2,2, 2-trifluoroethanol and dioxane, and then reacted with tosylate to produce (2,2, 2-trifluoroethyl) ether, the preparation of 2,2, 2-trifluoroethyl sodium is carried out in the presence of dioxane from metallic sodium, the production process is complicated, and the requirement for equipment performance is high, the production raw materials are not easy to store and are not environment-friendly, and in addition, the purity of bis (2,2, 2-trifluoroethyl) ether produced by the method is less than 99%.
Disclosure of Invention
Therefore, it is necessary to provide a synthesis method and application of bis (2,2, 2-trifluoroethyl) ether which has high oxidation resistance, good flame retardancy, high purity and safe production.
The chemical reaction principle for preparing bis (2,2, 2-trifluoroethyl) ether is as follows:
CF3-CH2Cl+CF3-CH2OH+KOH→CF3-CH2-O-CH2-CF3+KCl+H2O
wherein the chemical reaction principle for preparing the 1,1, 1-trifluoro-2-chloroethane is as follows:
CCl2＝CHCl+3HF→CF3-CH2Cl+2HCl
the synthesis method of bis (2,2, 2-trifluoroethyl) ether comprises the following steps:
1) preparing 1,1, 1-trifluoro-2-chloroethane;
2) adding 550 parts by weight of ethylene glycol 500-1.1 parts by weight, 0.9-1.1 parts by weight of potassium hydroxide and 100 parts by weight of trifluoroethanol into a pressure reaction kettle, sealing the reaction kettle, introducing 130 parts by weight of 1,1, 1-trifluoro-2-chloroethane 110-4 parts by weight, stirring and heating to 70-80 ℃ for reaction for 2-4 hours;
3) controlling the system temperature between 70 and 90 ℃, adding a polar solvent into the system, uniformly stirring, and filtering potassium chloride solid precipitate to obtain a filtrate;
4) the filtrate was rectified.
In one embodiment, the stirring speed in step 2) is 150-.
In one embodiment, the polar solvent in step 3) is water, and the water is 8 to 10 parts by weight.
In one embodiment, the stirring time in step 3) is 8 to 15 minutes.
In one embodiment, the distillation in step 4) is completed in a distillation column, the number of plates of the column is 15-21, the bottom temperature is 158-168 ℃, the top temperature is 70-80 ℃, the reflux ratio is 0.5-1.5, and the pressure is 8-15 kPa.
In one embodiment, the preparation of 1,1, 1-trifluoro-2-chloroethane in step 1) comprises the steps of:
s1, adding a catalyst into a 1,1, 1-trifluoro-2-chloroethane reaction kettle, heating the reaction kettle by steam to 100 ℃, introducing hydrogen fluoride, trichloroethylene and chlorine into the reaction kettle at a certain speed, and continuously adding the raw materials into the reaction kettle, wherein the pressure of the reaction kettle is controlled to be 0.7-0.8 Mpa, and the reaction temperature is controlled to be 100-115 ℃.
S2, opening a valve of the gas buffer tank, and controlling the temperature of the reaction bubbler to be 65-85 ℃. And (3) opening a water inlet valve of the condenser, and controlling the top temperature of the condenser to be 40-45 ℃.
S3, starting a cryogenic system, cooling the emptying tail gas and receiving the emptying tail gas. And (3) rectifying the collected crude product 1,1, 1-trifluoro-2-chloroethane by a rectifying tower to remove alkali and wash the product with water, and then sending the product to the alkaline hydrolysis section in the step 2).
In one embodiment, the ventilation speed in step S1 is: the hydrogen fluoride is less than 250L/h, the trichloroethylene is less than 180L/h, and the chlorine is 12-15 Kg/h.
In one of the embodiments, the catalyst is antimony pentachloride.
Application of bis (2,2, 2-trifluoroethyl) ether in lithium battery electrolyte.
The invention has the beneficial effects that:
the process has the advantages of easily available raw materials, no limitation of supply, simple equipment requirement, no special material requirement, simple process, completely meeting the production requirement, clean production, reduction of equipment cost, increase of the competitive capacity of company products and improvement of economic benefit.
The method is characterized in that 1,1, 1-trifluoro-2-chloroethane and trifluoroethanol are subjected to alkaline hydrolysis by potassium hydroxide to produce bis (2,2, 2-trifluoroethyl) ether, and the DCS automatic control reaction is adopted, so that artificial operation fluctuation in the reaction process is avoided, the reaction is more stable, the production safety is greatly improved, the product quality is improved, and the production cost is reduced.
The invention respectively prepares 1,1, 1-trifluoro-2-chloroethane with low impurity content and bis (2,2, 2-trifluoroethyl) ether on the basis of the 1,1, 1-trifluoro-2-chloroethane, the yield of the prepared product is more than 97.5 percent, the purity is more than 99.98 percent, and the water content of the prepared product is less than 0.001 percent, and the prepared product can be used as a solvent of a non-flammable electrolyte or a non-aqueous lithium ion battery electrolyte and applied to the field of lithium battery electrolyte solution.
Detailed Description
The synthesis method of bis (2,2, 2-trifluoroethyl) ether comprises the following steps:
1) preparing 1,1, 1-trifluoro-2-chloroethane;
preferably, as an implementable mode, the preparation of 1,1, 1-trifluoro-2-chloroethane further comprises the steps of:
s1, adding a catalyst into a 1,1, 1-trifluoro-2-chloroethane reaction kettle, heating the reaction kettle by steam to 100 ℃, introducing hydrogen fluoride, trichloroethylene and chlorine into the reaction kettle at a certain speed, and continuously adding the raw materials into the reaction kettle, wherein the pressure of the reaction kettle is controlled to be 0.7-0.8 Mpa, and the reaction temperature is controlled to be 100-115 ℃.
It should be noted that the catalyst used in this step is a catalyst commonly used for halogenated alkanes, and may be antimony pentachloride or other metal halides.
Preferably, in this step, the aeration rate is: the hydrogen fluoride is less than 250L/h, the trichloroethylene is less than 180L/h, and the chlorine is 12-15 Kg/h.
S2, opening a valve of the gas buffer tank, and controlling the temperature of the reaction bubbler to be 65-85 ℃. And (3) opening a water inlet valve of the condenser, and controlling the top temperature of the condenser to be 40-45 ℃.
The invention improves the yield and purity of the 1,1, 1-trifluoro-2-chloroethane by controlling and adjusting the aeration rate and the temperature.
S3, starting a cryogenic system, cooling the emptying tail gas and receiving the emptying tail gas. The gas is prepared by adopting the gas raw material, so that the reaction rate and the reaction uniformity are increased, and the deep cooling is adopted, so that the control of the reaction process is facilitated, and the generation and the collection of the target reactant can be ensured. And (3) rectifying the collected crude product 1,1, 1-trifluoro-2-chloroethane by a rectifying tower to remove alkali and wash the product with water, and then sending the product to the alkaline hydrolysis section in the step 2).
It should be noted that the distillation of crude 1,1, 1-trifluoro-2-chloroethane through a rectifying column to remove the alkaline water is a common purification method of halogenated alkane, and is not explained here.
2) Adding 550 parts by weight of ethylene glycol 500-1.1 parts by weight, 0.9-1.1 parts by weight of potassium hydroxide and 100 parts by weight of trifluoroethanol into a pressure reaction kettle, sealing the reaction kettle, introducing 130 parts by weight of 1,1, 1-trifluoro-2-chloroethane 110-4 parts by weight, stirring and heating to 70-80 ℃ for reaction for 2-4 hours;
the stirring speed in the reaction kettle is preferably kept at 150-300/h.
3) Controlling the system temperature between 70 and 90 ℃, adding a polar solvent into the system, uniformly stirring, and filtering potassium chloride solid precipitate to obtain a filtrate;
preferably, the polar solvent in this step may be selected from water, methanol, ethanol or a mixture thereof, and the inventors have found that the addition of 8 to 10 parts by weight of water minimizes other impurities in the filtrate obtained in the present invention.
Preferably, the stirring time is 8-15 minutes, the reaction time is short, and the control is easy.
4) The filtrate was rectified.
Preferably, the rectification is carried out in a rectification column having a tray number of 15-21, a bottom temperature of 158-168 ℃, a top temperature of 70-80 ℃, a reflux ratio of 0.5-1.5, and a pressure of 8-15 kPa. The rectification time is 0.5-2 hours.
Application of bis (2,2, 2-trifluoroethyl) ether in lithium battery electrolyte.
The following are specific examples (the following examples, unless otherwise specified, do not contain other components not specifically indicated except for unavoidable impurities). The hydrogen fluoride, trichloroethylene, chlorine, ethylene glycol, potassium hydroxide, trifluoroethanol, and catalysts used in the following examples were all commercially available products.
Examples 1,
Adding antimony pentachloride serving as a catalyst into a 1,1, 1-trifluoro-2-chloroethane reaction kettle, heating the reaction kettle by steam until the temperature reaches 100 ℃, continuously adding raw materials into the reaction kettle according to the conditions that hydrogen fluoride is less than 250L/h, trichloroethylene is less than 180L/h and chlorine is 12-15 Kg/h, and controlling the pressure of the reaction kettle to be 0.7-0.8 MPa and the reaction temperature to be 100-115 ℃. And opening a valve to the gas buffer tank, and controlling the temperature of the reaction bubbler to be 65-85 ℃. And (3) opening a water inlet valve of the condenser, and controlling the top temperature of the condenser to be 40-45 ℃. And starting the cryogenic system, and cooling and collecting the emptying tail gas. The collected crude product 1,1, 1-trifluoro-2-chloroethane is rectified by a rectifying tower to remove alkali and washed by water, and then is sent to an alkaline hydrolysis section.
Adding 550kg of ethylene glycol, 1.1kg of potassium hydroxide and 100kg of trifluoroethanol into a pressure reaction kettle, sealing the reaction kettle, introducing 1,1, 1-trifluoro-2-chloroethane, stopping introducing the 1,1, 1-trifluoro-2-chloroethane when the introduction amount of the 1,1, 1-trifluoro-2-chloroethane reaches 130kg, and heating to 70 ℃ at the rotating speed of 300r/min for reaction for 4 hours. After the reaction is finished, adding 10kg of water into the reaction system, stirring for 10 minutes, filtering to remove potassium chloride solid precipitate to obtain filtrate, and then rectifying the filtrate by a rectifying tower, wherein the tower plates of the rectifying tower are 15-21 layers, the tower bottom temperature is 158-168 ℃, the tower top temperature is 70-80 ℃, the reflux ratio is 0.5-1.5, and the pressure is 8-15kPa, so that the yield of the bis (2,2, 2-trifluoroethyl) ether is 97.4%, and the product has no pungent odor and is not detected by peroxide in the product through sampling analysis. High pressure liquid chromatography purity: 99.984 percent and the water content is less than 0.001 percent.
Example 2
Adding antimony pentachloride serving as a catalyst into a 1,1, 1-trifluoro-2-chloroethane reaction kettle, heating the reaction kettle by steam until the temperature reaches 100 ℃, continuously adding raw materials into the reaction kettle according to the conditions that hydrogen fluoride is less than 250L/h, trichloroethylene is less than 180L/h and chlorine is 12-15 Kg/h, and controlling the pressure of the reaction kettle to be 0.7-0.8 MPa and the reaction temperature to be 100-115 ℃. And opening a valve to the gas buffer tank, and controlling the temperature of the reaction bubbler to be 65-85 ℃. And (3) opening a water inlet valve of the condenser, and controlling the top temperature of the condenser to be 40-45 ℃. And starting the cryogenic system, and cooling and collecting the emptying tail gas. The collected crude product 1,1, 1-trifluoro-2-chloroethane is rectified by a rectifying tower to remove alkali and washed by water, and then is sent to an alkaline hydrolysis section.
Adding 500kg of ethylene glycol, 1.0kg of potassium hydroxide and 100kg of trifluoroethanol into a pressure reaction kettle, sealing the reaction kettle, introducing 1,1, 1-trifluoro-2-chloroethane, stopping introducing the 1,1, 1-trifluoro-2-chloroethane when the introduction amount of the 1,1, 1-trifluoro-2-chloroethane reaches 118kg, and heating to 75 ℃ at the rotating speed of 200r/min for reaction for 3 hours. After the reaction is finished, adding 8kg of water into the reaction system, stirring for 10 minutes, filtering to remove potassium chloride solid precipitate to obtain filtrate, and then rectifying the filtrate by a rectifying tower, wherein the tower plates of the rectifying tower are 15-21 layers, the tower bottom temperature is 158-168 ℃, the tower top temperature is 70-80 ℃, the reflux ratio is 0.5-1.5, and the pressure is 8-15kPa to obtain the bis (2,2, 2-trifluoroethyl) ether with the yield of 97.7 percent, and the sampling analysis shows that the product has no pungent odor, and the peroxide in the product is not detected. High pressure liquid chromatography purity: 99.985 percent and the water content is less than 0.001 percent.
Example 3
Adding antimony pentachloride serving as a catalyst into a 1,1, 1-trifluoro-2-chloroethane reaction kettle, heating the reaction kettle by steam until the temperature reaches 100 ℃, continuously adding raw materials into the reaction kettle according to the conditions that hydrogen fluoride is less than 250L/h, trichloroethylene is less than 180L/h and chlorine is 12-15 Kg/h, and controlling the pressure of the reaction kettle to be 0.7-0.8 MPa and the reaction temperature to be 100-115 ℃. And opening a valve to the gas buffer tank, and controlling the temperature of the reaction bubbler to be 65-85 ℃. And (3) opening a water inlet valve of the condenser, and controlling the top temperature of the condenser to be 40-45 ℃. And starting the cryogenic system, and cooling and collecting the emptying tail gas. The collected crude product 1,1, 1-trifluoro-2-chloroethane is rectified by a rectifying tower to remove alkali and washed by water, and then is sent to an alkaline hydrolysis section.
Adding 500kg of ethylene glycol, 0.9kg of potassium hydroxide and 100kg of trifluoroethanol into a pressure reaction kettle, sealing the reaction kettle, introducing 1,1, 1-trifluoro-2-chloroethane, stopping introducing the 1,1, 1-trifluoro-2-chloroethane when the introduction amount of the 1,1, 1-trifluoro-2-chloroethane reaches 110kg, and raising the temperature at least 80 ℃ at the rotating speed of 150r/min for reaction for 2 hours. After the reaction is finished, adding 9kg of water into the reaction system, stirring for 10 minutes, filtering to remove potassium chloride solid precipitate to obtain filtrate, and then rectifying the filtrate by a rectifying tower, wherein the tower plates of the rectifying tower are 15-21 layers, the tower bottom temperature is 158-168 ℃, the tower top temperature is 70-80 ℃, the reflux ratio is 0.5-1.5, and the pressure is 8-15kPa, so that the yield of the bis (2,2, 2-trifluoroethyl) ether is 96.6%, and the product has no pungent odor and is not detected by peroxide in the product through sampling analysis. High pressure liquid chromatography purity: 99.981% and the water content is less than 0.001%.
Comparative example 1
For example, in U.S. Pat. No. 3,3363006 bis (2,2, 2-trifluoroethyl) ether and a process for producing the same, 23 parts of metallic sodium is charged into 300 parts of dry dioxane in a reactor equipped with a stirrer and a reflux condenser. The dioxane was heated to reflux with stirring. 150 parts of sodium 2,2, 2-trifluoroethoxide are added very slowly over a period of about one hour, or until the sodium has completely reacted to form sodium 2,2, 2-trifluoroethylate. 250 parts of 2,2, 2-trifluoroethyl-p-toluenesulfonate, which was prepared by reacting 2,2, 2-trifluoroethanol with p-toluenesulfonyl chloride, was placed in another reactor and heated to about 160 ℃ and 185 ℃. In the second reactor, the previously prepared sodium 2,2, 2-trifluoroethyl ether is added very slowly and the bis (2,2, 2-trifluoroethyl) ether is formed continuously and distilled off together with dioxane from the reactor into a cooled receiving vessel. The condensed water from the reactor was fractionated to give 46.5 parts of product having a boiling point of 55-73 ℃ and the crude product was washed successively with concentrated HCl, 62% H2 SO 4, concentrated H2 SO 4 and 5% NaOH solution. This was dehydrated on a drying agent and then fractionated in a distillation column to recover 20 parts of bis (2,2, 2-trifluoroethyl) ether. High pressure liquid chromatography purity: 98.294%, and water content is 0.009%.
Comparative example 2
For example, the preparation method of 1,1, 1-trifluoro-2-chloroethane provided by Chinese invention patent CN200910185098 is that 450g of antimony pentachloride is added into a 1500ml high-pressure reaction kettle, 36.12g of anhydrous hydrogen fluoride is added from the bottom of the reaction kettle, namely the addition amount of the anhydrous hydrogen fluoride is 1.2 times of the molar mass of the antimony pentachloride, the temperature is slowly increased while adding, the temperature is controlled to be between 80 and 90 ℃ after the addition of the anhydrous hydrogen fluoride is finished, 1,1, 2, 2-tetrachloroethane is added according to 45g per hour, the anhydrous hydrogen fluoride is simultaneously added, the addition amount of the anhydrous hydrogen fluoride is 3 times of the molar mass of the 1,1, 2, 2-tetrachloroethane, namely the mass is 16.07 g/hour, the internal pressure of the reaction kettle is controlled to be between 0.8 and 1.0MPa by adjusting the discharging speed, chlorine gas is introduced into the reaction kettle after 5 hours of reaction, the chlorine gas introduction amount is 0.45 g/hour per hour, the obtained reaction product is a mixed gas containing hydrogen fluoride, chlorine, hydrogen chloride and HCFC-133a, the product is cooled to 20-30 ℃ by water, then deep cooling is carried out by brine with the temperature of minus 15 ℃, then the product is led into an alkaline washing kettle with sodium hydroxide solution for alkaline washing to obtain HCFC-133a gas, the gas is dried by a molecular sieve, and then the gas is fractionated by a fractionating tower to obtain HCFC-133a finished products with the purity of more than 99.6%, the fractionation pressure is 0.7-1.5 Mpa, the temperature of the kettle of the fractionating tower is 60-90 ℃, the temperature of the top of the fractionating tower is 30-50 ℃, the comprehensive yield is 92.3 percent calculated by 1,1, 2, 2-tetrachloroethane.
130kg of 1,1, 1-trifluoro-2-chloroethane obtained in the above step was taken, and the rest was prepared into bis (2,2, 2-trifluoroethyl) ether in the same manner as in example condition 1, and the yield of bis (2,2, 2-trifluoroethyl) ether obtained was 92.7%, and the purity by sampling analysis and high pressure liquid chromatography was: 99.5 percent and the water content is less than 0.001 percent.
As can be seen from comparative example 1 and examples 1 to 3, the process has more readily available raw materials, can be free from supply limitation, and has simple equipment requirements, while sodium as a raw material has high equipment requirements and requires special material requirements. The invention has simple process and can realize clean and continuous production. In the washing process, only water can be used, compared with a comparative example in which concentrated sulfuric acid and concentrated hydrochloric acid are used, the method is safer to produce, other impurities such as chloride ions and sulfate ions cannot be introduced, the purity of the method can reach more than 99.98 percent, and the method meets the application of the solvent serving as the lithium battery electrolyte in the field of lithium batteries.
As can be seen from comparative example 2 and example 1,1, 1-trifluoro-2-chloroethane prepared in comparative example 2 can be mixed with 1,1, 2, 2-tetrachloroethane raw material, 1,1, 2, 2-tetrachloroethane and 1,1, 1-trifluoro-2-chloroethane have similar structures and close melting points, rectification is easier to generate azeotrope, separation is not easy, and the process does not use 1,1, 2, 2-tetrachloroethane as starting material, so that the 1,1, 1-trifluoro-2-chloroethane prepared in the invention has easier purity fractionation and higher purity, and the yield and purity of the subsequently prepared bis (2,2, 2-trifluoroethyl) ether are better than those of the bis (2,2, 2-trifluoroethyl) ether.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.

Claims (8)

1. The synthesis method of bis (2,2, 2-trifluoroethyl) ether is characterized by comprising the following steps: the method comprises the following steps:
preparing 1,1, 1-trifluoro-2-chloroethane;
adding 550 parts by weight of ethylene glycol 500-1.1 parts by weight, 0.9-1.1 parts by weight of potassium hydroxide and 100 parts by weight of trifluoroethanol into a pressure reaction kettle, sealing the reaction kettle, introducing 130 parts by weight of 1,1, 1-trifluoro-2-chloroethane 110-4 parts by weight, stirring and heating to 70-80 ℃ for reaction for 2-4 hours;
controlling the system temperature between 70 and 90 ℃, adding a polar solvent into the system, uniformly stirring, and filtering potassium chloride solid precipitate to obtain a filtrate;
the filtrate was rectified.
2. The process for the synthesis of bis (2,2, 2-trifluoroethyl) ether according to claim 1, wherein:
the stirring speed in the step 2) is 150-.
3. The process for the synthesis of bis (2,2, 2-trifluoroethyl) ether according to claim 1, wherein: the polar solvent in the step 3) is water, and the weight part of the water is 8-10.
4. The process for the synthesis of bis (2,2, 2-trifluoroethyl) ether according to claim 1, wherein: the stirring time in the step 3) is 8-15 minutes.
5. The process for the synthesis of bis (2,2, 2-trifluoroethyl) ether according to claim 1, wherein:
the rectification in the step 4) is completed in a rectifying tower, the tower plate number of the tower is 15-21 layers, the tower bottom temperature is 158-168 ℃, the tower top temperature is 70-80 ℃, the reflux ratio is 0.5-1.5, and the pressure is 8-15 kPa.
6. The process for the synthesis of bis (2,2, 2-trifluoroethyl) ether according to claim 1, wherein:
the step 1) of preparing the 1,1, 1-trifluoro-2-chloroethane further comprises the following steps:
s1, adding a catalyst into a 1,1, 1-trifluoro-2-chloroethane reaction kettle, heating the reaction kettle by steam to 100 ℃, introducing hydrogen fluoride, trichloroethylene and chlorine into the reaction kettle at a certain speed, and continuously adding the raw materials into the reaction kettle, wherein the pressure of the reaction kettle is controlled to be 0.7-0.8 Mpa, and the reaction temperature is controlled to be 100-115 ℃;
s2, opening a valve of a gas buffer tank, and controlling the temperature of a reaction bubbler to be 65-85 ℃; opening a water inlet valve of the condenser, and controlling the top temperature of the condenser to be 40-45 ℃;
s3, starting a cryogenic system, cooling the vented tail gas, collecting the discharged tail gas, rectifying the collected crude product 1,1, 1-trifluoro-2-chloroethane by a rectifying tower to remove alkali, washing with water, and sending to the alkaline hydrolysis section in the step 2).
7. The method for synthesizing bis (2,2, 2-trifluoroethyl) ether according to claim 6, wherein the aeration rate in step S1 is: the hydrogen fluoride is less than 250L/h, the trichloroethylene is less than 180L/h, and the chlorine is 12-15 Kg/h.
8. The method for synthesizing bis (2,2, 2-trifluoroethyl) ether according to claim 6, wherein the catalyst is antimony pentachloride.
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