CN114908360B - Synthesis process of perfluoro-isobutyronitrile - Google Patents

Synthesis process of perfluoro-isobutyronitrile Download PDF

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CN114908360B
CN114908360B CN202210701361.3A CN202210701361A CN114908360B CN 114908360 B CN114908360 B CN 114908360B CN 202210701361 A CN202210701361 A CN 202210701361A CN 114908360 B CN114908360 B CN 114908360B
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isobutyronitrile
perfluoroisobutyronitrile
electrolytic
raw material
mass ratio
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CN114908360A (en
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陈华峰
韩文锋
杨宇航
别超
刘兵
单长林
杨华涛
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Zhejiang Nuoya Fluorine Chemical Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B3/00—Electrolytic production of organic compounds
    • C25B3/01—Products
    • C25B3/11—Halogen containing compounds
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B3/00—Electrolytic production of organic compounds
    • C25B3/01—Products
    • C25B3/09—Nitrogen containing compounds
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B3/00—Electrolytic production of organic compounds
    • C25B3/20—Processes
    • C25B3/27—Halogenation
    • C25B3/28—Fluorination
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The application discloses a novel synthesis process of environment-friendly insulating gas perfluoro-isobutyronitrile. The application adopts isobutyronitrile ((CH) 3 ) 2 CHCN) is used as raw material, and is synthesized into perfluoroisobutyronitrile by one-step method in the presence of electrolytic fluorine source solution, conductive agent, promoter and solubilizer, the electrolytic temperature is controlled between 20 ℃ and 25 ℃, the voltage is between 7 and 10V, and the current is controlled at 3+/-0.5A/dm 2 . The limited electrochemical fluorination synthesis process can eliminate the traditional complex and lengthy chemical synthesis means, the target product can be synthesized only by one step, the conversion rate can reach 100%, the selectivity is 80-90%, and the byproduct is hydrogen, so that the method is environment-friendly; the other additives can be reused, a large amount of waste liquid and solid waste are not generated, and the electrofluorination process belongs to a mature industrial system, has the capability of industrialization, and has great prospect for synthesizing the perfluoroisobutyronitrile.

Description

Synthesis process of perfluoro-isobutyronitrile
Technical Field
The application belongs to the technical field of electrochemical fluorination processes, and particularly relates to a synthesis process of perfluoroisobutyronitrile.
Background
The european union has implemented greenhouse gas quota systems starting from 2015 and has imposed carbon tax starting from 2021. Limited by the carbon emission control targets related to Paris agreement, china is faced with huge emission reduction pressure, and perfluoro-isobutyronitrile has huge market application prospect and actual need.
Perfluoro-isobutyronitrile (C) 4 F 7 N) is used as a novel environment-friendly insulating and arc extinguishing gas, the greenhouse effect index (GWP) is only 2210, is far lower than that of sulfur hexafluoride (gwp=23500), can be used for replacing the traditional sulfur hexafluoride insulating gas, and greatly reduces the problem of atmospheric temperature and room effect. It can be combined with CO 2 、N 2 、O 2 Or one or more of air, and is filled into a sealed shell of medium-voltage or high-voltage equipment and an electric component of a solid dielectric layer. The perfluoroisobutyronitrile is used in medium-high voltage power equipment and has the following characteristics: the environment-friendly, excellent in insulating property and arc extinguishing property, good in compatibility with materials in a switch, low in toxicity and free of flash point, meets the requirements of health and safety, and can adapt to the requirements of severe low-temperature environment.
The synthesis method of the perfluoro-isobutyronitrile disclosed at present is mainly a traditional chemical method and an electroless fluorination method. Traditional chemical methods are classified into chemical synthesis and chemical cleavage methods.
The chemical cracking method mainly adopts conditions of high temperature, ultraviolet rays and the like to pyrolyze raw material chemicals so as to separate the perfluorinated isobutyronitrile, wherein the method comprises various modes of nitrogen-containing aromatic heterocycle ultraviolet pyrolysis, diazine compound pyrolysis, triazine compound pyrolysis, nitrogen-containing polycyclic compound pyrolysis and the like. The equation is shown below. The method has strict requirements, raw materials are difficult to synthesize, and large-scale production cannot be realized.
Chemical synthesis methods are of a large variety, but most of the methods involve severe reaction conditions, or the reaction process is complex and tedious, or the reactant structure is complex, and the reaction efficiency is low. For example, US3752840 reports the addition reaction of perfluoropropene with ethanedinitrile in the presence of potassium fluoride and hydrocyanic acid to give heptafluoroisobutyronitrile in a yield of 64.3%.
Li Li in patent CN108863847a provides a method for synthesizing heptafluoroisobutyronitrile by reacting perfluoroolefin as a raw material under the protection of nitrogen or inert gas, hexafluoropropylene is introduced at-70 ℃ and reacted at 50 ℃ for 10 hours, and the heptafluoroisobutyronitrile is obtained by distillation and collection at different temperatures according to the difference of boiling points of the raw material and the product.
The process of reacting perfluoro-isobutyryl fluoride with an ammonia solution to obtain perfluoro-isobutyramide and dehydrating is described in detail in patent CN109748814a and patent CN109320436 a.
In patent CN111349019a and patent CN110642749a, tosyl chloride is directly used to react with heptafluoroisobutyramide to prepare heptafluoroisobutyronitrile, and the reaction equation is as follows:
all the above routes have the problems of excessive reaction steps, complicated process, difficult raw material acquisition, excessive cost and the like, and a chemical synthesis method for the product of the perfluoroisobutyronitrile is not a particularly effective process method. Because the raw material isobutyronitrile compound has poor conductivity and is insoluble in hydrogen fluoride, no relevant electrofluorination process of the product is reported at present.
Disclosure of Invention
In view of the above problems in the prior art, it is an object of the present application to provide a novel process for the electrochemical fluorination of isobutyronitrile to perfluoroisobutyronitrile. Since the raw material isobutyronitrile is not soluble in or salified with hydrogen fluoride, the conductivity is very weak, and thus, no electrofluorination of isobutyronitrile has been reported before.
According to the application, by changing the electrolytic fluorine source solvent and adding the conductive agent, the accelerator and the solubilizer, the solubility and the conductivity of the raw materials and the solvent are improved, the isobutyronitrile is improved into a feasible and efficient electrolytic material, and finally the perfluoro-isobutyronitrile can be synthesized through a one-step method.
The application relates to a synthesis process of perfluoro-isobutyronitrile, which adopts an electric fluorination process, specifically uses isobutyronitrile as a raw material, and synthesizes the perfluoro-isobutyronitrile by a one-step method in the presence of electrolytic fluorine source solution, conductive agent, accelerator and solubilizer; the reaction equation is as follows:
further, the application also defines that the conductive agent is one of fluoride salt, preferably KF, agF, csF or NaF, and most preferably CsF, and the mass ratio of the conductive agent to the isobutyronitrile is 25:1-200:1, preferably 50:1.
Further, the application also defines that the accelerator is crown ether compound, preferably 18-crown (ether) -6 or 15-crown (ether) -5, the mass ratio of the conductive agent to the accelerator is 1:1-10:1, preferably 3:1, wherein the structural formula of the 18-crown (ether) -6 or 15-crown (ether) -5 is shown as follows:
further, the application also defines that the solubilizing agent is a hydrofluoroether compound, preferably HFE-374, HFE-347, HFE-356mec or HFE-458; the mass ratio of the solubilizer to the isobutyronitrile serving as an electrolysis raw material is 1:1-10:1, preferably 3:1;
wherein the structural formulas of HFE-374, HFE-347, HFE-356mec and HFE-458 are as follows:
furthermore, the application also defines that the electrolytic fluorine source solution is a hydrogen fluoride salt solution of triethylamine or tripropylamine, the feeding mass ratio of hydrogen fluoride to triethylamine or tripropylamine is 3-10:1, and the mass ratio of hydrogen fluoride to tripropylamine is 3:1.
Further, the application also defines that the mass ratio of the electrolytic fluorine source solution to the isobutyronitrile is 2:1-10:1, preferably 10:3.
Further, the application also defines that the electrolysis temperature is 15-25 ℃, preferably 20 ℃, the voltage is 7-10V, and the current is controlled to be 3+/-0.5A/dm 2 。
Further, the application also defines that the charging ratio of the electrolytic fluorine source solution, the electrolytic raw material, the conductive agent, the accelerator and the solubilizer is 100:30:0.6:0.2:10.
The application also defines the synthesis of perfluoroisobutyronitrile from isobutyronitrile by electrochemical fluorination, using the following process steps:
1) Adding a proper amount of solubilizer into the raw materials, stirring and mixing uniformly, adding the conductive agent and the accelerator into the mixed solution of the raw materials and the solubilizer according to a proportion, and stirring uniformly again to prepare a modified raw material mixed solution;
2) After preparing a salt solution of hydrogen fluoride and amine in a corresponding proportion according to the requirement, adding the salt solution into an electrolytic tank, and keeping the temperature at a low temperature; then the modified raw material mixed solution is slowly led into an electrolytic tank, and stirring and aging processes are started, generally for 4 to 5 hours;
3) And starting condensation reflux and power supply, and starting electrochemical fluorination. In the reaction process, the temperature of the electrolytic tank is controlled to be about 15-25 ℃. The target product is in a gas phase, and is obtained by cooling, liquefying and collecting after the tail gas pipe is cleaned by alkali liquor.
The solubilizer in the step 1) is mainly a hydrofluoroether product, and the isobutyronitrile and the hydrogen fluoride are mutually insoluble and are easy to delaminate, so that the electrolysis effect is poor. The solubilizer can well solve the problem, the hydrofluoroether product can dissolve both organic compounds and fluorinated products, and the hydrofluoroether and isobutyronitrile can well form a mixed solution, so that the electrolysis efficiency is improved. Meanwhile, the hydrofluoroether has certain electrical insulation property, is not easy to be broken down electrically, and can continuously react.
In addition, in the step 1), the conductive agent is fluoride salt and the accelerant is crown ether type substance. Since the raw material isobutyronitrile cannot form salt in the hydrogen fluoride solution, the conductivity is very weak; the fluoride salt can provide F ions in the hydrogen fluoride, so that the conductivity of the electrolyte is increased, the crown ether can further improve the ion release effect of the fluoride salt, and the consumption is small, so that the influence on an electrolysis experiment is avoided. However, too much fluoride will damage the corrosion electrode plate, too much crown ether is costly and too little will not have the desired effect, so it is most preferred when the ratio of isobutyronitrile, fluoride and crown ether is 50:1:0.3.
In the step 2), mainly a mixed solution of hydrogen fluoride and organic amine in a proper proportion is prepared, and the organic amine generally adopts triethylamine and tripropylamine, and the aim is that: a controlling voltage and conducting current intensity; and part b, the solubility is enhanced 3. The volatility of hydrogen fluoride is reduced, the escape loss is reduced, but too much added amine salt can also cause the generation of a large amount of byproducts, the electric quantity is wasted, the electrolysis power is reduced, and meanwhile, jelly corrosion can occur on an electrolysis plate and needs to be cleaned regularly. Therefore, the proper proportion is well regulated, and the mass 3:1, 6:1 and 9:1 solutions of hydrogen fluoride and triethylamine and the mass 3:1, 6:1 and 9:1 solutions of hydrogen fluoride and tripropylamine generally have better effects, wherein the comprehensive effect of the mass 3:1 solutions of hydrogen fluoride and tripropylamine is the best. The aging step is beneficial to improving the effect of the additive, and the best effect can be achieved before the reaction.
And 3) after formally starting the reaction, controlling the reaction temperature to be 20-25 ℃. The boiling point of the raw materials is higher, but the boiling point of the perfluorinated products is low, the perfluorinated products are directly changed into gas, and the gas is discharged from a tail gas port. The boiling point of the hydrogen fluoride is 19 ℃, and the hydrogen fluoride can be boiled in the reaction kettle, so that a condensing reflux device is needed to reflux the HF, and the amine salt in the HF is also beneficial to reducing the escape amount of the hydrogen fluoride.
Finally, removing entrained hydrogen fluoride from the alkali liquor from the gas phase port, and removing byproduct hydrogen through freezing and liquefying to obtain the target product of perfluoroisobutyronitrile. Meanwhile, the conductive agent, the accelerant and the solubilizer are difficult to be electrolytically fluorinated compared with the raw materials, so that the conductive agent, the accelerant and the solubilizer can be continuously applied, and after being added once, the conductive agent, the accelerant and the solubilizer do not need to be added for multiple times and can be supplemented in a period.
Compared with the prior art, the electrochemical fluorination method can be adopted to synthesize the target product in one step, the conversion rate can reach 100%, the selectivity is 80% -90%, and the byproduct is hydrogen, thus being environment-friendly. The other additives can be reused, a large amount of waste liquid and solid waste are not generated, and the electrofluorination process belongs to a mature industrial system, has the capability of industrialization, and has great prospect for synthesizing the perfluoroisobutyronitrile.
Detailed Description
The application will be further illustrated with reference to specific examples, but the scope of the application is not limited thereto. The present application will be described in further detail with reference to preferred embodiments, so that those skilled in the art can better understand the technical aspects of the present application. The percentages in the application are mass percent unless specified otherwise.
Example 1: 1.2kg of hydrofluoroether HFE 347 was added to 3.6kg of isobutyronitrile as an electrolytic raw material, and mixed and stirred well. Then, 72g of cesium fluoride and 24g of 18-crown (ether) -6 (hereinafter abbreviated as crown ether unless otherwise noted) were added to the mixed solution, respectively, and stirred again uniformly to prepare a modified raw material mixed solution.
Adding 9kg of hydrogen fluoride and 3kg of tripropylamine into an electrolytic tank, uniformly mixing and stirring, controlling the temperature to be about 0 ℃, slowly adding the prepared mixed solution of the modified electrolytic raw material into the electrolytic tank, and predicting that the dripping is completed within about 3 hours. After the dripping is completed, stirring is started for half an hour, then stirring is closed, and standing and ageing are carried out for 4-5 hours.
And starting an electrofluorination experiment, controlling the condensation reflux at-20 ℃ and the electrolytic tank at 20+/-5 ℃, and slowly rising the voltage from 6V until the voltage is kept at about 10V, and keeping the current above 80A. As the reaction proceeds, the product is continuously produced. And removing escaped hydrogen fluoride from the tail gas through alkali liquor, and then freezing at the temperature of minus 40 ℃ to obtain a liquefied crude product, and simultaneously, directly discharging byproduct hydrogen to the atmosphere.
After monitoring the end of the electrofluorination reaction, the liquefied perfluoroisobutyronitrile crude product was charged into an empty gas cylinder storage tank, and weighed to obtain 8.23kg of crude product, and the product structure and molar crude yield were determined by GC-MS to be 80.9%. Purifying by cryogenic rectification, washing and drying, compressing into a gas cylinder, and determining the purity to be 95.4% by gas chromatography.
Comparative example 1: by adopting the traditional electrofluorination process, the electrofluorination operation is the same as that of the example 1, 3.6kg of the electrolytic raw material isobutyronitrile is added into 12kg of hydrogen fluoride, the reaction is controlled at about 20 ℃, the voltage is controlled at about 10V, the current is very low, the raw material and the hydrogen fluoride are layered, no target product is detected after the reaction is carried out for 15 hours, and the hydrogen fluoride has an escape phenomenon.
Comparative example 2: the electrofluorination was carried out in the same manner as in example 1, and 3.6kg of isobutyronitrile as an electrolytic raw material was added to a mixture of 9kg of hydrogen fluoride and 3kg of tripropylamine, the reaction was controlled at about 20℃and the voltage was controlled at about 10V and the current was controlled at about 20A, and the raw material and hydrogen fluoride were partially dissolved. After the end of the electrofluorination reaction is monitored, a target product is generated. The weight of the crude product was 2.2kg and the molar crude yield was 21.63%.
Comparative example 3: the electrofluorination was carried out in the same manner as in example 1, and 3.6kg of isobutyronitrile as an electrolytic raw material and HFE-3471.2kg of hydrofluoroether were mixed and added to 9kg of hydrogen fluoride and 3kg of tripropylamine, the reaction was controlled at about 0℃and the voltage was controlled at about 10V and the current was controlled at about 30A, whereby the raw material and hydrogen fluoride were dissolved. After the end of the electrofluorination reaction is monitored, a target product is generated. The weight of the crude product was 4.5kg and the molar crude yield was 44.23%.
Comparative example 4: the electrofluorination was carried out in the same manner as in example 1, and 3.6kg of the electrolytic starting material isobutyronitrile, 72g of cesium fluoride and 24g of crown ether were mixed and added to 9kg of hydrogen fluoride and 3kg of tripropylamine, the reaction was controlled at about 0℃and the voltage was controlled at about 10V, the current was 50A, and the starting material and hydrogen fluoride were partially dissolved. After the end of the electrofluorination reaction is monitored, a target product is generated. The weight of the crude product was 3.1kg and the molar crude yield was 30.47%.
The results of example 1 and comparative examples 1 to 4 are shown in Table 1.
TABLE 1 results for example 1, comparative examples 1-4
Example 2:
the same procedure as in example 1 was followed, and 1.2kg of hydrofluoroether HFE-347 was added to 3.6kg of isobutyronitrile as an electrolytic raw material, 72g of cesium fluoride and 24g of crown ether were added to the mixture, and after mixing uniformly, to the electrolytic mixture of 9kg of hydrogen fluoride and 3kg of triethylamine, the electric fluorination test was started.
After monitoring the end of the electrofluorination reaction, the liquefied perfluoroisobutyronitrile crude product was charged into an empty gas cylinder storage tank and weighed to obtain a crude product with a mass of 7.83kg and a molar crude yield of 76.96%.
Example 3:
the procedure of example 1 was followed, except that 1.2kg of hydrofluoroether HFE-347 was added to 3.6kg of isobutyronitrile as an electrolytic raw material, 72g of cesium fluoride and 24g of crown ether were added to the mixture, and after mixing uniformly, the mixture was added to an electrolytic mixture of 11kg of hydrogen fluoride and 1.1kg of tripropylamine, and the electric fluorination experiment was started.
After monitoring the end of the electrofluorination reaction, the liquefied perfluoroisobutyronitrile crude product was charged into an empty gas cylinder storage tank, and weighed to obtain a crude product with a mass of 6.21kg and a molar crude yield of 61.04%.
Example 4:
the procedure of example 1 was followed, except that 1.2kg of hydrofluoroether HFE-347 was added to 3.6kg of isobutyronitrile as an electrolytic raw material, 72g of potassium fluoride and 24g of crown ether were added to the mixture, and after mixing uniformly, the mixture was added to an electrolytic mixture of 9kg of hydrogen fluoride and 3kg of tripropylamine, and the electric fluorination test was started.
After monitoring the end of the electrofluorination reaction, the liquefied perfluoroisobutyronitrile crude product was charged into an empty gas cylinder storage tank and weighed to obtain a crude product with a mass of 7.54kg and a molar crude yield of 74.11%.
Example 5:
the procedure of example 1 was followed, except that 1.2kg of hydrofluoroether HFE-347 was added to 3.6kg of isobutyronitrile as an electrolytic raw material, 72g of cesium fluoride (crown ether was not added) was added to the mixture, and after mixing uniformly, it was added to an electrolytic mixture of 9kg of hydrogen fluoride and 3kg of tripropylamine, and the electric fluorination experiment was started.
After the end of the electrofluorination reaction was monitored, the liquefied perfluoroisobutyronitrile crude product was charged into an empty gas cylinder storage tank, and weighed to obtain a crude product with a mass of 6.3kg and a molar crude yield of 61.92%.
Example 6:
the procedure of example 1 was followed, except that 1.2kg of hydrofluoroether HFE-347 was added to 3.6kg of isobutyronitrile as an electrolytic raw material, 72g of cesium fluoride and 24g of 15-crown (ether) -5 were added to the mixture, and after mixing uniformly, the mixture was added to an electrolytic mixture of 9kg of hydrogen fluoride and 3kg of tripropylamine, and the electric fluorination test was started.
After monitoring the end of the electrofluorination reaction, the liquefied perfluoroisobutyronitrile crude product was charged into an empty gas cylinder storage tank, and weighed to obtain a crude product with a mass of 7.6kg and a molar crude yield of 74.7%.
Example 7:
the procedure of example 1 was followed, except that 1.2kg of hydrofluoroether HFE-458 was added to 3.6kg of isobutyronitrile as an electrolytic raw material, 72g of cesium fluoride and 24g of crown ether were added to the mixture, and after mixing uniformly, the mixture was added to an electrolytic mixture of 9kg of hydrogen fluoride and 3kg of tripropylamine, and the electric fluorination test was started.
After monitoring the end of the electrofluorination reaction, the liquefied perfluoroisobutyronitrile crude product was charged into an empty gas cylinder storage tank, and weighed to obtain a crude product with a mass of 8.0kg and a molar crude yield of 78.63%.
Example 8:
the procedure of example 1 was followed, except that 1.2kg of hydrofluoroether HFE-356mec was added to 3.6kg of isobutyronitrile as an electrolytic raw material, 72g of cesium fluoride and 24g of crown ether were added to the mixture, and after mixing uniformly, the mixture was added to an electrolytic mixture of 9kg of hydrogen fluoride and 3kg of tripropylamine, and the electric fluorination test was started.
After monitoring the end of the electrofluorination reaction, the liquefied perfluoroisobutyronitrile crude product was charged into an empty gas cylinder storage tank and weighed to obtain a crude product with a mass of 7.8kg and a molar crude yield of 76.67%.
Example 9:
the procedure of example 1 was followed, except that 0.36kg of hydrofluoroether HFE-347 was added to 3.6kg of isobutyronitrile as an electrolytic raw material, 72g of cesium fluoride and 24g of crown ether were added to the mixture, and after mixing uniformly, the mixture was added to an electrolytic mixture of 9kg of hydrogen fluoride and 3kg of tripropylamine, and the electric fluorination test was started.
After monitoring the end of the electrofluorination reaction, the liquefied perfluoroisobutyronitrile crude product was charged into an empty gas cylinder storage tank, and weighed to obtain a crude product with a mass of 5.84kg and a molar crude yield of 57.40%.
Example 10:
the procedure of example 1 was followed, except that 3.6kg of hydrofluoroether HFE-347 was added to 3.6kg of isobutyronitrile as an electrolytic raw material, 72g of cesium fluoride and 24g of crown ether were added to the mixture, and after mixing uniformly, the mixture was added to an electrolytic mixture of 9kg of hydrogen fluoride and 3kg of tripropylamine, and the electric fluorination test was started.
After the end of the electrofluorination reaction was monitored, the liquefied perfluoroisobutyronitrile crude product was charged into an empty gas cylinder storage tank, and weighed to obtain a crude product with a mass of 6.12kg and a molar crude yield of 60.15%. The addition of too much insulating hydrofluoroether will result in an increase in electrolysis time of 5 hours over other groups with an increase in power consumption.
Example 11:
the procedure of example 1 was followed, except that 1.2kg of hydrofluoroether HFE-347 was added to 3.6kg of isobutyronitrile as an electrolytic raw material, 72g of cesium fluoride and 7.2g of crown ether were added to the mixture, and after mixing uniformly, the mixture was added to an electrolytic mixture of 9kg of hydrogen fluoride and 3kg of tripropylamine, and the electric fluorination experiment was started.
After monitoring the end of the electrofluorination reaction, the liquefied perfluoroisobutyronitrile crude product was charged into an empty gas cylinder storage tank, and weighed to obtain a crude product with a mass of 7.33kg and a molar crude yield of 72.04%.
Example 12:
the procedure of example 1 was followed, except that 1.2kg of hydrofluoroether HFE-347 was added to 3.6kg of isobutyronitrile as an electrolytic raw material, 72g of cesium fluoride and 72g of crown ether were added to the mixture, and after mixing uniformly, the mixture was added to an electrolytic mixture of 9kg of hydrogen fluoride and 3kg of tripropylamine, and the electric fluorination test was started.
After the end of the electrofluorination reaction is monitored, the liquefied perfluoroisobutyronitrile crude product is filled into an empty gas cylinder storage tank, and the crude product is weighed to obtain the crude product with the mass of 7.89kg and the molar crude yield of 77.55%.
Example 13:
the procedure of example 1 was followed, except that 1.2kg of hydrofluoroether HFE-347 was added to 3.6kg of isobutyronitrile as an electrolytic raw material, 900g of cesium fluoride and 90g of crown ether were added to the mixture, and after mixing uniformly, the mixture was added to an electrolytic mixture of 9kg of hydrogen fluoride and 3kg of tripropylamine, and the electric fluorination test was started.
After monitoring the end of the electrofluorination reaction, the liquefied perfluoroisobutyronitrile crude product was charged into an empty gas cylinder storage tank, and weighed to obtain a crude product with a mass of 3.32kg and a molar crude yield of 32.63%.
Example 14:
the procedure of example 1 was followed, except that 1.2kg of hydrofluoroether HFE-347 was added to 3.6kg of isobutyronitrile as an electrolytic raw material, 18g of cesium fluoride and 6g of crown ether were added to the mixture, and after mixing uniformly, the mixture was added to an electrolytic mixture of 9kg of hydrogen fluoride and 3kg of tripropylamine, and the electric fluorination test was started.
After monitoring the end of the electrofluorination reaction, the liquefied perfluoroisobutyronitrile crude product was charged into an empty gas cylinder storage tank, and weighed to obtain 3.09kg of crude product with a molar crude yield of 30.37%.
Example 15:
the procedure of example 1 was followed, except that 0.6kg of hydrofluoroether HFE-347 was added to 1.8kg of isobutyronitrile as an electrolytic raw material, 36g of cesium fluoride and 12g of crown ether were added to the mixture, and after mixing uniformly, the mixture was added to an electrolytic mixture of 9kg of hydrogen fluoride and 3kg of tripropylamine, and the electric fluorination test was started.
After monitoring the end of the electrofluorination reaction, the liquefied perfluoroisobutyronitrile crude product was charged into an empty gas cylinder storage tank, and weighed to obtain 3.8kg of crude product with a molar crude yield of 74.7%.
Example 16:
the procedure of example 1 was followed, except that 1.5kg of hydrofluoroether HFE-347 was added to 4.5kg of isobutyronitrile as an electrolytic raw material, 90g of cesium fluoride and 30g of crown ether were added to the mixture, and after mixing uniformly, the mixture was added to an electrolytic mixture of 9kg of hydrogen fluoride and 3kg of tripropylamine, and the electric fluorination test was started.
After the end of the electrofluorination reaction was monitored, the liquefied perfluoroisobutyronitrile crude product was charged into an empty gas cylinder storage tank, and weighed to obtain a crude product with a mass of 6.56kg and a molar crude yield of 51.58%.
What has been described in this specification is merely an enumeration of possible forms of implementation for the inventive concept and may not be considered limiting of the scope of the present application to the specific forms set forth in the examples.

Claims (12)

1. A synthesis process of perfluoroisobutyronitrile adopts an electrofluorination process and is characterized in that isobutyronitrile is used as a raw material, and the perfluoroisobutyronitrile is synthesized by a one-step method in the presence of electrolytic fluorine source solution, a conductive agent, an accelerator and a solubilizer; the reaction equation is as follows:
；
the conductive agent is fluorine salt, and the mass ratio of the conductive agent to the isobutyronitrile is 1:50;
the accelerator is crown ether compound, and the mass ratio of the conductive agent to the accelerator is 1:1-10:1;
the solubilizer is a hydrofluoroether compound, and the mass ratio of the solubilizer to the electrolytic raw material isobutyronitrile is 1:1-10:1;
the electrolytic fluorine source solution is a hydrogen fluoride salt solution of triethylamine or tripropylamine, and the feeding mass ratio of hydrogen fluoride to triethylamine or tripropylamine is 3-10:1.
2. The process for synthesizing perfluoroisobutyronitrile according to claim 1, wherein the conductive agent is one of KF, agF, csF and NaF.
3. The synthesis process of perfluoroisobutyronitrile according to claim 1, wherein the accelerator is 18-crown (ether) -6 or 15-crown (ether) -5, and the mass ratio of the conductive agent to the accelerator is 3:1.
4. The process for synthesizing perfluoroisobutyronitrile according to claim 1, wherein the accelerator is 18-crown (ether) -6 or 15-crown (ether) -5.
5. The synthesis process of perfluoroisobutyronitrile according to claim 1, wherein the mass ratio of the conductive agent to the accelerator is 3:1.
6. The process for synthesizing perfluoroisobutyronitrile according to claim 1, wherein the solubilizing agent is HFE-374, HFE-347, HFE-356mec or HFE-458, and the mass ratio of the solubilizing agent to the electrolytic raw material isobutyronitrile is 3:1.
7. The process for synthesizing perfluoroisobutyronitrile according to claim 1, wherein the mass ratio of hydrogen fluoride to tripropylamine is 3:1.
8. The synthesis process of perfluoroisobutyronitrile according to claim 1, wherein the mass ratio of electrolytic fluorine source solution to isobutyronitrile is 2:1-10:1.
9. The process for synthesizing perfluoroisobutyronitrile according to claim 1, wherein the mass ratio of electrolytic fluorine source solution to isobutyronitrile is 10:3.
10. The process for synthesizing perfluoroisobutyronitrile according to any one of claims 1 to 9, wherein the electrolysis temperature is 15 to 25 ℃, the voltage is 7 to 10V, and the current is controlled at 3.+ -. 0.5A/dm 2 。
11. The process for the synthesis of perfluoroisobutyronitrile according to any of claims 1 to 9, characterized in that the electrolysis temperature is 20 ℃.
12. The process for synthesizing perfluoroisobutyronitrile according to any one of claims 1 to 9, wherein the mass ratio of electrolytic fluorine source solution, electrolytic raw material, conductive agent, accelerator and solubilizer is 100:30:0.6:0.2:10.
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