CN114908360A - Synthesis process of perfluoroisobutyronitrile - Google Patents
Synthesis process of perfluoroisobutyronitrile Download PDFInfo
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Abstract
The invention discloses a novel synthesis process of environment-friendly insulating gas perfluoroisobutyronitrile. The invention adopts isobutyronitrile ((CH) 3 ) 2 CHCN) as raw material, under the existence of electrolytic fluorine source solution, conductive agent, promoter and solubilizer, synthesizing the perfluoroisobutyronitrile by one step method, controlling the electrolytic temperature at 20-25 ℃, the voltage at 7-10V and the current at 3 +/-0.5A/dm 2 . By adopting the limited electrochemical fluorination synthesis process, the traditional complex and long chemical synthesis means can be abandoned, the target product can be synthesized by only one step, meanwhile, the conversion rate can reach 100%, the selectivity is 80-90%, the byproduct is hydrogen, and the process is green and environment-friendly; other additives can be repeatedly used, no large amount of waste liquid and solid waste are generated, the electrofluorination process belongs to a mature industrial system, and the process has the industrialization capability and is used for perfluoroisobutyronitrileThe synthesis of (A) has great prospect.
Description
Technical Field
The invention belongs to the technical field of electrochemical fluorination processes, and particularly relates to a synthesis process of perfluoroisobutyronitrile.
Background
The european union started to implement the greenhouse gas quota system in 2015 and collected carbon taxes in 2021. Being limited by the carbon emission control target related to Paris agreement, China will face huge emission reduction pressure, and perfluoroisobutyronitrile has huge market application prospect and practical needs.
Perfluoroisobutyronitrile (C) 4 F 7 N) is used as a novel environment-friendly insulating and arc-extinguishing gas, has a Global Warming Potential (GWP) of only 2210, which is much 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 greenhouse effect. It can be mixed with CO 2 、N 2 、O 2 Or one or more of air, and filling the mixture into a sealed shell of medium-voltage or high-voltage equipment and an electrical component of a solid dielectric layer for use. The perfluoroisobutyronitrile is used in medium-high voltage power equipment and has the following characteristics: the environment-friendly switch has the advantages of friendly environmental characteristics, excellent insulating property, excellent arc extinguishing property, good compatibility with materials in the switch, low toxicity, no flash point, health and safety requirements and adaptability to severe low-temperature environment requirements.
The presently disclosed synthetic method of perfluoroisobutyronitrile is mainly a conventional chemical method, an electroless fluorination method. Conventional chemical methods are divided into chemical synthesis and chemical cleavage methods.
The chemical cracking method is mainly characterized in that raw material chemicals are pyrolyzed under the conditions of high temperature, ultraviolet rays and the like so as to separate the perfluoroisobutyronitrile, wherein the conditions comprise various modes of ultraviolet pyrolysis of nitrogen-containing aromatic heterocycles, pyrolysis of diazine compounds, pyrolysis of triazine compounds, pyrolysis of nitrogen-containing polycyclic compounds and the like. The equation is shown below. The method has harsh requirements and conditions, and raw materials are difficult to synthesize, so that large-scale production cannot be realized.
The chemical synthesis methods have many kinds, but most of them involve harsh reaction conditions, or the reaction process is complicated, or the structure of the reactant is complicated, and the reaction efficiency is low. For example, U.S. Pat. No. 3,182,840 reported that perfluoropropene and ethanedinitrile undergo an addition reaction in the presence of potassium fluoride and hydrocyanic acid to give heptafluoroisobutyronitrile in a 64.3% yield.
Li 108863847A provides a method for synthesizing heptafluoroisobutyronitrile by reacting perfluoroolefin as raw material under the protection of nitrogen or inert gas, introducing hexafluoropropylene at-70 ℃, reacting at 50 ℃ for 10h, and distilling and collecting heptafluoroisobutyronitrile at different temperatures according to different boiling points of the raw material and the product.
The process of reacting perfluoroisobutyryl fluoride with ammonia solution to give perfluoroisobutyramide and dehydrating is described in detail in patent CN109748814A and patent CN 109320436A.
In patent CN111349019A and patent CN110642749A, tosyl chloride is directly reacted with heptafluoroisobutyramide to obtain heptafluoroisobutyronitrile, and the reaction equation is shown as follows:
all the routes have the problems of excessive reaction steps, complicated process, difficult obtainment of raw materials, high cost and the like, and the chemical synthesis method has no particularly effective process method for the product of the perfluoroisobutyronitrile. Because the isobutyronitrile compound as a raw material 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, the present invention is directed to a novel electrofluorination process for electrochemical fluorination of isobutyronitrile to produce perfluoroisobutyronitrile. The isobutyronitrile used as a raw material cannot be dissolved in hydrogen fluoride, cannot form a salt with hydrogen fluoride, and has weak conductivity, so that no report about electrofluorination of isobutyronitrile is available before.
According to the invention, the electrolytic fluorine source solvent is changed, the conductive agent, the accelerator and the solubilizer are added, the solubility and the conductivity of the raw material and the solvent are improved, the isobutyronitrile is improved into a feasible and efficient electrolytic material, and finally the perfluoroisobutyronitrile can be synthesized through a one-step method.
The invention provides a synthesis process of perfluoroisobutyronitrile, which adopts an electrofluorination process, particularly adopts isobutyronitrile as a raw material, and synthesizes the isobutyronitrile into perfluoroisobutyronitrile by a one-step method in the presence of electrolytic fluorine source solution, a conductive agent, an accelerant and a solubilizer; the reaction equation is as follows:
furthermore, the invention also limits that the conductive agent is villiaumite, preferably one of KF, AgF, CsF or NaF, and most preferably CsF, and the mass ratio of the conductive agent to isobutyronitrile is 25: 1-200: 1, and preferably 50: 1.
Furthermore, the invention also defines that the accelerant is a crown ether compound, preferably 18-crown (ether) -6 or 15-crown (ether) -5, the mass ratio of the conductive agent to the accelerant 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 invention also defines that the solubilizer is a hydrofluoroether compound, preferably HFE-374, HFE-347, HFE-356mec or HFE-458; the mass ratio of the solubilizer to the raw material isobutyronitrile for electrolysis is 1: 1-10: 1, preferably 3: 1;
wherein the structural formulas of HFE-374, HFE-347, HFE-356mec and HFE-458 are shown as follows:
furthermore, the invention also defines that the electrolytic fluorine source solution is triethylamine or tripropylamine hydrogen fluoride solution, the feeding mass ratio of hydrogen fluoride to triethylamine or tripropylamine is 3-10:1, and the preferred mass ratio of hydrogen fluoride to tripropylamine is 3: 1.
Furthermore, the mass ratio of the electrolytic fluorine source solution to the isobutyronitrile is limited to be 2: 1-10: 1, and preferably 10: 3.
Furthermore, the invention also limits the electrolysis temperature to be 15-25 ℃, preferably 20 ℃, the voltage to be 7-10V and the current to be controlled to be 3 +/-0.5A/dm 2 。
Furthermore, the invention also defines the feeding ratio of the electrolytic fluorine source solution, the electrolytic raw material, the conductive agent, the promoter and the solubilizer as 100:30:0.6:0.2: 10.
The invention 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 in proportion, and stirring uniformly again to prepare a modified raw material mixed solution;
2) after preparing a salt solution with hydrogen fluoride and amine in a corresponding ratio according to requirements, adding the salt solution into an electrolytic cell, and keeping the temperature at a low temperature; then slowly introducing the modified raw material mixed solution into an electrolytic tank, starting stirring and aging processes, wherein the time is generally 4-5 hours;
3) the condensation reflux and power supply are turned on to start the electrochemical fluorination. And in the reaction process, controlling the temperature of the electrolytic bath to be about 15-25 ℃. The target product is a gas phase, and is obtained by washing the tail gas pipe with alkali liquor, cooling, liquefying and collecting.
In the step 1), the solubilizer is mainly a hydrofluoroether product, and isobutyronitrile and hydrogen fluoride are mutually insoluble and are easy to delaminate, so that the electrolytic 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, is not easy to be broken down electrically and can continuously react.
In addition, in the step 1), the conductive agent is villaumite and the accelerator is crown ether substances. The isobutyronitrile serving as the raw material cannot form salt in a hydrogen fluoride solution, so that the conductivity is very weak; the fluorine 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 fluorine salt, the using amount is small, and the electrolysis experiment cannot be influenced. However, too much fluorine salt may damage the electrode plate, too much crown ether is expensive, too little crown ether may not achieve the target effect, and therefore, it is preferable that the ratio of isobutyronitrile, fluorine salt and crown ether is 50:1: 0.3.
The step 2) is mainly to prepare a mixed solution of hydrogen fluoride and organic amine in a proper proportion, wherein the organic amine generally adopts triethylamine and tripropylamine, and the purpose is as follows: a, controlling voltage and conducting current intensity; part b enhances the solubility 3. the volatility of the hydrogen fluoride is reduced, the escape loss is reduced, but excessive addition of amine salt can also cause generation of a large amount of byproducts, waste electricity, reduce the electrolytic power, and simultaneously cause jelly corrosion on an electrolytic plate, which needs to be cleaned regularly. Therefore, the appropriate proportion is prepared, and generally, solutions with the mass ratios of 3:1, 6:1 and 9:1 of hydrogen fluoride and triethylamine and solutions with the mass ratios of 3:1, 6:1 and 9:1 of hydrogen fluoride and tripropylamine have better effects, wherein the solution with the mass ratio of 3:1 of hydrogen fluoride and tripropylamine has the best comprehensive effect. The aging step is beneficial to improving the effect of the additive, and the optimal effect can be achieved before reaction.
And 3) after the reaction is formally started, controlling the reaction temperature to be 20-25 ℃. Because the boiling point of the raw material is higher, but the boiling point of the perfluorinated product is low, the perfluorinated product directly turns into gas and is discharged from a tail gas port. The boiling point of the hydrogen fluoride is 19 ℃, the hydrogen fluoride can boil in the reaction kettle, so a condensation reflux device is needed for refluxing the HF, and meanwhile, the amine salt in the HF is also beneficial to reducing the escape amount of the hydrogen fluoride.
And finally, removing hydrogen fluoride carried in the alkali liquor from the gas phase outlet, and removing a by-product hydrogen gas through freezing and liquefying to obtain the target product perfluoroisobutyronitrile. Meanwhile, compared with the raw materials, the conductive agent, the accelerator and the solubilizer are difficult to be electrolytically fluorinated, so the conductive agent, the accelerator and the solubilizer can be continuously used, and can be periodically supplemented without being added for many times after being added once.
Compared with the prior art, the method of electrochemical fluorination can synthesize the target product by only one step, meanwhile, the conversion rate can reach 100%, the selectivity is 80-90%, the byproduct is hydrogen, and the method is green and environment-friendly. Other additives can be repeatedly used, no large amount of waste liquid and solid waste are generated, the electro-fluorination process belongs to a mature industrial system, and the process has industrial capacity and great prospect for the synthesis of perfluoroisobutyronitrile.
Detailed Description
The present invention is further illustrated by the following examples, which should not be construed as limiting the scope of the invention. In order to make the technical solutions of the present invention better understood by those skilled in the art, the present invention will be further described in detail with reference to the following preferred embodiments. In the present application, unless otherwise specified, all percentages are by mass.
Example 1: 1.2kg of hydrofluoroether HFE 347 was added to 3.6kg of isobutyronitrile as an electrolytic raw material, and the mixture was stirred uniformly. Thereafter, 72g of cesium fluoride and 24g of 18-crown (ether) -6 (hereinafter simply referred to as crown ether unless otherwise specified) were added to the mixed solution, respectively, and stirred uniformly again to prepare a modified raw material mixed solution.
9kg of hydrogen fluoride and 3kg of tripropylamine are added to the electrolytic bath, mixed and stirred uniformly, the temperature is controlled to be about 0 ℃, then the prepared mixed solution of the modified electrolytic raw materials is slowly added to the electrolytic bath, and about 3 hours of dropwise addition is expected to be completed. After the dropwise addition is finished, starting stirring for half an hour, stopping stirring, and standing and aging for 4-5 hours.
Starting the electrofluorination experiment, controlling the condensation reflux at-20 ℃ and the electrolytic cell at 20 +/-5 ℃, and slowly raising the voltage from 6V until the voltage is kept at about 10V, and keeping the current at more than 80A. As the reaction proceeds, product formation continues. And (3) removing escaping hydrogen fluoride from the tail gas by alkali liquor, freezing at-40 ℃ to obtain a liquefied crude product, and directly discharging a byproduct hydrogen gas into the atmosphere.
Monitoring till the electro-fluorination reaction is finished, filling the liquefied perfluoroisobutyronitrile crude product into an empty gas cylinder storage tank, weighing to obtain 8.23kg of crude product, and determining the product structure and the molar crude yield by GC-MS to be 80.9%. Purifying by low temperature rectification, washing, drying, compressing into a gas cylinder, and determining the purity to be 95.4% by gas chromatography.
Comparative example 1: the traditional electrofluorination process is adopted, the electrofluorination operation is the same as that in the example 1, 3.6kg of electrolytic raw material isobutyronitrile is added into 12kg of hydrogen fluoride, the reaction is controlled to be about 20 ℃, the voltage is controlled to be about 10V, the current is very low, the raw material and the hydrogen fluoride are layered, after the reaction is carried out for 15 hours, the generation of a target product is not detected, and the hydrogen fluoride has the escape phenomenon.
Comparative example 2: the electrofluorination operation was carried out in the same manner as in example 1, except that 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 a voltage of about 10V and a current of about 20A, and the raw material was partially dissolved in hydrogen fluoride. And monitoring until the electro-fluorination reaction is finished, and generating a target product. The crude product was weighed to a mass of 2.2kg and the molar crude yield was 21.63%.
Comparative example 3: in the same manner as in example 1, 3.6kg of electrolytic raw materials isobutyronitrile and hydrofluoroether HFE-3471.2kg were mixed and added to 9kg of hydrogen fluoride and 3kg of tripropylamine, and the reaction was controlled at about 0 ℃ under a voltage of about 10V and a current of about 30A, whereby the raw materials were dissolved in hydrogen fluoride. And monitoring until the electro-fluorination reaction is finished, and generating a target product. The crude product weighed 4.5kg and the molar crude yield was 44.23%.
Comparative example 4: in the same manner as in example 1, 3.6kg of electrolytic raw materials isobutyronitrile, 72g of cesium fluoride and 24g of crown ether were mixed and added to 9kg of hydrogen fluoride and 3kg of tripropylamine, and the reaction was carried out at about 0 ℃ under a voltage of about 10V and a current of 50A, thereby partially dissolving the raw materials and hydrogen fluoride. And monitoring until the electro-fluorination reaction is finished, and generating a target product. The crude product was weighed to a mass of 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 of example 1 and comparative examples 1 to 4
Example 2:
the same electrofluorination operation as in example 1 was carried out by adding 1.2kg of hydrofluoroether HFE-347 to 3.6kg of the electrolytic raw material isobutyronitrile, adding 72g of cesium fluoride and 24g of crown ether to the mixed solution, respectively, mixing them uniformly, adding the mixture to an electrolytic mixed solution of 9kg of hydrogen fluoride and 3kg of triethylamine, and starting the electrofluorination experiment.
After the end of the electrofluorination reaction, the liquefied perfluoroisobutyronitrile crude product was charged into an empty gas cylinder storage tank and weighed to obtain 7.83kg of crude product mass and 76.96% of molar crude yield.
Example 3:
in the same manner as in example 1, 1.2kg of hydrofluoroether HFE-347 was prepared and added to 3.6kg of isobutyronitrile as an electrolytic raw material, 72g of cesium fluoride and 24g of crown ether were added to the mixed solution, respectively, and after mixing them uniformly, the mixture was added to an electrolytic mixed solution of 11kg of hydrogen fluoride and 1.1kg of tripropylamine, and an electrofluorination experiment was started.
After the end of the electrofluorination reaction, the liquefied perfluoroisobutyronitrile crude product was charged into an empty gas cylinder storage tank and weighed to obtain 6.21kg of crude product mass and 61.04% of molar crude yield.
Example 4:
the same electrofluorination operation as in example 1 was carried out by preparing 1.2kg of hydrofluoroether HFE-347 and adding it to 3.6kg of the electrolytic raw material isobutyronitrile, adding 72g of potassium fluoride and 24g of crown ether to the mixed solution, mixing them uniformly and adding them to an electrolytic mixed solution of 9kg of hydrogen fluoride and 3kg of tripropylamine, and starting the electrofluorination experiment.
After the end of the electrofluorination reaction, the liquefied perfluoroisobutyronitrile crude product was charged into an empty gas cylinder storage tank and weighed to obtain 7.54kg of crude product mass and 74.11% of molar crude yield.
Example 5:
in the same manner as in example 1, 1.2kg of hydrofluoroether HFE-347 was prepared and added to 3.6kg of isobutyronitrile as an electrolytic raw material, 72g of cesium fluoride (without crown ether) was added to each of the mixed solutions, and after mixing them uniformly, the mixture was added to an electrolytic mixed solution of 9kg of hydrogen fluoride and 3kg of tripropylamine, and an electrofluorination experiment was started.
After the electro-fluorination reaction is monitored to be finished, the liquefied perfluoroisobutyronitrile crude product is filled into an empty gas cylinder storage tank, and the crude product is weighed to obtain 6.3kg of mass and 61.92% of molar crude yield.
Example 6:
in the same manner as in example 1, 1.2kg of hydrofluoroether HFE-347 was added to 3.6kg of an electrolytic raw material, i.e., isobutyronitrile, and 72g of cesium fluoride and 24g of 15-crown (ether) -5 were added to the mixture, and after mixing them uniformly, the mixture was added to an electrolytic mixture of 9kg of hydrogen fluoride and 3kg of tripropylamine, and an electrofluorination experiment was started.
After the electro-fluorination reaction is monitored to be finished, the liquefied perfluoroisobutyronitrile crude product is filled into an empty gas cylinder storage tank, and the crude product is weighed to obtain 7.6kg of mass and 74.7% of molar crude yield.
Example 7:
the same electrofluorination operation as in example 1 was carried out by preparing 1.2kg of hydrofluoroether HFE-458, adding it to 3.6kg of isobutyronitrile as an electrolytic raw material, adding 72g of cesium fluoride and 24g of crown ether to the mixed solution, mixing them uniformly, adding it to 9kg of an electrolytic mixed solution of hydrogen fluoride and 3kg of tripropylamine, and starting the electrofluorination experiment.
After the end of the electrofluorination reaction, the liquefied perfluoroisobutyronitrile crude product was charged into an empty gas cylinder storage tank and weighed to obtain 8.0kg of crude product mass and 78.63% of molar crude yield.
Example 8:
the same electrofluorination operation as in example 1 was carried out by preparing 1.2kg of hydrofluoroether HFE-356mec and adding it to 3.6kg of the electrolytic raw material isobutyronitrile, adding 72g of cesium fluoride and 24g of crown ether to the mixed solution, mixing them uniformly and adding them to an electrolytic mixed solution of 9kg of hydrogen fluoride and 3kg of tripropylamine, and starting the electrofluorination experiment.
After the end of the electrofluorination reaction, the liquefied perfluoroisobutyronitrile crude product was charged into an empty gas cylinder storage tank and weighed to obtain 7.8kg of crude product mass and 76.67% of molar crude yield.
Example 9:
in the same manner as in example 1, 0.36kg of hydrofluoroether HFE-347 was prepared and added to 3.6kg of isobutyronitrile as an electrolytic raw material, 72g of cesium fluoride and 24g of crown ether were added to the mixed solution, respectively, and after mixing them uniformly, the mixture was added to an electrolytic mixed solution of 9kg of hydrogen fluoride and 3kg of tripropylamine, and an electrofluorination experiment was started.
After the end of the electrofluorination reaction, the liquefied perfluoroisobutyronitrile crude product was charged into an empty gas cylinder storage tank and weighed to obtain 5.84kg of crude product mass and 57.40% of molar crude yield.
Example 10:
in the same manner as in example 1, 3.6kg of hydrofluoroether HFE-347 was prepared and added to 3.6kg of isobutyronitrile as an electrolytic raw material, 72g of cesium fluoride and 24g of crown ether were added to the mixed solution, respectively, and after mixing them uniformly, the mixture was added to 9kg of an electrolytic mixed solution of hydrogen fluoride and 3kg of tripropylamine, and an electrofluorination experiment was started.
After the end of the electrofluorination reaction, the liquefied perfluoroisobutyronitrile crude product was charged into an empty gas cylinder storage tank and weighed to obtain 6.12kg of crude product mass and 60.15% of molar crude yield. The addition of too much insulating hydrofluoroether results in an increase in electrolysis time of 5h over the other groups, with an increase in power consumption.
Example 11:
in the same manner as in example 1, 1.2kg of hydrofluoroether HFE-347 was prepared and 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 mixed solution, respectively, and after mixing them uniformly, the mixture was added to an electrolytic mixed solution of 9kg of hydrogen fluoride and 3kg of tripropylamine, and an electrofluorination experiment was started.
After the end of the electrofluorination reaction, the liquefied perfluoroisobutyronitrile crude product was charged into an empty gas cylinder storage tank and weighed to obtain 7.33kg of crude product mass and 72.04% of molar crude yield.
Example 12:
the same electrofluorination operation as in example 1 was carried out by preparing 1.2kg of hydrofluoroether HFE-347 and adding it to 3.6kg of the electrolytic raw material isobutyronitrile, adding 72g of cesium fluoride and 72g of crown ether to the mixture, mixing them uniformly and adding them to an electrolytic mixture of 9kg of hydrogen fluoride and 3kg of tripropylamine, and starting the electrofluorination experiment.
After the end of the electrofluorination reaction, the liquefied perfluoroisobutyronitrile crude product was charged into an empty gas cylinder storage tank and weighed to obtain 7.89kg of crude product mass and 77.55% molar crude yield.
Example 13:
the same electrofluorination operation as in example 1 was carried out by preparing 1.2kg of hydrofluoroether HFE-347 and adding it to 3.6kg of the electrolytic raw material isobutyronitrile, adding 900g of cesium fluoride and 90g of crown ether to the mixture, mixing them uniformly and adding them to an electrolytic mixture of 9kg of hydrogen fluoride and 3kg of tripropylamine, and starting the electrofluorination experiment.
After 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 mass of 3.32kg and a molar crude yield of 32.63%.
Example 14:
the same electrofluorination operation as in example 1 was carried out by preparing 1.2kg of hydrofluoroether HFE-347 and adding it to 3.6kg of the electrolytic raw material isobutyronitrile, adding 18g of cesium fluoride and 6g of crown ether to the mixture, mixing them uniformly and adding them to an electrolytic mixture of 9kg of hydrogen fluoride and 3kg of tripropylamine, and starting the electrofluorination experiment.
After 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 mass of 3.09kg and a molar crude yield of 30.37%.
Example 15:
in the same manner as in example 1, 0.6kg of hydrofluoroether HFE-347 was prepared and added to 1.8kg of isobutyronitrile as an electrolytic raw material, 36g of cesium fluoride and 12g of crown ether were added to the mixed solution, respectively, and after mixing them uniformly, the mixture was added to an electrolytic mixed solution of 9kg of hydrogen fluoride and 3kg of tripropylamine, and an electrofluorination experiment was started.
After 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 mass of 3.8kg and a molar crude yield of 74.7%.
Example 16:
the same electrofluorination operation as in example 1 was carried out by preparing 1.5kg of hydrofluoroether HFE-347 and adding it to 4.5kg of the electrolytic raw material isobutyronitrile, adding 90g of cesium fluoride and 30g of crown ether to the mixture, mixing them uniformly and adding them to an electrolytic mixture of 9kg of hydrogen fluoride and 3kg of tripropylamine, and starting the electrofluorination experiment.
After the end of the electrofluorination reaction, the liquefied perfluoroisobutyronitrile crude product was charged into an empty gas cylinder storage tank and weighed to obtain 6.56kg of crude product mass and 51.58% of molar crude yield.
The statements in this specification merely set forth a list of implementations of the inventive concept and the scope of the present invention should not be construed as limited to the particular forms set forth in the examples.
Claims (8)
1. A synthetic process of perfluoroisobutyronitrile adopts an electrofluorination process, and is characterized in that isobutyronitrile is used as a raw material and is synthesized into perfluoroisobutyronitrile by a one-step method in the presence of electrolytic fluorine source solution, a conductive agent, an accelerant and a solubilizer; the reaction equation is as follows:
2. the process for synthesizing perfluoroisobutyronitrile according to claim 1, wherein the conductive agent is a fluorine salt, preferably one of KF, AgF, CsF or NaF, and most preferably CsF, and the mass ratio of the conductive agent to isobutyronitrile is 25:1 to 200:1, and preferably 50: 1.
3. The process for synthesizing perfluoroisobutyronitrile according to claim 1, wherein the accelerator is a crown ether compound, preferably 18-crown (ether) -6 or 15-crown (ether) -5, and the mass ratio of the conductive agent to the accelerator is 1: 1-10: 1, preferably 3: 1.
4. The process according to claim 1, wherein the solubilizer is a hydrofluoroether compound, preferably HFE-374, HFE-347, HFE-356mec or HFE-458, and the mass ratio of the solubilizer to the raw material isobutyronitrile is 1:1 to 10:1, preferably 3: 1.
5. The process according to claim 1, wherein 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 preferably the mass ratio of hydrogen fluoride to tripropylamine is 3: 1.
6. The process for synthesizing perfluoroisobutyronitrile according to claim 1, wherein the mass ratio of the electrolytic fluorine source solution to isobutyronitrile is 2: 1-10: 1, preferably 10: 3.
7. The process according to any one of claims 1 to 6, wherein the electrolysis temperature is 15 to 25 ℃, preferably 20 ℃, the voltage is 7 to 10V, and the current is controlled to be 3 +/-0.5A/dm 2 。
8. The process according to any one of claims 1 to 6, wherein the mass ratio of the electrolytic fluorine source solution to the electrolytic raw material to the conductive agent to the accelerator to the solubilizing agent is 100:30:0.6:0.2: 10.
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| US20020008039A1 (en) * | 2000-06-28 | 2002-01-24 | Andreas Bulan | Process for preparing perfluorinated organic compounds by electrochemical fluorination |
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| CN111205197A (en) * | 2020-01-02 | 2020-05-29 | 黎明化工研究设计院有限责任公司 | Method and device for continuously preparing heptafluoroisobutyramide |
| CN111848444A (en) * | 2020-08-14 | 2020-10-30 | 福建省漳平市九鼎氟化工有限公司 | Synthesis method of perfluoroisobutyronitrile |
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| EP1080251A1 (en) * | 1998-05-08 | 2001-03-07 | Minnesota Mining And Manufacturing Company | Electrochemical fluorination of alkane substrate |
| US20020008039A1 (en) * | 2000-06-28 | 2002-01-24 | Andreas Bulan | Process for preparing perfluorinated organic compounds by electrochemical fluorination |
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