CN108863847B - Preparation method of perfluoronitrile compound - Google Patents
Preparation method of perfluoronitrile compound Download PDFInfo
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- CN108863847B CN108863847B CN201811056607.6A CN201811056607A CN108863847B CN 108863847 B CN108863847 B CN 108863847B CN 201811056607 A CN201811056607 A CN 201811056607A CN 108863847 B CN108863847 B CN 108863847B
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C253/00—Preparation of carboxylic acid nitriles
- C07C253/30—Preparation of carboxylic acid nitriles by reactions not involving the formation of cyano groups
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Abstract
The invention relates to the technical field of organic synthesis, in particular to a preparation method of perfluoronitrile compounds. The invention discloses a preparation method of perfluoronitrile compounds, which comprises the following steps: under the replacement protection of nitrogen or inert gas, reacting perfluoroalkene compound, metal fluoride and cyanogen chloride to obtain perfluoronitrile compound. The preparation method adopts a one-pot method to synthesize the perfluoronitrile compound, has simple operation, produces sodium chloride or potassium chloride as a byproduct of the reaction, has no pollution to the environment, and is easy to operate after treatment. In addition, the perfluoronitrile compound prepared by the preparation method has high yield, the highest yield is 82.1%, the purity is high and is higher than 99.3%, and the technical problems that the existing perfluoronitrile compound has low yield and is uneconomical are solved.
Description
Technical Field
The invention relates to the technical field of organic synthesis, in particular to a preparation method of perfluoronitrile compounds.
Background
GIS (gas-insulated switched capacitor) is an English abbreviation of gas insulated fully-closed combined electrical appliance and is widely applied to the field of high-voltage electricity. SF6Gases are widely used in GIS because of their excellent insulating and arc-extinguishing properties. However, SF6Has a Global Warming Potential (GWP) of about 22800 (CO, estimated time to Global Warming Potential of 100 years)2GWP of 1) (Stocker, t.f.; qin, g. -k.d.; plattner, m.; tignor, s.k.; allen, j.; boschung, a.; ipcc, 2013; climate Change 2013 The Physical Science basis, The description of Working Group I to The Fifth Association Report of The Interactive Panel on Climate Change; cambridge University Press, Cambridge, United Kingdom and New York, NY, USA,2013), so it is listed as one of six greenhouse gases that need to be strictly controlled for use in the Kyoto protocol, and finally SF is made6The wide application of gas in the field of high-voltage transformation is greatly discounted. In recent years, some famous electric power companies such as ABB, 3M, etc. have conducted a lot of research to find SF6The substitute gas or the mixed gas and achieves certain results.
3M company has conducted a large number of experiments and research studies to determine SF6One of the two alternatives is perfluoronitrile compound (2,3,3, 3-tetrafluoro-2-trifluoromethyl-propionitrile), the boiling point of which is-4.7 ℃, and the perfluoronitrile compound can be mixed with most of gas for use, and has the advantage of low operation temperature; in addition, the insulating property is excellent, and the high-voltage power cable is completely suitable for a high-voltage electrical equipment GIS; finally, its GWP is only 2210, much lower than SF6A gas.
However, the existing perfluoronitrile compound preparation method has the defects that the yield of the perfluoronitrile compound is low and the method is not economical.
Disclosure of Invention
The invention provides a preparation method of perfluoronitrile compounds, which solves the technical problems of low yield and uneconomic efficiency of the conventional perfluoronitrile compounds.
The specific technical scheme is as follows:
the invention provides a preparation method of perfluoronitrile compounds, which comprises the following steps:
under the replacement protection of nitrogen or inert gas, reacting perfluoroalkene compound, metal fluoride and cyanogen chloride to obtain perfluoronitrile compound.
The protective gas is preferably nitrogen.
The device for the reaction is a reaction kettle, and the temperature for charging the perfluoroalkene compound into the reaction kettle is-70 ℃ to-50 ℃, preferably-70 ℃.
Preferably, the perfluoronitrile compound is perfluoroisobutyronitrile.
Preferably, the molar ratio of the perfluoroolefin compound to the cyanogen chloride is 1.5: 1-1: 1, more preferably 1.1: 1;
the molar ratio of the metal fluoride to the cyanogen chloride is 1.2: 1-1: 1, more preferably 1.1: 1.
preferably, the reaction time is 3 to 15 hours, more preferably 6 to 15 hours, and further preferably 10 hours;
the reaction temperature is 40 ℃ to 80 ℃, and more preferably 50 ℃.
Preferably, the reaction also requires the addition of a catalyst.
Preferably, the catalyst is a phase transfer catalyst;
the phase transfer catalyst is selected from 18-crown-6 or tetrabutylammonium chloride.
In the embodiment of the invention, no catalyst is added in the reactions of the first to third embodiments, and the catalyst is added in the reaction of the fourth embodiment, so that the yield of the perfluoroisobutyronitrile added with the catalyst is high and is 82.1%.
Preferably, the amount of the catalyst is 0.5 mol% to 3 mol%, more preferably 2 mol%, of the amount of the cyanogen chloride.
Preferably, after the reaction is finished and before the perfluoronitrile compound is obtained, the method further comprises: removing the unreacted perfluoroolefin compound, and collecting a fraction at-5 ℃.
Preferably, the removing of the unreacted perfluoroolefin compound is specifically: volatilizing the reaction solution after the reaction is finished at 5-10 ℃, collecting volatile components, and volatilizing the volatile components at-25-15 ℃ to remove the unreacted perfluoroethylene compounds.
And (3) cooling the reaction liquid to 5-10 ℃ in an alcohol low-temperature cooling tank for volatilization to prevent the solvent from being carried out by gas.
The temperature at which the volatile components were collected was-40 ℃.
In the embodiment of the invention, the volatile component mainly comprises hexafluoropropylene, perfluoroisobutyronitrile and a solvent brought out along with gas.
It should be noted that the entire process of collecting the perfluoroolefin is a purification process according to the difference in boiling point between the respective substances.
Preferably, the reaction is carried out in an aprotic solvent system;
the aprotic solvent is selected from benzonitrile, acetonitrile, N-dimethylformamide, diethylene glycol dimethyl ether or ethylene glycol dimethyl ether, more preferably acetonitrile and diethylene glycol dimethyl ether, and further preferably acetonitrile.
More preferably, the ratio of the mass of solvent to the total mass of reactants is 1.5: 1-3: 1.
preferably, the perfluoroolefin compound is perfluoropropene.
Preferably, the metal fluoride is selected from potassium fluoride or sodium fluoride.
In the embodiment of the invention, the specific reaction formula of the perfluoronitrile compound is as follows:
the invention provides a preparation method of perfluoronitrile compounds, which comprises the following steps: reacting perfluoroolefin compound, metal fluoride and cyanogen chloride to obtain perfluoronitrile compound. The preparation method adopts a one-pot method to synthesize the perfluoronitrile compound, has simple operation, easily obtained cyanogen chloride raw material, no environmental pollution because the byproduct of the reaction is sodium chloride or potassium chloride, and easy operation of post-treatment. In addition, the perfluoronitrile compound prepared by the preparation method has high yield, the highest yield is 70.4%, and the purity is higher than 99.3%.
Detailed Description
The embodiment of the invention provides a perfluoronitrile compound, which is used for solving the technical problems of low yield and uneconomic efficiency of the conventional perfluoronitrile compound.
In order to make the objects, features and advantages of the present invention more obvious and understandable, the technical solutions in the embodiments of the present invention will be clearly and completely described below, and it should be apparent that the embodiments described below are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example one
Under the protection of nitrogen replacement, 12.76g (0.22mol) of potassium fluoride, 12.29g (0.20mol) of cyanogen chloride and 100mL of acetonitrile were added to a 500mL dry autoclave, 33.00g (0.22mol) of perfluoropropylene was slowly charged at a low temperature of-70 ℃ and the reaction was carried out under a closed condition at 50 ℃ for 10 hours. After the reaction is finished, the reaction solution is volatilized at the temperature of 5 ℃ in an alcohol low-temperature cooling tank, volatile components are collected at the temperature of-40 ℃, the volatile components are volatilized at the temperature of-20 ℃ to remove unreacted hexafluoropropylene, and then the perfluoroisobutyronitrile 27.60g of the product with the boiling point of-5 ℃ is obtained by volatilization and collection, and the yield is 70.4%.
Example two
Under the protection of nitrogen replacement, 9.24g (0.22mol) of sodium fluoride, 12.29g (0.20mol) of cyanogen chloride and 100mL of acetonitrile were added into a 500mL dry autoclave, 33.00g (0.22mol) of perfluoropropylene was slowly charged at a low temperature of-70 ℃ and the reaction was carried out under a closed condition at 50 ℃ for 10 hours. After the reaction is finished, the reaction solution is volatilized at the temperature of 5 ℃ in an alcohol low-temperature cooling tank, volatile components are collected at the temperature of-40 ℃, the volatile components are volatilized at the temperature of-20 ℃ to remove unreacted hexafluoropropylene, and then the perfluoroisobutyronitrile with the boiling point of-5 ℃ is obtained by volatilization and collection, wherein the yield is 70.2%.
EXAMPLE III
Under the protection of nitrogen replacement, 12.76g (0.22mol) of potassium fluoride, 12.29g (0.20mol) of cyanogen chloride and 100mL of diethylene glycol dimethyl ether were added to a 500mL dry autoclave, 33.00g (0.22mol) of perfluoropropylene was slowly charged at a low temperature of-70 ℃ and the reaction was carried out under a closed condition at 50 ℃ for 10 hours. After the reaction is finished, the reaction solution is volatilized at the temperature of 5 ℃ in an alcohol low-temperature cooling tank, volatile components are collected at the temperature of-40 ℃, the volatile components are volatilized at the temperature of-20 ℃ to remove unreacted hexafluoropropylene, and then perfluoro isobutyronitrile 25.60g with the boiling point of-5 ℃ is obtained by volatilization and collection, and the yield is 65.3%.
Example four
Under the protection of nitrogen replacement, 12.76g (0.22mol) of potassium fluoride, 12.29g (0.20mol) of 18-crown-61.056 g (4nmol), 12.29g (0.20mol) of cyanogen chloride and 100mL of acetonitrile were added to a 500mL dry autoclave, 33.00g (0.22mol) of perfluoropropylene was slowly charged at a low temperature of-70 ℃ and the mixture was reacted at 50 ℃ for 5 hours under a sealed condition. After the reaction is finished, the reaction solution is volatilized at the temperature of 5 ℃ in an alcohol low-temperature cooling tank, volatile components are collected at the temperature of-40 ℃, the volatile components are volatilized at the temperature of-20 ℃ to remove unreacted hexafluoropropylene, and then the perfluoroisobutyronitrile with the boiling point of-5 ℃ is obtained by volatilization and collection, wherein the yield is 82.1%.
EXAMPLE five
Under the protection of nitrogen replacement, 12.76g (0.22mol) of potassium fluoride, 21.18g (0.20mol) of cyanogen bromide and 100mL of acetonitrile are added into a 500mL dry autoclave, 33.00g (0.22mol) of perfluoropropylene is slowly filled at the low temperature of-70 ℃, and the reaction is carried out for 10 hours under a sealed condition at the temperature of 50 ℃. Volatilizing the reaction liquid in an alcohol low-temperature cooling tank at the temperature of 5 ℃ below zero, collecting volatile components at the temperature of-40 ℃, volatilizing the volatile components at the temperature of-20 ℃ to remove unreacted hexafluoropropylene to obtain 2-bromoperfluoropropane, and not obtaining perfluoroisobutyronitrile.
EXAMPLE six
The detection of the first to fourth examples was carried out by gas chromatography.
As shown in table 1, the purity of the perfluoroisobutyronitrile prepared in the first to fourth embodiments of the present invention is 99.3% or more, and other components may be solvent carried out, wherein, cyanogen bromide is used as a reaction raw material, and the perfluoroisobutyronitrile cannot be prepared because cyanogen bromide and cyanogen chloride have electronegativity difference.
Table 1 examples one to example pentaperfluoroisobutyronitrile purity
| Purity of | Example one | Example two | EXAMPLE III | Example four | EXAMPLE five |
| Perfluoroisobutyronitrile | 99.4％ | 99.5％ | 99.3％ | 99.3％ | Is free of |
| Other Components | 0.6％ | 0.5％ | 0.7％ | 0.7％ | Is free of |
The above-mentioned embodiments are only used for illustrating the technical solutions of the present invention, and not for limiting the same; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.
Claims (8)
1. A method for preparing perfluoronitrile compounds, which is characterized by comprising the following steps:
under the replacement protection of nitrogen or inert gas, reacting perfluoroalkene compounds, metal fluorides and cyanogen chloride to obtain perfluoronitrile compounds;
the metal fluoride is sodium fluoride or potassium fluoride;
the perfluoroolefin compound is perfluoropropylene;
the reaction time is 3-15 h;
the reaction temperature is 40-80 ℃.
2. The production method according to claim 1, wherein the molar ratio of the perfluoroolefin compound to the cyanogen chloride is 1.5: 1-1: 1;
the molar ratio of the metal fluoride to the cyanogen chloride is 1.2: 1-1: 1.
3. the method of claim 1, wherein the reaction further comprises adding a catalyst.
4. The production method according to claim 3, wherein the catalyst is a phase transfer catalyst;
the phase transfer catalyst is selected from 18-crown-6 or tetrabutylammonium chloride.
5. The method according to claim 3 or 4, wherein the catalyst is used in an amount of 0.5 to 3 mol% based on the cyanogen chloride.
6. The method according to claim 1, wherein the method further comprises, after completion of the reaction and before obtaining the perfluoronitrile compound: removing the unreacted perfluoroolefin compound, and collecting a fraction at-5 ℃.
7. The process according to claim 6, wherein the removal of unreacted perfluoroolefin is specifically: volatilizing the reaction solution after the reaction is finished at 5-10 ℃, collecting volatile components, and volatilizing the volatile components at-25-15 ℃ to remove the unreacted perfluoroethylene compounds.
8. The process according to claim 1, wherein the reaction is carried out in an aprotic solvent system;
the aprotic solvent is selected from benzonitrile, acetonitrile, N-dimethylformamide, diethylene glycol dimethyl ether or ethylene glycol dimethyl ether.
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| CN108863847B (en) * | 2018-09-11 | 2020-12-04 | 广东电网有限责任公司 | Preparation method of perfluoronitrile compound |
| CN114105821B (en) * | 2020-08-28 | 2023-09-12 | 浙江省化工研究院有限公司 | Preparation method of heptafluoroisobutyronitrile |
| CN113683530B (en) * | 2021-09-03 | 2023-10-27 | 化学与精细化工广东省实验室 | Method for preparing heptafluoroisobutyronitrile by gas phase hydrocyanation |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3752840A (en) * | 1971-07-09 | 1973-08-14 | Allied Chem | Process for preparing fluoroperhaloalkyl nitriles |
| CN107935884A (en) * | 2017-11-30 | 2018-04-20 | 北京宇极科技发展有限公司 | The preparation method of perfluor nitrile |
| CN108424375A (en) * | 2018-04-20 | 2018-08-21 | 北京宇极科技发展有限公司 | The preparation method of perfluor nitrile |
| CN108863847A (en) * | 2018-09-11 | 2018-11-23 | 广东电网有限责任公司 | A kind of preparation method of perfluor nitrile compounds |
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| CN1007977B (en) * | 1984-06-04 | 1990-05-16 | 拜尔股份公司 | Process for the preparation of 7-amino-1-cyclopxopyl-6, 8-dihalogeno-1, 4-dihydro-4-oxo-3-quinolinecarboxylic acids |
| US5866711A (en) * | 1996-09-13 | 1999-02-02 | E. I. Du Pont De Nemours And Company | Fluorocyanate and fluorocarbamate monomers and polymers thereof |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3752840A (en) * | 1971-07-09 | 1973-08-14 | Allied Chem | Process for preparing fluoroperhaloalkyl nitriles |
| CN107935884A (en) * | 2017-11-30 | 2018-04-20 | 北京宇极科技发展有限公司 | The preparation method of perfluor nitrile |
| CN108424375A (en) * | 2018-04-20 | 2018-08-21 | 北京宇极科技发展有限公司 | The preparation method of perfluor nitrile |
| CN108863847A (en) * | 2018-09-11 | 2018-11-23 | 广东电网有限责任公司 | A kind of preparation method of perfluor nitrile compounds |
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