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CN-122010698-A - Preparation method of perfluoromethoxy methylene vinyl ether

CN122010698ACN 122010698 ACN122010698 ACN 122010698ACN-122010698-A

Abstract

The invention relates to the technical field of fluorine chemical engineering, in particular to a preparation method of perfluoro methoxy methylene vinyl ether, which comprises the following steps of S1) carrying out ozone cracking reaction by taking perfluoro olefin as a raw material, separating and purifying to obtain trifluoro methyl chloroformate, S2) reacting trifluoro methyl chloroformate with fluorine gas and halogenated olefin to generate fluorohalogenether, and S3) dehalogenating or halogenated hydrogen of the fluorohalogenether to obtain perfluoro methoxy methylene vinyl ether. The technical scheme provided by the invention has the advantages of 1) low cost of raw materials, industrialized production of fluoroolefin serving as a main raw material for preparing the trifluoromethyl fluoroformate, 2) mild process conditions, simplicity, safety and reliability, 3) good reaction selectivity, easy separation of products and high yield, and 4) low cost of the perfluoromethoxy methylene vinyl ether prepared by the method and suitable for industrial scale-up production.

Inventors

  • ZHOU JICANG
  • WANG JIANXIN
  • ZHOU YUJI
  • CHEN RUICAO
  • YU QIANG
  • GAN ZHIXING
  • YU DINGHUI

Assignees

  • 漳平市九鼎泰天科技有限公司
  • 福建省漳平市九鼎氟化工有限公司

Dates

Publication Date
20260512
Application Date
20260130

Claims (10)

  1. 1. A method for preparing perfluoromethoxy methylene vinyl ether, comprising the following steps: S1) performing an ozone cracking reaction by taking perfluoroolefin as a raw material, and separating and purifying to obtain trifluoromethyl fluoformate; s2) reacting trifluoromethyl chloroformate with fluorine gas and halogenated olefin to generate fluorohalogenether; s3) dehalogenating or carrying out halogenated hydrogen on the fluorohalogeno ether to obtain the perfluoromethoxy methylene vinyl ether.
  2. 2. The process according to claim 1, wherein the perfluoroolefin is hexafluoropropylene, perfluoro-2-butene, perfluoro-2-methyl-2-pentene, perfluoro-4-methyl-2-pentene or perfluoro-3-isopropyl-4-methyl-2-pentene.
  3. 3. The method according to claim 1, wherein the molar ratio of the perfluoroolefin to ozone is 1 (0.1-8); the temperature of the ozone cracking reaction is-100 ℃ to 100 ℃; The pressure of the ozone cracking reaction is 1-10 kg.
  4. 4. The method according to claim 1, wherein a reaction modifier is added during the ozone cracking reaction; the reaction modifier includes an alcohol and/or an acidic compound.
  5. 5. The method of claim 4, wherein the reaction modifier comprises one or more of fluorocarbonic acid, fluorocarbon alcohol; the mass ratio of the reaction regulator to the perfluorinated olefin is (0:100) - (80:20).
  6. 6. The method of claim 5, wherein the fluorocarbonic acid comprises one or more of trifluoroacetic acid, pentafluoropropionic acid, heptafluorobutyric acid; The fluorocarbon alcohol comprises one or more of trifluoroethanol, tetrafluoropropanol, pentafluoropropanol, hexafluoroisopropanol and octafluoropentanol.
  7. 7. The method according to claim 1, wherein in the step S2), the halogenated olefin has a structure represented by the following formula a, and the fluorohalogenether has a structure represented by the following formula b: A formula (a); Formula b; Wherein X, Y is independently selected from H or halogen atoms, and is not simultaneously H.
  8. 8. The method according to claim 1, wherein in the step S2), the solvent for the reaction is selected from perhalogenated solvents; the molar ratio of the trifluoromethyl chloroformate to the halogenated olefin is 3:1-1:3; the reaction temperature is-150 to-50 ℃.
  9. 9. The process according to claim 1, wherein the dehalogenation or the hydrogen halide is performed under the action of an active metal and a reducing catalyst.
  10. 10. The method of claim 9, wherein the active metal is selected from zinc; The reducing catalyst is selected from zinc chloride.

Description

Preparation method of perfluoromethoxy methylene vinyl ether Technical Field The invention relates to the technical field of fluorine chemical engineering, in particular to a preparation method of perfluoromethoxy methylene vinyl ether. Background Perfluoromethoxy methylene vinyl ether (MOVE) is a high-performance fluorine-containing monomer, combines the characteristics of perfluoroalkyl, oxygen element, vinyl and the like, has excellent high-temperature resistance, low-temperature resistance and corrosion resistance, has unique advantages in certain applications, and is a key raw material for synthesizing low-temperature fluororubber. Trifluoromethyl chloroformate is a key raw material for preparing perfluoromethoxy methylene vinyl ether, but is not readily available. The synthesis OF the trifluoromethyl fluoformate has been reported in some patents and literatures at home and abroad, but has the following defects that firstly, the reaction raw materials relate to inflammable and explosive dangerous substances such as CO, fluorine gas, CF 3 OF and the like or some expensive reagents which are difficult to produce on a large scale, secondly, the reaction selectivity is poor, the product is not easy to control, the yield is low, and thirdly, the reaction conditions are severe, corrosive components are contained in the product, and the requirement on equipment is high. In view of the above, there are great obstacles to the industrial production of trifluoromethyl chloroformate. So that the perfluoromethoxy methylene vinyl ether is difficult to realize industrial production and has extremely high cost. Disclosure of Invention In view of the above, the technical problem to be solved by the invention is to provide a preparation method of perfluoromethoxy methylene vinyl ether, which is suitable for industrial production of perfluoromethoxy methylene vinyl ether. In order to achieve the above purpose, the invention provides a preparation method of perfluoromethoxy methylene vinyl ether, which comprises the following steps: S1) performing an ozone cracking reaction by taking perfluoroolefin as a raw material, and separating and purifying to obtain trifluoromethyl fluoformate; s2) reacting trifluoromethyl chloroformate with fluorine gas and halogenated olefin to generate fluorohalogenether; s3) dehalogenating or carrying out halogenated hydrogen on the fluorohalogeno ether to obtain the perfluoromethoxy methylene vinyl ether. Preferably, the perfluoroolefin is hexafluoropropylene, perfluoro-2-butene, perfluoro-2-methyl-2-pentene, perfluoro-4-methyl-2-pentene or perfluoro-3-isopropyl-4-methyl-2-pentene, and more preferably, the perfluoroolefin is hexafluoropropylene, perfluoro-2-methyl-2-pentene or perfluoro-4-methyl-2-pentene. In some embodiments, step S1) above comprises the following process: 1) Ozone oxidation cracking of perfluoroolefin to obtain acyl fluoride mixture including trifluoromethyl chloroformate; 2) And (3) separating and purifying the mixture to obtain the trifluoromethyl fluoformate. The ozone cracking reaction adopts ozone-oxygen mixed gas, wherein the concentration of ozone is 1% -50%, and the concentration is volume concentration. In some embodiments of the present invention, the concentration of ozone in the oxygen ozone gas mixture is about 100 mg/L. Preferably, the molar ratio of the perfluoroolefin to the ozone consumed is 1 (0.1 to 8), more preferably 1 (0.1 to 5). The temperature of the ozone cracking reaction is-100 ℃ to 100 ℃, more preferably-80 ℃ to 80 ℃, still more preferably-60 ℃ to 60 ℃, and still more preferably-50 ℃ to 50 ℃. In some embodiments of the invention, the temperature of the ozone-cracking reaction is-50 ℃, -45 ℃, -40 ℃, -20 ℃, 0 ℃, 25 ℃, 40 ℃, 50 ℃, 60 ℃, or 70 ℃, or a range value having any of the above values as an upper or lower limit. The pressure of the ozone cracking reaction is 1-10 kg, more preferably 1-8 kg, and still more preferably 1-6 kg. Furthermore, in the ozone cracking reaction, a reaction regulator can be added according to the requirement to dilute the raw materials and regulate and control the composition of the product. The reaction modifier is a proton-containing compound, preferably comprising an alcohol and/or an acidic compound. Preferably, the reaction regulator is one or more of fluorocarbon acid and fluorocarbon alcohol. More preferably, the fluorocarbonic acid includes one or more of trifluoroacetic acid, pentafluoropropionic acid, heptafluorobutyric acid, and the like, and the fluorocarbon alcohol includes one or more of trifluoroethanol, tetrafluoropropanol, pentafluoropropanol, hexafluoroisopropanol, octafluoropentanol, and the like. The mass ratio of the reaction regulator to the perfluorinated olefin is preferably (0:100) - (80:20). The ozone-cracking reaction may be operated in a batch manner or in a continuous manner. The batch operation is preferably carried out by adding perfluoroolefin, fluorocarbon solvent and reaction regulator i