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CN-122013207-A - Synthesis method of sodium tetrafluoropropionate

CN122013207ACN 122013207 ACN122013207 ACN 122013207ACN-122013207-A

Abstract

The invention relates to the technical field of chemical synthesis, and particularly discloses an electro-synthesis method of sodium tetrafluoropropionate, wherein the electro-catalytic oxidation technology is used for preparing titanium-based active metal coating oxide or nickel-based active metal coating oxide as an anode, nickel as a cathode, adding a metal ion catalyst comprising soluble nickel salt, oxidizing tetrafluoropropanol under alkaline conditions to obtain sodium tetrafluoropropionate, the electrolysis can be carried out under mild conditions, the electrolysis is environment-friendly, the technical scheme of high yield is obtained through screening under various conditions, the electro-catalytic system is continuously optimized, and the electrolysis yield is improved, so that the method is an efficient and green synthesis method of sodium tetrafluoropropionate.

Inventors

  • XU HAICHAO
  • YAN ZHIWEI

Assignees

  • 厦门大学

Dates

Publication Date
20260512
Application Date
20241111

Claims (10)

  1. 1. The electrosynthesis method of sodium tetrafluoropropionate comprises adding substrate tetrafluoropropanol into electrolyte, and electrolyzing by electrifying with titanium-based active metal coating oxide or nickel-based active metal coating oxide as anode and nickel as cathode to obtain sodium tetrafluoropropionate with the reaction formula as follows: the electrolyte comprises soluble nickel salt and alkali, and the solvent is water.
  2. 2. The method for electrosynthesis of sodium tetrafluoropropionate according to claim 1, wherein the concentration of tetrafluoropropanol in the alkaline electrolyte is 0.5 to 5mmol/ml.
  3. 3. The method for electrosynthesis of sodium tetrafluoropropionate according to any one of claims 1 or 2, characterized in that the alkaline charge of the electrolyte is selected from sodium hydroxide, potassium hydroxide, and/or the alkaline charge concentration is 0.5-10 mmol/ml, preferably 3.6mmol/ml.
  4. 4. A method of electrosynthesis of sodium tetrafluoropropionate according to any one of claims 1 to 3, characterized in that the current density is selected from 5-300 mA/cm 2 , preferably 20mA/cm 2 .
  5. 5. The method for electrosynthesis of sodium tetrafluoropropionate according to any one of claims 1 to 4, wherein the electrolysis temperature is 20 to 60 ℃.
  6. 6. The method according to any one of claims 1 to 5, wherein the cathode material is nickel flakes, nickel mesh or foam nickel.
  7. 7. The method according to claims 1 to 6, wherein the added soluble nickel salt comprises one or more of nickel sulphate, nickel acetate, nickel nitrate and/or the soluble nickel salt concentration is 0.001-0.1 mmol/mL, preferably 0.05mmol/mL.
  8. 8. The method for electrosynthesis of sodium tetrafluoropropionate according to any one of claims 1 to 7, wherein the method for producing a titanium-based active metal-plated oxide electrode or a nickel-based active metal-plated oxide electrode comprises: S1, polishing a titanium sheet or a nickel sheet, ultrasonically cleaning with acid and water, washing with alcohol, and drying; s2, preparing an electroplating solution comprising soluble nickel salt and alkali; And S3, placing the titanium sheet or the nickel sheet into electroplating liquid, and electroplating by using alternating current to respectively obtain the titanium-based active metal coating oxide electrode or the nickel-based active metal coating oxide electrode.
  9. 9. The method according to claim 8, wherein the nickel salt in the electroplating solution in the step S2 is selected from nickel sulfate and nickel nitrate, and/or the molar ratio of nickel ions to alkali in the electroplating solution in the step S2 is (52.0-71.0): (47.5-52.5), and/or the alkali in the step S2 is selected from potassium hydroxide and sodium hydroxide.
  10. 10. The method according to any one of claims 8 or 9, wherein the waveform of the S3 step alternating current is an asymmetric square wave, and/or the S3 step alternating current has a frequency of 1/55 to 1/65 hz, preferably 1/60 hz, and/or the S3 step asymmetric square wave has a duty cycle of 50 to 70%, preferably 67%, and/or the S3 step alternating current has a current density of 5 to 30ma/cm 2 .

Description

Synthesis method of sodium tetrafluoropropionate Technical Field The invention relates to the technical field of chemical synthesis, and particularly discloses a method for synthesizing sodium tetrafluoropropionate. Background The traditional preparation process of the sodium tetrafluoropropionate serving as a novel herbicide involves nucleophilic addition reaction of tetrafluoroethylene and a highly toxic raw material sodium cyanide in a specific solvent system, and then decomposition is carried out under mild alkaline conditions to generate a target product. This route is dominant in China and is distinguished by mild and easily controllable reaction conditions, high conversion efficiency and good yield. However, the process requires the use of high-purity tetrafluoroethylene and high-toxicity sodium cyanide, and the cyanide ion residue in the product also greatly limits the market application of the process, so that the use of the method is limited abroad. Another method is to use tetrafluoropropanol as raw material and potassium permanganate as oxidant. The use of potassium permanganate has the problem of great pollution, and the green chemistry principle is violated. Under the background, chinese patent CN101125811A proposes an innovative method for synthesizing sodium tetrafluoropropionate by using hydrogen peroxide as an oxidant. The hydrogen peroxide method not only simplifies the reaction products and lightens the environmental burden, but also is beneficial to reducing the whole production cost due to lower hydrogen peroxide cost. However, this strategy also faces challenges, such as the product yield is to be improved, and hydrogen peroxide itself still has a certain risk, limiting its wide application. In view of this, it is important to develop an oxidation technique that is both green and safe, while providing sustainability. Disclosure of Invention In order to solve the problems in the prior art, the first aspect of the invention discloses an electrosynthesis method of sodium tetrafluoropropionate, which comprises the steps of putting a substrate tetrafluoropropanol into electrolyte, and carrying out electrolysis by electrifying by taking titanium-based active metal coating oxide or nickel-based active metal coating oxide as an anode and taking nickel as a cathode to obtain sodium tetrafluoropropionate, wherein the reaction formula is as follows: the electrolyte comprises soluble nickel salt and alkali, and the solvent is water. In some embodiments of the first aspect, the concentration of tetrafluoropropanol in the alkaline electrolyte is 0.5 to 5mmol/ml, in some embodiments 0.5mmol/ml, in some embodiments 1.5mmol/ml, in some embodiments 2.5mmol/ml, in some embodiments 3.5mmol/ml, in some embodiments 5.0mmol/ml. In some embodiments of the first aspect, the alkaline charge of the electrolyte is selected from sodium hydroxide, potassium hydroxide. In some embodiments of the first aspect, the alkaline feed concentration is 0.5 to 10.0mmol/ml, in some embodiments 0.5mmol/ml, in some embodiments 3.5mmol/ml, in some embodiments 6.5mmol/ml, in some embodiments 10.0mmol/ml, in some preferred embodiments of the first aspect, the alkaline feed concentration is 3.6mmol/ml. In some embodiments of the first aspect, the current density is selected from 5-300 mA/cm 2, and in some preferred embodiments of the first aspect, the current density is selected from 20mA/cm 2. In some embodiments of the first aspect, the electrolysis temperature is 20 to 60 ℃, in some embodiments 30 ℃, in some embodiments 40 ℃, in some embodiments 50 ℃, in some embodiments 60 ℃. In some embodiments of the first aspect, the cathode material is nickel flakes, nickel mesh, or nickel foam. In particular embodiments of some of the first aspects, the added soluble nickel salt comprises one or more of nickel sulfate, nickel acetate, nickel nitrate. In some specific embodiments of the first aspect, the concentration of the soluble nickel salt is 0.001-0.1 mmol/mL, in some embodiments 0.03mmol/mL, in some embodiments 0.06mmol/mL, in some embodiments 0.09mmol/mL, and in some preferred embodiments of the first aspect, the concentration of the soluble nickel salt is 0.05mmol/mL. In some embodiments of the first aspect, the method for preparing a titanium-based active metal-plated oxide electrode or a nickel-based active metal-plated oxide electrode includes: S1, polishing a titanium sheet or a nickel sheet, ultrasonically cleaning with acid and water, washing with alcohol, and drying; s2, preparing an electroplating solution comprising soluble nickel salt and alkali; and S3, placing the titanium sheet or the nickel sheet into electroplating liquid, and electroplating the titanium sheet by using alternating current to respectively obtain the titanium-based active metal coating oxide electrode or the nickel-based active metal coating oxide electrode. In some specific embodiments of the first aspect, the nickel salt in the plating solution in th