阅读说明：本技术 一种六氟环氧丙烷的制备方法 (Preparation method of hexafluoropropylene oxide ) 是由 唐念 李丽 黎晓淀 周永言 张曼君 于 2019-10-14 设计创作，主要内容包括：本申请属于无机化学的技术领域,尤其涉及一种六氟环氧丙烷的制备方法。本申请提供了一种六氟环氧丙烷的制备方法,包括以下步骤：在溶剂存在的条件下,以氮氧化合物为氧化剂,以六氟丙烯为原料反应得到六氟环氧丙烷；其中,所述溶剂选自强极性不含氟溶剂和含氟溶剂。本申请公开了一种六氟环氧丙烷的制备方法,能有效解决目前制备六氟环氧丙烷的方法存在的无法同时兼得高产率与低反应风险的的技术缺陷。(The application belongs to the technical field of inorganic chemistry, and particularly relates to a preparation method of hexafluoropropylene oxide. The application provides a preparation method of hexafluoropropylene oxide, which comprises the following steps: under the condition of solvent existence, nitrogen oxide is taken as oxidant, hexafluoropropylene is taken as raw material to react to obtain hexafluoropropylene oxide; wherein the solvent is selected from the group consisting of a strongly polar non-fluorine-containing solvent and a fluorine-containing solvent. The application discloses a preparation method of hexafluoropropylene oxide, which can effectively solve the technical defect that the existing preparation method of hexafluoropropylene oxide can not simultaneously achieve high yield and low reaction risk.)

1. A preparation method of hexafluoropropylene oxide is characterized by comprising the following steps:

under the condition of solvent existence, nitrogen oxide is taken as oxidant, hexafluoropropylene is taken as raw material to react to obtain hexafluoropropylene oxide; wherein the solvent is selected from the group consisting of a strongly polar non-fluorine-containing solvent and a fluorine-containing solvent.

2. The method according to claim 1, wherein the molar ratio of the nitrogen oxide compound to the hexafluoropropylene is 1.0:1.0 to 2.0: 1.0.

3. The method of claim 1, wherein the nitroxide compound is selected from a fatty amine nitroxide compound and/or a heterocyclic amine nitroxide compound.

4. The method according to claim 4, wherein the fatty amine nitroxide compound is selected from one or more of trimethylamine nitroxide compound, triethylamine nitroxide compound, tripropylamine nitroxide compound, tributylamine nitroxide compound, N-dimethylethylamine nitroxide compound, N-dimethylaniline nitroxide compound and N, N-dimethylphenylamine nitroxide compound.

5. The method of claim 1, wherein the heterocyclic amine oxy-nitride compound is selected from one or more of pyrrole oxy-nitride, pyrrolidine oxy-nitride, pyridine oxy-nitride, piperidine oxy-nitride, piperazine oxy-nitride and quinoline oxy-nitride.

6. The method of claim 1, wherein the strongly polar non-fluorine containing solvent is selected from one or more of acetonitrile, N-dimethylformamide, and N, N-dimethylsulfoxide.

7. The method according to claim 1, wherein the fluorine-containing solvent is one or more selected from the group consisting of 1,1, 2-trichloro-1, 2, 2-trifluoroethane, 1, 1-dichloro-1-fluoroethane, 2, 2-dichloro-1, 1, 1-trifluoroethane and 1,1,1,3, 3-pentafluorobutane.

8. The method of claim 1, wherein the reaction temperature is-40 ℃ to 30 ℃.

9. The method of claim 1, wherein the reaction temperature is-15 ℃ to 20 ℃.

10. The preparation method according to claim 1, wherein the reaction is carried out in a tank reactor, and a mass transfer mechanism is arranged inside the tank reactor; and a heat transfer mechanism is arranged on the outer wall of the kettle type reactor.

Technical Field

The application belongs to the technical field of inorganic chemistry, and particularly relates to a preparation method of hexafluoropropylene oxide.

Background

Hexafluoropropylene oxide is an important fluorine-containing compound, and can be used as an intermediate or a precursor in the field of fluorine-containing fine products to prepare a series of fluorine-containing medicine and pesticide intermediates. Meanwhile, since hexafluoropropylene oxide is perfluoroepoxide, the hexafluoropropylene oxide can be used as a fluorine-containing working medium to be applied to the field of electrical insulation by utilizing the fluorine-containing and unsaturated physicochemical characteristics of the hexafluoropropylene oxide. The hexafluoropropylene oxide is gas at normal temperature, has a boiling point of-27.4 ℃, can be pressurized, liquefied and stably stored under the conditions of no acid and no alkali, has no self-polymerization risk, has good material compatibility and has good application prospect.

Hexafluoropropylene oxide has been synthesized through a number of routes, a typical route being:

1) oxidation reagent method: the method takes hexafluoropropylene as a raw material, hydrogen peroxide or sodium hypochlorite solution as an oxidant, and prepares a product in a polar solvent in a low-temperature environment (usually about-40 ℃), wherein the yield is generally about 50%.

2) Direct oxidation method: the method takes hexafluoropropylene as a raw material and oxygen as an oxidant, and the product is obtained through the catalytic action of a catalyst. The method has good atom economy and cheap raw materials, but the reaction activity of molecular oxygen is low, so the method is generally carried out at high temperature, the technical difficulty is high, and the reaction risk is high. As disclosed in the US3775438 patent, silica gel compound is used as a catalyst, and the reaction is carried out at the temperature of 140 ℃ and 280 ℃ by acidification treatment, the yield is 31 percent, and the selectivity is 74.7 percent. JP52053804 uses a copper-containing silicic acid/alumina compound or ion exchange zeolite as a catalyst, and the reaction is carried out at a temperature of 250 ℃ and 350 ℃, with a yield of 32% and a selectivity of 72.2%.

3) Liquid phase oxidation: the method takes hexafluoropropylene as a raw material and oxygen as an oxidant, and the hexafluoropropylene and the oxygen are oxidized in a high-pressure container to prepare the hexafluoropropylene/propylene/. As disclosed in JP9052886, the reaction temperature is 140 ℃ and the pressure is 25-40kg/cm2, the yield can reach 65% and the conversion rate is 73%, using perfluorocarboxylic acid fluoride as a solvent. JP57134473 discloses the use of perfluoropolyethers as solvents at a temperature of 110 ℃ and a pressure of 10-40kg/cm²The yield thereof was found to be 83.9%.

Among the above methods, the oxidation reagent method has a low reaction risk, but has a drawback of low yield; the direct oxidation method is carried out at high temperature, the technical difficulty is high, the reaction risk is high, and the yield is low; although the liquid phase oxidation method has high yield, the method has certain reaction risk because of a batch process and difficult obtainment of a catalyst and is carried out at high temperature and high pressure. The existing hexafluoropropylene oxide synthesis method can not simultaneously achieve the technical defects of high yield and low reaction risk.

Disclosure of Invention

In view of this, the present application discloses a method for preparing hexafluoropropylene oxide, which can effectively solve the technical defect that the existing method for preparing hexafluoropropylene oxide cannot simultaneously achieve high yield and low reaction risk.

The application provides a preparation method of hexafluoropropylene oxide, which comprises the following steps:

under the condition of solvent existence, nitrogen oxide is taken as oxidant, hexafluoropropylene is taken as raw material to react to obtain hexafluoropropylene oxide; wherein the solvent is selected from the group consisting of a strongly polar non-fluorine-containing solvent and a fluorine-containing solvent.

Specifically, the structural formula of the oxynitride is shown asWherein R is₁Selected from methyl, ethyl, propyl, butyl, piperidine, pyrrole and the like, R₂Selected from methyl, ethyl, propyl, butyl, piperidine, pyrrole, and the like.

Specifically, the structural formula of the hexafluoropropylene oxide is

Preferably, the molar ratio of the oxynitride to the hexafluoropropylene is 1.0:1.0 to 2.0: 1.0.

Specifically, the hexafluoropropylene is selected from cooled liquefied hexafluoropropylene or hexafluoropropylene gas.

Preferably, the nitroxide is selected from a fatty amine nitroxide and/or a heterocyclic amine nitroxide.

Preferably, the fatty amine nitroxide is selected from one or more of trimethylamine nitroxide, triethylamine nitroxide, tripropylamine nitroxide, tributylamine nitroxide, N-dimethylethylamine nitroxide, N-dimethylaniline nitroxide and N, N-dimethylphenylamine nitroxide.

Preferably, the heterocyclic amine nitroxide compound is selected from one or more of pyrrole nitroxide compounds, pyrrolidine nitroxide compounds, pyridine nitroxide compounds, piperidine nitroxide compounds, piperazine nitroxide compounds and quinoline nitroxide compounds.

Preferably, the strongly polar fluorine-free solvent is selected from one or more of acetonitrile, N-dimethylformamide and N, N-dimethyl sulfoxide.

Preferably, the fluorine-containing solvent is selected from one or more of 1,1, 2-trichloro-1, 2, 2-trifluoroethane, 1, 1-dichloro-1-fluoroethane, 2, 2-dichloro-1, 1, 1-trifluoroethane and 1,1,1,3, 3-pentafluorobutane.

Preferably, the temperature of the reaction is-40 ℃ to 30 ℃.

Preferably, the temperature of the reaction is-15 ℃ to 20 ℃.

Preferably, the reaction is carried out in a kettle type reactor, and a mass transfer mechanism is arranged in the kettle type reactor; and a heat transfer mechanism is arranged on the outer wall of the kettle type reactor.

More preferably, the mass transfer mechanism is selected from a static distributor, magnetic stirring or mechanical stirring; the heat transfer mechanism comprises a double-layer jacket and an external cold-hot circulating bath device, the double-layer jacket is sleeved on the outer wall of the kettle type reactor, and the external cold-hot circulating bath device is connected with the double-layer jacket, so that the external cold-hot circulating bath device can adjust the temperature inside the kettle type reactor by controlling the temperature of the double-layer jacket.

Specifically, the kettle-type reactor is provided with a gas-phase material inlet, a solid-phase material inlet, a liquid-phase material inlet and a discharge hole. The gas phase material inlet is used for butting a gas phase storage container, introducing a gas phase substance into the kettle type reactor, and has the functions of reaction overpressure protection and pressure relief. The solid phase material inlet is used for feeding solid phase material raw materials. The liquid phase material inlet is used for feeding liquid phase materials and has the function of sampling analysis. The discharge port is used for releasing liquid phase materials and has the function of sampling analysis.

Specifically, the material of the tank reactor is selected from glass, glass lining, stainless steel, carbon steel or hasse alloy.

The application discloses a preparation method of hexafluoropropylene oxide, under the condition of solvent existence, nitrogen oxide is used as an oxidant, hexafluoropropylene is used as a raw material, and hexafluoropropylene is reacted to obtain the hexafluoropropylene oxide. Through the oxidation of the high-efficiency oxidant and the dispersion and mass transfer of the solvent, hexafluoropropylene oxide is prepared without the need of reaction under severe conditions such as high temperature and high pressure, and experimental data show that the preparation method has the advantages of high yield and high selectivity. The hexafluoropropylene oxide prepared by the preparation method provided by the application can be used as an intermediate/precursor for preparing fluorine-containing fine chemical intermediates or single-working substances to be applied to the field of electrical insulation.

Drawings

In order to more clearly illustrate the embodiments of the present application or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below.

FIG. 1 shows a block diagram of a tank reactor as provided herein.

Specifically, fig. 1 includes: a gas phase material inlet 1; a solid phase material inlet 2; a liquid phase material inlet 3; a main reactor 4; a discharge port 5; the gas phase material inlet 1, the solid phase material inlet 2 and the liquid phase material inlet 3 are respectively arranged at the top of the main reactor 4, the discharge port 5 is arranged at the bottom of the main reactor 4, the material of the reaction inner wall of the main reactor 4 can be glass, glass lining, stainless steel, carbon steel or hass alloy, and a mass transfer mechanism is arranged in the main reactor 4; the mass transfer mechanism can be a static distributor, magnetic stirring or mechanical stirring; the outer wall of main reactor 4 is equipped with heat transfer mechanism, and heat transfer mechanism includes that double-deck cover presss from both sides and external cold and hot circulation bath device, and double-deck cover is established at the outer wall of main reactor 4, and external cold and hot circulation bath device is connected with double-deck cover, and external cold and hot circulation bath device is through the temperature of controlling double-deck cover in order to adjust the temperature of the inside of main reactor 4. The gas-phase material inlet 1 is used for butting a gas-phase storage container, introducing gas-phase substances and having the functions of reaction overpressure protection and pressure relief. The solid phase material inlet 2 is used for feeding solid phase material raw materials. The liquid phase material inlet 3 is used for feeding liquid phase materials and has the function of sampling analysis. The discharge port 5 is used for releasing liquid phase materials and has the function of sampling analysis.

Detailed Description

The application provides a preparation method of hexafluoropropylene oxide, which is used for solving the technical defects that the method for preparing hexafluoropropylene oxide in the prior art is low in yield, high in cost and difficult to store in a system.

The technical solutions in the embodiments of the present application will be described clearly and completely below, and it should be understood that the described embodiments are only a part of the embodiments of the present application, 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 application.

The raw materials used in the following examples are all commercially available or self-made.