阅读说明：本技术 3,3,3-三氟碳酸丙烯酯的制备方法 (Preparation method of 3,3, 3-propylene trifluorocarbonate ) 是由 闫彩桥 葛建民 王军 郝俊 张民 武利斌 侯荣雪 于 2019-05-05 设计创作，主要内容包括：3,3,3-三氟碳酸丙烯酯的制备方法,属于电池电解液共溶剂或添加剂的技术领域,以3,3,3-三氟-1,2-环氧丙烷为原料制备,包括以下步骤：A、将3,3,3-三氟-1,2-环氧丙烷和0.1mol/L的盐酸水溶液混合,加入全氟磺酸树脂,于35-45℃条件下反应3-5小时,自然冷却至室温,向其中加入碱性溶液,pH7.0,反应30-60min,减压蒸馏,过滤,分馏得到3,3,3-三氟-1,2-丙二醇；B、以甲苯为溶剂,向其中加入碳酸二甲酯和步骤A得到的3,3,3-三氟-1,2-丙二醇,加入钯铜催化剂,加热至50-120℃,反应4-5小时,蒸出甲醇,得到3,3,3-三氟碳酸丙烯酯。本发明采用3,3,3-三氟-1,2-环氧丙烷为原料,制备成3,3,3-三氟-1,2-丙二醇,与碳酸二甲酯、以钯铜催化剂催化合成,可操作性强,最终产品的产率达87％以上。(A preparation method of 3,3, 3-trifluoro propylene carbonate belongs to the technical field of battery electrolyte cosolvent or additive, takes 3,3, 3-trifluoro-1, 2-epoxypropane as raw material for preparation, and comprises the following steps: A. mixing 3,3, 3-trifluoro-1, 2-propylene oxide with 0.1mol/L hydrochloric acid aqueous solution, adding perfluorinated sulfonic acid resin, reacting at 35-45 ℃ for 3-5 hours, naturally cooling to room temperature, adding alkaline solution with pH of 7.0, reacting for 30-60min, distilling under reduced pressure, filtering, and fractionating to obtain 3,3, 3-trifluoro-1, 2-propylene glycol; B. and (2) taking toluene as a solvent, adding dimethyl carbonate and the 3,3, 3-trifluoro-1, 2-propylene glycol obtained in the step (A), adding a palladium-copper catalyst, heating to 50-120 ℃, reacting for 4-5 hours, and distilling out methanol to obtain the 3,3, 3-trifluoropropene carbonate. The invention adopts 3,3, 3-trifluoro-1, 2-epoxypropane as raw material to prepare 3,3, 3-trifluoro-1, 2-propanediol, which is catalytically synthesized with dimethyl carbonate by palladium-copper catalyst, the operability is strong, and the yield of the final product reaches more than 87%.)

The preparation method of 3,3, 3-trifluoro propylene carbonate is characterized in that the preparation method takes 3,3, 3-trifluoro-1, 2-epoxypropane as raw material and comprises the following steps:

A. mixing 3,3, 3-trifluoro-1, 2-propylene oxide with 0.1mol/L hydrochloric acid aqueous solution, adding perfluorinated sulfonic acid resin, reacting at 35-45 ℃ for 3-5 hours, naturally cooling to room temperature, adding alkaline solution with pH of 7.0, reacting for 30-60min, distilling under reduced pressure, filtering, and fractionating to obtain 3,3, 3-trifluoro-1, 2-propylene glycol;

B. and (2) taking toluene as a solvent, adding dimethyl carbonate and the 3,3, 3-trifluoro-1, 2-propylene glycol obtained in the step (A), adding a palladium-copper catalyst, heating to 50-120 ℃, reacting for 4-5 hours, and distilling out methanol to obtain the 3,3, 3-trifluoropropene carbonate.

2. The method for preparing 3,3, 3-trifluoropropene carbonate according to claim 1, wherein the alkaline solution in step A is a sodium hydroxide solution or a potassium hydroxide solution.

3. The process for producing propylene 3,3, 3-trifluorocarbonate according to claim 1, wherein 100ml of an aqueous hydrochloric acid solution of 0.1mol/L is added based on 1mol of 3,3, 3-trifluoro-1, 2-epoxypropane.

4. The process for producing propylene 3,3, 3-trifluorocarbonate according to claim 1, wherein the perfluorosulfonic acid resin is added in an amount of 0.1 to 0.5% by mass based on the mass of 3,3, 3-trifluoro-1, 2-epoxypropane.

5. The process for the preparation of propylene 3,3, 3-trifluorocarbonate according to claim 1, wherein the molar ratio of 3,3, 3-trifluoro-1, 2-propanediol to dimethyl carbonate is 1: (2-3).

6. The preparation method of 3,3, 3-trifluoropropene ester according to claim 1, wherein the palladium-copper catalyst is prepared from (10-15): 1 of bis (cyanophenyl) palladium dichloride and cuprous iodide.

7. The method for producing propylene 3,3, 3-trifluorocarbonate according to claim 1, wherein the amount of the palladium-copper catalyst added is 1 to 2% by mass of 3,3, 3-trifluoro-1, 2-propanediol.

Technical Field

The invention belongs to the technical field of a cosolvent or an additive of a battery electrolyte, and relates to a preparation method of a battery electrolyte additive 3,3, 3-trifluoropropylene carbonate.

Background

The lithium ion battery has been widely applied to the fields of electric automobiles, hybrid electric automobiles, aerospace and the like at present by virtue of the advantages of long service life, large specific capacity, no memory effect and the like. However, with the wide application of lithium ion batteries in the fields of electric vehicles, energy storage and the like, people put higher demands on lithium ion batteries, such as: higher energy density, wider use temperature, better safety, etc. In order to solve this problem, it is necessary to design, synthesize a new functional electrolyte or search for a suitable electrolyte additive to meet the application of the lithium ion battery in special cases.

The 3,3, 3-propylene carbonate with CAS number of 167951-80-6 has wide application in developing lithium ion battery electrolyte with special function. The outermost layer of the fluorine electron orbit has 7 electrons, has strong electronegativity and weak polarity, and the fluorine substitution can reduce the freezing point of a solvent, increase the flash point, improve the oxidation resistance and contribute to improving the contact performance between the electrolyte and an electrode. Therefore, the 3,3, 3-propylene carbonate trifluoride is used as a cosolvent or an additive of the lithium ion battery electrolyte, so that the low-temperature performance, the oxidation resistance, the flame retardant property and the wettability of the electrolyte to an electrode can be effectively improved, and the electrolyte with special functions is obtained. However, in terms of the existing 3,3, 3-trifluoro propylene carbonate synthesis technology, the problems of complex process, difficult realization of industrial production, high cost, low product yield and the like exist in the synthesis process, 3,3, 3-trifluoro-1, 2-epoxypropane is adopted to firstly hydrolyze to generate 3,3, 3-trifluoro-1, 2-propanediol, then the 3,3, 3-trifluoro-1, 2-propanediol is added into a large amount of dimethyl carbonate, and the product yield synthesized by taking alkali as a catalyst is generally less than 80%. Therefore, the research on the synthesis method of the 3,3, 3-trifluoro propylene carbonate has great practical significance.

Disclosure of Invention

The invention provides a preparation method of 3,3, 3-trifluoro propylene carbonate for solving the technical problems, the preparation process is stable, the yield of the product is greatly improved, and the preparation method has great practical significance.

The technical scheme adopted by the invention for realizing the purpose is as follows:

the preparation method of 3,3, 3-trifluoro propylene carbonate takes 3,3, 3-trifluoro-1, 2-epoxypropane as raw material, and comprises the following steps:

A. mixing 3,3, 3-trifluoro-1, 2-propylene oxide with 0.1mol/L hydrochloric acid aqueous solution, adding perfluorinated sulfonic acid resin, reacting at 35-45 ℃ for 3-5 hours, naturally cooling to room temperature, adding alkaline solution with pH of 7.0, reacting for 30-60min, distilling under reduced pressure, filtering, and fractionating to obtain 3,3, 3-trifluoro-1, 2-propylene glycol;

B. and (2) taking toluene as a solvent, adding dimethyl carbonate and the 3,3, 3-trifluoro-1, 2-propylene glycol obtained in the step (A), adding a palladium-copper catalyst, heating to 50-120 ℃, reacting for 4-5 hours, and distilling out methanol to obtain the 3,3, 3-trifluoropropene carbonate.

The alkaline solution in the step A is a sodium hydroxide solution or a potassium hydroxide solution.

Based on 1mol of 3,3, 3-trifluoro-1, 2-epoxypropane, 100 mol of 150ml of 0.1mol/L hydrochloric acid aqueous solution is added.

The addition amount of the perfluorinated sulfonic acid resin is 0.1-0.5 percent of the mass of the 3,3, 3-trifluoro-1, 2-propylene oxide.

The mol ratio of the 3,3, 3-trifluoro-1, 2-propanediol to the dimethyl carbonate is 1: (2-3).

The palladium-copper catalyst is prepared from the following components in percentage by mass (10-15): 1 of bis (cyanophenyl) palladium dichloride and cuprous iodide.

The invention has the beneficial effects that:

the 3,3, 3-trifluoro-1, 2-propylene oxide is adopted as a raw material to prepare the 3,3, 3-trifluoro-1, 2-propylene glycol, and the 3,3, 3-trifluoro-1, 2-propylene glycol is synthesized with dimethyl carbonate by using a palladium-copper catalyst, the operability is strong, the yield of the final product reaches more than 87 percent, compared with the prior method that the 3,3, 3-trifluoro-1, 2-propylene oxide is firstly hydrolyzed to generate the 3,3, 3-trifluoro-1, 2-propylene glycol, and then the 3,3, 3-trifluoro-1, 2-propylene glycol is added into a large amount of dimethyl carbonate, and the yield of the product synthesized by using alkali as the catalyst is improved by 25 percent.

The key point of the invention is that perfluorosulfonic acid resin is added when preparing 3,3, 3-trifluoro-1, 2-propylene glycol, and palladium-copper catalyst is adopted when synthesizing 3,3, 3-trifluoropropene carbonate, thus obtaining high yield and high purity.

Detailed Description

The present invention will be further described with reference to the following examples.