Preparation method for joint production of 3,3,3-trifluoro-1,2-propanediol and 4-trifluoromethylethylene carbonate

A technology of trifluoromethyl ethylene carbonate and propylene glycol is applied in the field of preparation of fluorine-containing alcohol and fluorine-containing five-membered cyclic carbonate, and can solve the problems of harsh reaction conditions, complex reaction system, low reaction efficiency, etc. Mild conditions, good atom economy, and high reaction yields

Active Publication Date: 2021-02-23
XIAN MODERN CHEM RES INST
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  • Abstract
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Problems solved by technology

This method is carried out intermittently in a high-pressure reactor, the reaction efficiency is low, and there is a risk of metal tungsten residue in the product, which does not meet the high-quality requirements of battery-grade reagents
[0010] Although some reports about TFPG or TFPC have been published, there are no public reports about the co-production of TFPG and TFPC. More importantly, there are various degrees of existence in these methods such as harsh reaction conditions, poor safety performance; reaction atom economy. Poor performance, low yield; many reaction steps, complex reaction system; highly toxic and harmful substances involved, unfriendly to the environment; metal residues, low product quality and other deficiencies, Cheng needs to develop a mild reaction condition, easy operation, atom economy Preparation method for co-production of 3,3,3-trifluoro-1,2-propanediol and 4-trifluoromethylethylene carbonate with good product distribution

Method used

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  • Preparation method for joint production of 3,3,3-trifluoro-1,2-propanediol and 4-trifluoromethylethylene carbonate
  • Preparation method for joint production of 3,3,3-trifluoro-1,2-propanediol and 4-trifluoromethylethylene carbonate
  • Preparation method for joint production of 3,3,3-trifluoro-1,2-propanediol and 4-trifluoromethylethylene carbonate

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preparation example Construction

[0020] The preparation method of co-production TFPG and TFPC provided by the present invention comprises the following steps: taking 3,3,3-trifluoropropylene oxide as raw material, reacting with carbon dioxide in the presence of hydrogen halide solution and organic base, the reaction temperature 70°C-180°C, reaction pressure 0.1MPa-5MPa, after the reaction is completed, the obtained crude 3,3,3-trifluoro-1,2-propanediol and 4-trifluoromethylethylene carbonate are separated and purified Target products TFPG and TFPC.

[0021]The hydrogen halide solution in the present invention is one or more combinations of hydrogen iodide solution, hydrogen bromide solution, hydrogen chloride solution or hydrogen fluoride solution, preferably commercially available hydroiodic acid with a mass percentage of 55%-58%, and a mass percentage of 48% One or more combinations of hydrobromic acid, hydrochloric acid of 36-38% by mass percent, hydrofluoric acid of 40% by mass percent; among the present ...

Embodiment 1

[0030] Add 3,3,3-trifluoropropylene oxide (0.3mol), 48% HBr solution (15mmol), triethylamine (15mmol) successively into a 50mL stainless steel autoclave equipped with stirring, and use CO 2 Replace the reactor twice, start stirring and heat to 100°C, and continuously feed CO 2 Keep the reaction pressure at 0.5MPa, react for 4h, then cool to room temperature, slowly release excess CO 2 gas, 3,3,3-trifluoro-1,2-propanediol and 4-trifluoromethylethylene carbonate crude products were obtained, and the product distribution was analyzed by gas chromatography, wherein the contents of TFPG and TFPC were 21.2% and 78.4%, respectively. 44.3 g of the target product 3,3,3-trifluoro-1,2-propanediol and 4-trifluoromethylethylene carbonate were obtained, and the calculated yield was 98.7%. The reaction results are shown in Table 1.

[0031] Gas chromatography analysis conditions: Agilent 7820 gas chromatography, hydrogen flame ionization detector, DB-5 capillary column (30m×0.320mm×0.25μm),...

Embodiment 2-11

[0033] Embodiment 2~11 is reacted according to the same method in embodiment 1, and conditions such as the hydrogen halide solution that it adopts, organic base, reaction temperature, reaction pressure, reaction time and corresponding reaction result, product distribution are as shown in table 1 .

[0034] Table 1

[0035]

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Abstract

The invention discloses a preparation method for the joint production of 3,3,3-trifluoro-1,2-propanediol and 4-trifluoromethylethylene carbonate, which comprises the following steps: in the presence of hydrogen halide solution and organic base , 3,3,3-trifluoropropylene oxide reacts with carbon dioxide, the reaction temperature is 70°C-180°C, the reaction pressure is 0.1MPa-5MPa, and the reaction is completed to obtain 3,3,3-trifluoro-1,2-propanediol and 4-trifluoromethyl ethylene carbonate crude product, through separation, refining to obtain the target product 3,3,3-trifluoro-1,2-propanediol and 4-trifluoromethyl ethylene carbonate, wherein the hydrogen halide consumption is 0.5%-20% of the molar weight of 3,3,3-trifluoropropylene oxide, and the amount of organic base is 0.5%-20% of the molar weight of 3,3,3-trifluoropropylene oxide. The invention has the characteristics of mild reaction conditions, simple operation, good reaction atom economy, and adjustable product distribution, and is mainly used for the joint production of 3,3,3-trifluoro-1,2-propanediol and 4-trifluoromethyl vinyl carbonate.

Description

technical field [0001] The invention relates to a preparation method of fluorine-containing alcohol and fluorine-containing five-membered cyclic carbonate, in particular to a method for co-production of 3,3,3-trifluoro-1,2-propanediol (TFPG) and 4-trifluoromethane The preparation method of ethylene carbonate (TFPC). Background technique [0002] The introduction of trifluoromethyl into organic compounds can significantly change the acidity, dipole moment, polarity, lipophilicity, and chemical and metabolic stability of the compound. Compounds containing trifluoromethyl are widely used in defense industry, high-tech industry and life increasingly important role in science. 3,3,3-Trifluoro-1,2-propanediol (TFPG), as a kind of fluorine-containing alcohol, contains a trifluoromethyl group and two hydroxyl groups in its structure. It has a unique structure, excellent performance, and broad application prospects; 3, 3,3-Trifluoropropene carbonate (TFPC) is an important trifluoro...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C07D317/36C07C29/10C07C31/42
CPCC07C29/103C07D317/36C07C31/42
Inventor 马辉吕剑王博赵波秦越谷玉杰曾纪珺贾兆华涂东怀李春迎
Owner XIAN MODERN CHEM RES INST
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