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US-20260125354-A1 - METHOD FOR SYNTHESIZING CYCLIC CARBONATE

US20260125354A1US 20260125354 A1US20260125354 A1US 20260125354A1US-20260125354-A1

Abstract

Provided is a method for synthesizing a cyclic carbonate, and more specifically to a method for synthesizing a cyclic carbonate, comprising a step for (i) mixing a compound of chemical formula 1 represented by chemical formula 1 below with a hydrogen carbonate (MHCO 3 ), or (ii) mixing the compound of chemical formula 1 with a carbonate (M 2 CO 3 ) under acidic conditions. According to the method for synthesizing of the present invention, the use of carbon dioxide, ethylene oxide, propylene oxide, and the like is unnecessary, and a cyclic carbonate having various substituents may be obtained at a high yield even under atmospheric pressure at a relatively low temperature,

Inventors

  • Ki-Tae NAM
  • Young-In JO
  • Jun-Ho Jang

Assignees

  • SEOUL NATIONAL UNIVERSITY R&DB FOUNDATION

Dates

Publication Date
20260507
Application Date
20251231
Priority Date
20230703

Claims (10)

  1. 1 . A method for synthesizing a cyclic carbonate, comprising: (i) mixing a compound of chemical formula 1, represented by chemical formula 1 below, with hydrogen carbonate (MHCO 3 ), or (ii) mixing the compound of chemical formula 1 with carbonate (M 2 CO 3 ) under acidic conditions, In chemical formula 1 above, X is a halogen selected from the group consisting of fluorine, chlorine, bromine, and iodine, R 1 is hydrogen, R 2 is independently selected from the group consisting of a vinyl group, a hydroxyl group, and a halogen selected from the group consisting of fluorine, chlorine, bromine, and iodine, and M is a cation (M + ) selected from the group consisting of an alkali metal cation, an ammonium ion (NH 4 + ), a primary ammonium ion, a secondary ammonium ion, and a tertiary ammonium ion.
  2. 2 . The method for synthesizing a cyclic carbonate of claim 1 , wherein the compound represented by chemical formula 1 above is one of compounds represented by chemical formulas 1-1, 1-2, and 1-3 below,
  3. 3 . The method for synthesizing a cyclic carbonate of claim 1 , wherein the compound of chemical formula 1 above is in a liquid state.
  4. 4 . The method for synthesizing a cyclic carbonate of claim 1 , wherein the hydrogen carbonate (MHCO 3 ) is in a liquid state or in a solid state.
  5. 5 . The method for synthesizing a cyclic carbonate of claim 1 , wherein the acidic conditions are controlled by an acid selected from the group consisting of nitric acid, hydrochloric acid, bromic acid, formic acid, and acetic acid.
  6. 6 . The method for synthesizing a cyclic carbonate of claim 1 , wherein the mixing operation of (i) is performed at a temperature within a range of 40° C. or higher and lower than 150° C.
  7. 7 . The method for synthesizing a cyclic carbonate of claim 1 , wherein the mixing operation of (i) is performed by mixing the compound of chemical formula 1 with hydrogen carbonate (MHCO 3 ) in a molar ratio of 1:0.5 to 2.
  8. 8 . The method for synthesizing a cyclic carbonate of claim 1 , wherein the mixing operation of (i) or (ii) is performed under atmospheric pressure conditions.
  9. 9 . The method for synthesizing a cyclic carbonate of claim 2 , wherein the synthesized cyclic carbonate is one of compounds represented by chemical formulas 2-1, 2-2, and 2-3 below,
  10. 10 . The method for synthesizing a cyclic carbonate of claim 1 , wherein the mixing operation of (i) or (ii) is performed without a solvent; or is performed under water; at least one polar organic solvent selected from the group consisting of alcohol, dimethylformamide, acetone, ether and ester; or a mixture thereof.

Description

TECHNICAL FIELD The present disclosure relates to a method for synthesizing a cyclic carbonate, and more particularly, to a method for synthesizing a cyclic carbonate for converting a cyclic carbonate substituted with various substituents into a cyclic carbonate in high yield and high concentration without the addition of additional solvents, catalysts, and carbon dioxide, without the use of ethylene oxide, propylene oxide, or the like. BACKGROUND ART Ethylene carbonate and propylene carbonate are used not only as raw materials for polycarbonate, intermediates for pharmaceuticals, oxyalkylation agents in dye synthesis processes, process equipment protectors, and solvents in fiber production processes, but the scope of use thereof is also expanding recently, including as solvents for polymer electrolytes in secondary batteries. Synthesis of ethylene carbonate or propylene carbonate known in the prior art was performed by reacting carbon dioxide with ethylene oxide or propylene oxide in the presence of a catalyst, but the accompanying reaction requires high-temperature and high-pressure carbon dioxide gas or liquid to obtain an industrially useful reaction rate. In addition, in the case of ethylene oxide, in the process of synthesizing ethylene oxide from ethylene, there is a problem that a large amount of carbon dioxide is emitted. Since ethylene oxide or propylene oxide tend to be decomposed or polymerized under high-temperature and high-pressure conditions, various catalysts have been developed to alleviate the reaction conditions. For example, Japanese Patent Laid-Open No. Hei9-67365 discloses a method using K1 (potassium iodide) as a catalyst, and Japanese Patent Laid-Open No. Sho59-13776 discloses a method using a tetraalkyl phosphonium halide such as tributylmethyl phosphonium iodide as a catalyst. These patents describe that a yield of 50 to 95% is obtained when reacted at a temperature of 100 to 170° C. for 1 to 5 hours, but there may be a problem that, to obtain a high yield, the reaction should be performed at a high temperature for a long period of time, and a moisture content of raw materials, carbon dioxide and alkylene oxide, should be controlled to several hundred ppm or less. Thus, a method using an ion exchange resin has been proposed, but this method has the problem of low yield at 80 to 100° C. In summary, the prior art for commercially preparing various cyclic carbonates require a reaction of gaseous and liquid carbon dioxide at high temperatures and high pressures, and the moisture content of the raw materials should be very low, making the reaction conditions difficult. In addition, despite the development of various catalysts, the generation of carbon dioxide during the process of producing ethylene oxide is unavoidable. Accordingly, when a technology is developed that does not require the use of high-pressure carbon dioxide, solvents, and catalysts, and does not require the use of ethylene oxide or propylene oxide, and can obtain various cyclic carbonates as a result in high concentrations, it is expected to be widely applied in related fields. SUMMARY OF INVENTION Technical Problem An aspect of the present disclosure is to provide a method for synthesizing a cyclic carbonate substituted with various substituents without the need for the use of ethylene oxide and propylene oxide, carbon dioxide, solvents, catalysts, and the like. Solution to Problem Accordingly, according to an aspect of the present disclosure, a method for synthesizing a cyclic carbonate is provided, the method including (i) mixing a compound of chemical formula 1, represented by chemical formula 1 below, with hydrogen carbonate (MHCO3), or (ii) mixing the compound of chemical formula 1 with carbonate (M2CO3) under acidic conditions. In chemical formula 1 above, X is a halogen selected from the group consisting of fluorine, chlorine, bromine, and iodine, R1 is hydrogen,R2 is independently selected from the group consisting of a vinyl group, a hydroxyl group, and a halogen group selected from the group consisting of fluorine, chlorine, bromine, and iodine, andM is a cation (M+) selected from the group consisting of an alkali metal cation, an ammonium ion (NH4+), a primary ammonium ion, a secondary ammonium ion, and a tertiary ammonium ion. Advantageous Effects of Invention According to the present disclosure, according to the method for synthesizing a cyclic carbonate, the use or additional input of ethylene oxide, propylene oxide, and carbon dioxide may not be required, and various cyclic carbonate derivatives may be obtained in high yields even under relatively low temperature and low pressure conditions, and the use of a solvent may be excluded, so a subsequent purification process may be simple, which is preferable in terms of process economy. BRIEF DESCRIPTION OF DRAWINGS FIG. 1 illustrates the results of observing a product present in a reaction solution at 80° C. during the synthesis of a cyclic carbonate throu