One-step Synthesis of Dimethyl Carbonate by Reaction of Ethylene Oxide, Carbon Dioxide and Methanol Catalyzed by Inorganic Salts

doi:10.1007/s40242-025-5047-3

高等学校化学研究 ›› 2025, Vol. 41 ›› Issue (4): 948-954.doi: 10.1007/s40242-025-5047-3

One-step Synthesis of Dimethyl Carbonate by Reaction of Ethylene Oxide, Carbon Dioxide and Methanol Catalyzed by Inorganic Salts

ZHANG Ziwang, LI Dandan, HONG Yang GAO Guohua

State Key Laboratory of Petroleum Molecular & Process Engineering, Shanghai Key Laboratory of Green Chemistry and Chemical Processes, Institute of Eco-Chongming, School of Chemistry and Molecular Engineering, East China Normal University, Shanghai 202162, P. R. China

收稿日期:2025-03-27 接受日期:2025-05-07 出版日期:2025-08-01 发布日期:2025-07-24
通讯作者: GAO Guohua,ghgao@chem.ecnu.edu.cn E-mail:ghgao@chem.ecnu.edu.cn
基金资助:
This work was supported by the National Natural Science Foundation of China (No. 22172053), the National Key Research and Development Program of China (No. 2020YFA07100201), the Research Funds of Happiness Flower of East China Normal University (ECNU) (No. 2020ST2203), and the Shanghai Leading Academic Discipline Project, China (No. B409).

One-step Synthesis of Dimethyl Carbonate by Reaction of Ethylene Oxide, Carbon Dioxide and Methanol Catalyzed by Inorganic Salts

ZHANG Ziwang, LI Dandan, HONG Yang GAO Guohua

State Key Laboratory of Petroleum Molecular & Process Engineering, Shanghai Key Laboratory of Green Chemistry and Chemical Processes, Institute of Eco-Chongming, School of Chemistry and Molecular Engineering, East China Normal University, Shanghai 202162, P. R. China

Received:2025-03-27 Accepted:2025-05-07 Online:2025-08-01 Published:2025-07-24
Supported by:
This work was supported by the National Natural Science Foundation of China (No. 22172053), the National Key Research and Development Program of China (No. 2020YFA07100201), the Research Funds of Happiness Flower of East China Normal University (ECNU) (No. 2020ST2203), and the Shanghai Leading Academic Discipline Project, China (No. B409).

摘要/Abstract

摘要： In this study, various inorganic salts were investigated for the one-step synthesis of dimethyl carbonate (DMC) by reaction of ethylene oxide (EO), carbon dioxide (CO₂), and methanol (MeOH). The bi-component catalytic system of KI/NaCl achieved high activities and selectivity with a DMC yield of 83% and a by-product, 2-methoxyethanol (2-MET), yield of 2%. The reaction involved two tandem reactions of the cycloaddition of EO and CO₂ and the transesterification of EC and MeOH. Kinetic studies were conducted to investigate the reaction mechanism and found that the strongly nucleophilic KI was the active species of cycloaddition and weak Lewis basic NaCl was the active species of transesterification, respectively. In addition, transesterification was the rate-determining step in the synthesis of DMC. CO₂/KI was capable of synergistically suppressing the by-product 2-MET. This catalytic system exhibited a substrate generality for different epoxides.

关键词: One-step synthesis, Dimethyl carbonate, Inorganic salt, 2-Methoxyethanol, Bi-component catalytic system

Abstract: In this study, various inorganic salts were investigated for the one-step synthesis of dimethyl carbonate (DMC) by reaction of ethylene oxide (EO), carbon dioxide (CO₂), and methanol (MeOH). The bi-component catalytic system of KI/NaCl achieved high activities and selectivity with a DMC yield of 83% and a by-product, 2-methoxyethanol (2-MET), yield of 2%. The reaction involved two tandem reactions of the cycloaddition of EO and CO₂ and the transesterification of EC and MeOH. Kinetic studies were conducted to investigate the reaction mechanism and found that the strongly nucleophilic KI was the active species of cycloaddition and weak Lewis basic NaCl was the active species of transesterification, respectively. In addition, transesterification was the rate-determining step in the synthesis of DMC. CO₂/KI was capable of synergistically suppressing the by-product 2-MET. This catalytic system exhibited a substrate generality for different epoxides.

Key words: One-step synthesis, Dimethyl carbonate, Inorganic salt, 2-Methoxyethanol, Bi-component catalytic system

ZHANG Ziwang, LI Dandan, HONG Yang GAO Guohua. One-step Synthesis of Dimethyl Carbonate by Reaction of Ethylene Oxide, Carbon Dioxide and Methanol Catalyzed by Inorganic Salts[J]. 高等学校化学研究, 2025, 41(4): 948-954.

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One-step Synthesis of Dimethyl Carbonate by Reaction of Ethylene Oxide, Carbon Dioxide and Methanol Catalyzed by Inorganic Salts

One-step Synthesis of Dimethyl Carbonate by Reaction of Ethylene Oxide, Carbon Dioxide and Methanol Catalyzed by Inorganic Salts

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