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Mechanism and kinetics of epoxide ring-opening with carboxylic acids catalyzed by the corresponding carboxylates
Chemical Engineering Science ( IF 4.1 ) Pub Date : 2021-05-06 , DOI: 10.1016/j.ces.2021.116746
Zifei Yan , Zeyu Ma , Jian Deng , Guangsheng Luo

The ring-opening reactions of epoxides with carboxylic acids have great applications in the coating and polymer industry. However, the systematical study on the structure-activity relation of catalysts is still scarce. In this work, the carboxylate catalysts were directly prepared rather than using the traditional catalysts like amines or quaternary ammonium salts, thus removing the induction period and making the kinetic results more accurate and rigorous. The reaction orders of reactants and catalyst were obtained by kinetic experiments, and based on that, the kinetic equation and mechanism were put forward. The influences of solvent environment, as well as the structure and properties of catalysts on their activity were further studied. It was found that the alkalinity of the carboxylate ions and the electrostatic interaction are the key factors to affect the nucleophilicity of catalysts. Generally, the nucleophilicity is enhanced with the increase of cation radius and anion branches.



中文翻译:

相应羧酸盐催化的羧酸环氧化物开环的机理和动力学

环氧化合物与羧酸的开环反应在涂料和聚合物工业中具有重要的应用。然而,对催化剂的构效关系的系统研究仍然很少。在这项工作中,羧酸酯催化剂是直接制备的,而不是使用胺或季铵盐之类的传统催化剂,从而消除了诱导期,并使动力学结果更加准确和严格。通过动力学实验得到了反应物与催化剂的反应顺序,并在此基础上提出了动力学方程和机理。进一步研究了溶剂环境,催化剂的结构和性能对其活性的影响。发现羧酸根离子的碱度和静电相互作用是影响催化剂亲核性的关键因素。通常,亲核性随阳离子半径和阴离子分支的增加而增强。

更新日期:2021-05-14
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