本文选取取代的二乙醇胺(DEA)为模型化合物,利用量子化学方法研究了5种不同电负性的取代基(—CH3、—NH2、—OH、—OCH3、—F)分别在DEA氮原子的α和β位取代对仲胺与CO2不同反应路径之间的动力学竞争的影响.研究表明,从动力学方面来看,胺与CO2反应生成氨基甲酸盐是最可行的反应通道,其次是生成碳酸氢盐,而生成氨基甲酸难以实现.3条反应路径的动力学竞争顺序和伯胺是相同的.研究发现,反应能垒Ea除与胺的pK值相关外,还与胺的分子结构特性相关,比如:分子内氢键的形成会影响Ea.在将来的理想胺溶液的设计过程中,要综合考虑胺的pKs值及胺的微观结构对胺与CO2反应的动力学的影响.
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