环胺催化氨基甲酸酯形成的实验与理论研究

Experimental and Theoretical Study of Cyclic Amine Catalysed Urethane Formation.

作者信息

Waleed Hadeer Q, Pecsmány Dániel, Csécsi Marcell, Farkas László, Viskolcz Béla, Fejes Zsolt, Fiser Béla

机构信息

Institute of Chemistry, University of Miskolc, 3515 Miskolc-Egyetemváros, Hungary.

Higher Education and Industrial Cooperation Centre, University of Miskolc, 3515 Miskolc-Egyetemváros, Hungary.

出版信息

Polymers (Basel). 2022 Jul 13;14(14):2859. doi: 10.3390/polym14142859.

DOI:10.3390/polym14142859

PMID:35890635

原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC9316557/

Abstract

The alcoholysis of phenyl isocyanate (PhNCO) using stoichiometric butan-1-ol (BuOH) in acetonitrile in the presence of different cyclic amine catalysts was examined using a combined kinetic and mechanistic approach. The molecular mechanism of urethane formation without and in the presence of cyclic amine catalysts was studied using the G3MP2BHandHLYP composite method in combination with the SMD implicit solvent model. It was found that the energetics of the model reaction significantly decreased in the presence of catalysts. The computed and measured thermodynamic properties were in good agreement with each other. The results prove that amine catalysts are important in urethane synthesis. Based on the previous and current results, the design of new catalysts will be possible in the near future.

摘要

采用动力学和机理相结合的方法，研究了在不同环状胺催化剂存在下，苯异氰酸酯（PhNCO）与化学计量的丁醇（BuOH）在乙腈中的醇解反应。使用G3MP2BHandHLYP复合方法结合SMD隐式溶剂模型，研究了在不存在和存在环状胺催化剂的情况下聚氨酯形成的分子机理。结果发现，在催化剂存在下，模型反应的能量显著降低。计算得到的热力学性质与测量结果吻合良好。结果证明胺催化剂在聚氨酯合成中很重要。基于之前和当前的结果，在不久的将来有可能设计出新的催化剂。