脂肪族叔胺催化氨基甲酸酯的形成——一项实验与理论相结合的研究

Aliphatic tertiary amine catalysed urethane formation - a combined experimental and theoretical study.

作者信息

Waleed Hadeer Q, Csécsi Marcell, Konyhás Vivien, Boros Zsanett R, Viskolcz Béla, Fejes Zsolt, Fiser Béla

机构信息

Institute of Chemistry, University of Miskolc, Miskolc-Egyetemváros A/2, H-3515, Miskolc, Hungary.

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

出版信息

Phys Chem Chem Phys. 2022 Aug 31;24(34):20538-20545. doi: 10.1039/d2cp00728b.

DOI:10.1039/d2cp00728b

PMID:35997010

Abstract

A kinetic and mechanistic investigation of the alcoholysis of phenyl isocyanate (PhNCO) using stoichiometric butan-1-ol (BuOH) in acetonitrile in the presence of different tertiary amine catalysts was performed. The reaction mechanisms in the absence and presence of experimentally applied catalysts were described by using the G3MP2BHandHLYP composite method. The apparent activation energies obtained from the calculations were in good agreement with the experimental data (ΔΔ = <2 kJ mol). Both experimental and theoretical results proved the important effect of tertiary amine catalysts on urethane formation. These results can aid in polyurethane catalyst design and development.

摘要

在不同叔胺催化剂存在下，于乙腈中使用化学计量的丁醇（BuOH）对苯基异氰酸酯（PhNCO）的醇解反应进行了动力学和机理研究。通过使用G3MP2BHandHLYP复合方法描述了在不存在和存在实验应用催化剂的情况下的反应机理。计算得到的表观活化能与实验数据吻合良好（ΔΔ = <2 kJ mol）。实验和理论结果均证明了叔胺催化剂对聚氨酯形成的重要影响。这些结果有助于聚氨酯催化剂的设计与开发。