Polyurethanes (PUs) are widely used in different applications, and thus various synthetic procedures including one or more catalysts are applied to prepare them. For PU foams, the most important catalysts are nitrogen-containing compounds. Therefore, in this work, the catalytic effect of eight different nitrogen-containing catalysts on urethane formation will be examined. The reactions of phenyl isocyanate (PhNCO) and methanol without and in the presence of catalysts have been studied and discussed using the G3MP2BHandHLYP composite method. The solvent effects have also been considered by applying the SMD implicit solvent model. A general urethane formation mechanism has been proposed without and in the presence of the studied catalysts. The proton affinities (PA) were also examined. The barrier height of the reaction significantly decreased (∆E₀ > 100 kJ/mol) in the presence of the studied catalysts, which proves the important effect they have on urethane formation. The achieved results can be applied in catalyst design and development in the near future.

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.

A computational study of the stoichiometric reaction and catalytic effect of 2-dimethylaminoethanol (DMEA) in urethane formation was performed.