Searching for the Achilles' Heel of Urethane Linkage-An Energetic Perspective

A sudden increase in polyurethane (PU) production necessitates viable recycling methods for the waste generated. PU is one of the most important plastic materials with a wide range of applications; however, the stability of the urethane linkage is a major issue in chemical recycling. In this work, termination reactions of a model urethane molecule, namely methyl N-phenyl carbamate (MPCate), are investigated using G3MP2B3 composite quantum chemical method. Our main goal was to gain insights into the energetic profile of urethane bond termination and find an applicable chemical recycling method. Hydrogenation, hydrolysis, methanolysis, peroxidation, glycolysis, ammonolysis, reduction with methylamine and termination by dimethyl phosphite were explored in both gas and condensed phases. Out of these chemicals, degradation by H₂, H₂O₂ and CH₃NH₂ revealed promising results with lower activation barriers and exergonic pathways, especially in water solvation. Implementing these effective PU recycling methods can also have significant economic benefits since the obtained products from the reactions are industrially relevant substances. For example, aniline and dimethyl carbonate could be reusable in polymer technologies serving as potential methods for circular economy. As further potential transformations, several ionizations of MPCate were also examined including electron capture and detachment, protonation/deprotonation and reaction with OH^-. Alkaline digestion against the model urethane MPCate was found to be promising due to the relatively low activation energy. In an ideal case, the transformation of the urethane bond could be an enzymatic process; therefore, potential enzymes, such as lipoxygenase, were also considered for the catalysis of peroxidation, and lipases for methanolysis.