Density functional theory study on mechanisms of epoxy-phenol curing reaction.

A comprehensive picture on the mechanism of the epoxy-phenol curing reactions is presented using the density functional theory B3LYP/ 6-31G(d,p) and simplified physical molecular models to examine all possible reaction pathways. Phenol can act as its own promoter by using an addition phenol molecule to stabilize the transition states, and thus lower the rate-limiting barriers by 27.0-48.9 kJ/mol. In the uncatalyzed reaction, an epoxy ring is opened by a phenol with an apparent barrier of about 129.6 kJ/mol. In catalyzed reaction, catalysts facilitate the epoxy ring opening prior to curing that lowers the apparent barriers by 48.9-50.6 kJ/mol. However, this can be competed in highly basic catalysts such as amine-based catalysts, where catalysts are trapped in forms of hydrogen-bonded complex with phenol. Our theoretical results predict the activation energy in the range of 79.0-80.7 kJ/mol in phosphine-based catalyzed reactions, which agrees well with the reported experimental range of 54-86 kJ/mol.