Condensation reactions of phenolic resins VII: catalytic effect of sodium bicarbonate for the condensation of hydroxymethylphenols

Abstract

This article describes the catalytic effect of NaHCO₃ on condensation reactions of monomeric hydroxymethylphenols (HMPs) to elucidate the cure-acceleration mechanism. By comparison of the kinetics of self-condensations of HMPs, NaHCO₃ was proved to increase the reactivity of para-hydroxymethyl groups. The changes of ¹³C nuclear magnetic resonance (NMR) chemical shifts on each HMP system with the additive indicated that the addition of NaHCO₃ enhanced some molecular interactions between HMPs and NaHCO₃, facilitating a resonance effect that might play a similar role in dissociation of the phenolic hydroxyl groups of HMPs. In addition, computational modeling by molecular orbital calculations elucidated that hydrogen carbonate anion (HCO ⁻₃ ) forms an interaction between either the para-hydroxymethyl group and the phenolic hydroxyl group or between the two para-hydroxymethyl groups of HMPs by hydrogen bonds. From the experimental results, the authors proposed the mechanism of the catalytic action of NaHCO₃: it appears to be due to the delocalization of an electron initiated by the interaction of the para-hydroxymethyl groups and the phenolic hydroxyl of HMPs with HCO ⁻₃ through hydrogen bonds, which results in facilitating the formation of active species.