Condensation reactions of phenolic resins IV: Self-condensation of 2,4-dihydroxymethylphenol and 2,4,6-trihydroxymethylphenol (2)

Abstract

Kinetics of the self-condensation of 2,4-dihydroxymethylphenol (2,4-DHMP) and 2,4,6-trihydroxymethylphenol (THMP) were investigated to elucidate the mechanisms of the condensation of hydroxymethylphenols (HMPs). Rate equations were derived on the assumptions of the formation of quinone methide intermediates as unimolecular reactions and the occurrence of bimolecular reactions between undissociated HMPs, between undissociated HMP and dissociated HMP, and between dissociated HMPs. Rate constants were determined numerically by comparing the calculated reaction rates with observed ones. The results of analyses are as follows: (1) Both unimolecular and bimolecular reactions occur as the rate-determining steps during the self-condensation of 2,4-DHMP and THMP with low concentrations. (2) Nothing but bimolecular reactions occur as the rate-determining steps during the self-condensation of THMP with high concentrations. (3) Differences in the activation energy and the reaction rate due to the unimolecular process between 2,4-DHMP and THMP are small. (4) Rates of bimolecular reactions of THMP are about five times as large as those of 2,4-DHMP. (5) The values of the rate constants and the activation energy for the bimolecular reactions of THMP of low concentrations differ from those of THMP of high concentrations, indicating the difference in reaction mechanisms.