Peroxidase-Catalyzed Oxidative Polymerization of Bisphenols

Oxidative polymerization of bisphenolic monomers has been performed using peroxidase as catalyst in an aqueous organic solvent. Peroxidase induced the polymerization of an industrial product, bisphenol F, consisting of 2,2‘-, 2,4‘-, and 4,4‘-dihydroxydiphenylmethanes. Under the selected conditions, the quantitative formation of the polymer was observed. Among the isomers, 2,4‘- and 4,4‘-dihydroxydiphenylmethanes were polymerized to give the polymer in high yields, whereas no polymerization of the 2,2‘-isomer occurred. These data suggest that the radical transfer reaction between a phenoxy radical of the enzymatically polymerizable monomer and the enzymatically nonpolymerizable monomer frequently took place during the polymerization. Various 4,4‘-dihydroxyphenyl compounds were also polymerized by peroxidase catalyst. The polymerization behaviors, and solubility and thermal properties of the resulting polymers strongly depended on the bridge structure as well as the enzyme origin. Polymers from dihydroxydiphenylmethanes showed relatively high thermal stability.