Enzymatic Oxidative Polymerization of p-t-Butylphenol and Characterization of the Product Polymer

For structural control and analysis of an enzymatically synthesized polyphenol, peroxidase-catalyzed polymerization of p-t-butylphenol in a mixture of polar organic solvent and phosphate buffer has been examined in detail. The resulting products were subjected to preparative HPLC. Two dimers and one trimer were isolated and their structures were determined by 1H and 13C NMR. ESI-TOF mass analysis showed the formation of two kinds of dimer and of at least four kinds of trimer. These data clearly showed that the polymer was composed of a mixture of phenylene and oxyphenylene units. The ratio of phenylene and oxyphenylene units in the product could be controlled by changing the solvent composition. The phenylene unit linearly increased as a function of the water content in the mixed solvent.