NUMERICAL AND MONTE-CARLO SIMULATIONS OF PHENOLIC POLYMERIZATIONS CATALYZED BY PEROXIDASE

Numerical and Monte Carlo simulations of horseradish peroxidase-cataly zed phenolic polymerizations have been performed. Kinetic constants fo r the simulations were fit to data from the oxidation and polymerizati on of bisphenol A. Simulations of peroxidase-catalyzed phenolic polyme rization were run as a function of enzyme concentration and radical tr ansfer and radical coupling rate constants. Predictions were performed with respect to conversion vs. time and number average molecular weig ht and polydispersity vs. conversion. It is shown that the enzymatic p olymerization of phenols can be optimized with respect to high molecul ar weights by employing low enzyme concentrations and phenols with low radical coupling rate constants coupled with relatively high radical transfer rate constants. Such phenols may be identified by using linea r free energy relationships that relate radical reactivity to electron donating/withdrawing potential of the phenolic substituent. (C) 1993 John Wiley & Sons, Inc.