Increasing Molecular Mass in Enzymatic Lactone Polymerizations

Using a model developed for the enzyme-catalyzed polymerization and degradation of poly(caprolactone), we illustrate a method and the kinetic mechanisms necessary to improve molecular mass by manipulating equilibrium reactions in the kinetic pathway. For these polymerization/degradation reactions, a water/linear chain equilibrium controls the number of chains in solution. Here, we control the equilibrium by adding water-trapping molecular sieves in the batch polymerization reactions of ε-caprolactone. While ring-opening rates were mostly unaffected, the molecular mass shifted to higher molecular masses after complete conversion was reached, and a good agreement between the experimental and modeling results was found. These results provide a framework to improve the molecular mass for enzyme-catalyzed ring-opening polymerization of lactone.