Enzyme-catalyzed copolymerization of oxiranes with dicarboxylic acid anhydrides

Ring-opening copolymerizations of the oxiranes glycidyl phenyl ether (GPE) and diglycidyl ether of bisphenol A (DGEBA) with a dicarboxylic acid anhydride [methyl hexahydrophthalic anhydride, nadic anhydride, maleic anhydride (MA), or itaconic anhydride (IA)] were carried out with the lipases Candida cylindracea (CCL), Lipozyme TL-IM (LIM), and Novozyme 435 (N435) as catalysts. The CCL-catalyzed reaction of DGEBA with MA or IA (at a 1:2 molar ratio) at 80°C resulted in only partial curing. We monitored the reactions by Fourier transform infrared spectroscopy and by following the changes in the intensities of carbonyl stretching frequencies of the anhydride and ester groups. The reactivity of the oxirane group in GPE was higher than that in DGEBA; this may have been due to the higher viscosity of DGEBA. The reactivities of the enzymes for the copolymerization of the oxiranes and dicarboxylic acid anhydride were in the order LIM > CCL > N435.