Acid- and base-catalyzed hydrolyses of aliphatic polycarbonates and polyesters

Poly(propylene carbonate) (PPC) was synthesized by the zinc glutarate catalyzed copolymerization of carbon dioxide and propylene oxide (PO). Hydrolytic degradability of the PPC polymer was examined in tetrahydrofuran solutions containing 10 wt.% acidic or basic aqueous solutions of varying pH using viscometry and GPC analysis. Further, the hydrolysis behaviors of all PPC solutions were compared with those of poly((epsilon)-caprolactone) (PCL) and poly(d,l-lactic acid) (PLA). All polymers studied show higher degradability in strong basic conditions than in strong acidic conditions, but very low degradability in moderate acidic, basic and neutral conditions. Moreover, PPC is degraded less in strong acidic conditions than the polyesters, while in strong basic conditions, the polycarbonate is more easily degraded. The difference in degradabilities of these polymers in acidic conditions is associated with the different nucleophilicities of their carbonyl oxygen atoms, while in basic conditions the differences are associated with the different electrophilicities of the corresponding carbonyl carbon atoms. With regard to the hydrolysis results and the structural and chemical nature of the polymer backbones, degradation mechanisms are proposed for the acid- and base-catalyzed hydrolyses of PPC, PCL and PLA.