Tuning the Properties of Ester-Based Degradable Polymers by Inserting Epoxides into Poly(ϵ-caprolactone)

Graphical The reactions between poly( ϵ -caprolactone) and epoxides catalyzed by strong phosphazene bases result in ester-ether copolymers with high randomness owing to concurrent ring opening and transesterification. Enzymatic degradability of the copolymers can be bidirectionally regulated by the pendant group derived from the substituent of epoxide. A series of ester-ether copolymers were obtained via the reaction between α , ω -dihydroxyl poly( ϵ -caprolactone) (PCL) and ethylene oxide (EO) or monosubstituted epoxides catalyzed by strong phosphazene bases. The two types of monomeric units were distributed in highly random manners due to the concurrence of epoxide ring-opening and fast transesterification reactions. The substituent of epoxide showed an interesting bidirectional effect on the enzymatic degradability of the copolymer. Compared with PCL, copolymers derived from EO exhibited enhanced hydrophilicity and decreased crystallinity which then resulted in higher degradability. For the copolymers derived from propylene oxide and 1,2-butylene oxide, the hydrophobic alkyl pendant groups also allowed lower crystallinity of the copolymers thus higher degradation rates. However, further enlarging the pendant groups by using styrene oxide or 2-ethylhexyl glycidyl ether caused a decrease in the degradation rate, which might be ascribed to the higher bulkiness hindering the contact of ester groups with lipase.