Characterization and degradation of elastomeric four‐armed star copolymers based on caprolactone and L‐lactide

Abstract Although biodegradable polymers have found extensive applications in medical areas, there are limited reports that show elastomeric behavior. In this work, a biodegradable, elastomeric polymer is demonstrated from a four‐armed star copolymer. With a fixed middle core composition, comprising caprolactone (CL) and L‐lactide (LA), an elastomer is obtained by increasing the polylactide (PLA) end block lengths to obtain sufficient end block crystallinity. This increase suppressed the middle core's crystallinity yet ensured cocrystallization of the PLA ends of individual star copolymer chains to form a three‐dimensional network via physical crosslinking. Cyclic and creep test of the star copolymers showed that at least 75% of recovery was achieved. Degradation study of the copolymer showed that degradation first occurred in the caprolactone‐co‐lactide (CLLA) core, followed by degradation in the PLA ends. Chain scission in the middle core resulted in immediate formation of CL crystals within the core and increased crystallinity over time, in both CLLA core and PLA ends. © 2012 Wiley Periodicals, Inc. J Biomed Mater Res Part A: 100A:3436–3445, 2012.