Degradation of PCL‐MPEG diblock copolymer in rat plasma

Abstract The poly(ε‐caprolactone)‐co‐poly(ethylene glycol) (PCL‐MPEG) amphiphilic diblock copolymer with molar ratio of ε‐CL to MPEG 81:1 is synthesized via a ring‐opening polymerization without a catalyst. The M_w and M_n molecular weights and the polydispersities are 18,000, 11,000 g/mole and 1.55, respectively. The pegylated amphiphilic copolymer forms micelles with a low critical micelle concentration 6.71 × 10⁻⁸ mole/L, and the average particle size of copolymeric micelles is 62.3 ± 12.9 nm. The degradation behavior of diblock copolymer was studied in rat plasma at 37°C for 90 days. The changes of mass, composition, morphology, molecular weight, and thermal property of PCL‐MPEG copolymer were investigated. The decrease of copolymer mass shows two phases with rate constants of 1.91 × 10⁻¹ day⁻¹ in the first‐phase (1–24 h) and 1.77 × 10⁻³ day⁻¹ in the second‐phase (1–90 days). The degradation of labile ester linkage between PCL block and MPEG block accounts for continuous decrease of copolymer mass in plasma. The decrease of EG molar ratio from 1.30 to 0.67 and prominent reduction of enthalpy of fusion of remained copolymer from 116.5 to 85.2 J/g provide evidences of PCL‐MPEG chain scission. On the other hand, the presence of partially degraded copolymers in the residuals results in its polydispersity increased from 1.55 to 2.24 at the end of 90 days. Nevertheless, the surface erosion of copolymer makes the molecular weight not quite different from its original value. © 2007 Wiley Periodicals, Inc. J Biomed Mater Res, 2008