Hydrolytic Degradation of Porous Crosslinked Poly(ε-Caprolactone) Synthesized by High Internal Phase Emulsion Templating

Porous poly(ε-caprolactone) (PCL) scaffolds were fabricated using the high internal polymerization emulsion (HIPE) technique. Bis(ε-caprolactone-4-yl) (BCY) was utilized as crosslinker. The crosslinking density and the volume fraction of the dispersed phase were varied in order to study the potential effect of these parameters on the hydrolytic degradation at 37 °C and 60 °C. After different hydrolysis times the remaining solid samples were analyzed by Fourier transform infrared spectroscopy (FTIR) and scanning electron microscopy (SEM), while the degradation products in the aqueous aging solutions were analyzed by laser desorption ionization-mass spectrometry (LDI-MS). The effect of temperature on the degradation process and release of degradation products was, as expected, significant. The temperature effect was also shown by FTIR analysis that displayed a pronounced increase in the intensity of the hydroxyl-group absorption band after 70 days of hydrolysis at 60 °C indicating significant cleavage of the polymer chains. LDI-MS analysis proved the release of oligomers ranging from dimers to hexamers. The product patterns were similar, but the relative m/z signal intensities increased with increasing time, temperature and crosslinking density, indicating larger amounts of released products. The latter is probably due to the decreasing degree of crystallinity as a function of amount of crosslinker. The porous structure and morphology of the scaffolds were lost during the aging. The higher the crosslinking density, the longer the scaffolds retained their original porous structure and morphology.