Long term in vitro biostability of segmented polyisobutylene-based thermoplastic polyurethanes†.
Long term in vitro biostability of thermoplastic polyurethanes (TPUs) containing mixed polyisobutylene (PIB)/poly(tetramethylene oxide) (PTMO) soft segment was studied under accelerated conditions in 20% H2O2 solution containing 0.1M CoCl2 at 50°C to predict resistance to metal ion oxidative degradation (MIO) in vivo. The PIB-based TPUs showed significant oxidative stability as compared to the commercial controls Pellethane™ 2363-55D and 2363-80A. After 12 weeks in vitro the PIB-PTMO TPUs with 10–20% PTMO in the soft segment showed 6–10% weight loss whereas the Pellethane™ TPUs degraded completely in about 9 weeks. Attenuated total reflectance Fourier transform infrared spectroscopy confirmed the degradation of Pellethane™ samples via MIO by the loss of the ∼1110 cm−1 aliphatic C O C stretching peak height attributed to chain scission, and the appearance of a new peak at ∼1174 cm−1 attributed to crosslinking. No such changes were apparent in the spectra of the PIB-based TPUs. The PIB-based TPUs exhibited 10–30% drop in tensile strength compared to 100% for the Pellethane™ TPUs after 12 weeks. The molecular weight of the PIB-based TPUs decreased slightly (10–15%) at 12 weeks. The Pellethane™ TPUs showed a dramatic decrease in Mn and an increase in low molecular weight degradation product. Scanning electron microscopy (SEM) showed severe cracking in the Pellethane™ samples after 2 weeks, whereas the PIB-based TPUs exhibited a continuous surface morphology. The weight loss, tensile, and SEM data correlate well with each other and indicate excellent biostability of these materials.