Polydimethylsiloxane-Based Polyurethanes: Phase-Separated Morphology and In Vitro Oxidative Biostability

Three series of segmented polyurethane block copolymers were synthesized using 4,4'-methylenediphenyl diisocyanate (MDI) and 1,4-butanediol (BDO) or 1,3-bis(4-hydroxybutyl)tetramethyl disiloxane (BHTD) as the hard segments, and soft segments composed of poly(dimethyl siloxane) (PDMS)-based and poly(hexamethylene oxide) (PHMO) macrodiols. Copolymers synthesized with the PDMS macrodiol and PDMS and PHMO macrodiol mixtures consist of three microphases: a PDMS phase, hard domains, and a mixed phase of PHMO (when present), PDMS ether end-group segments and some dissolved hard segments. Degrees of phase separation were characterized using small-angle X-ray scattering by applying a pseudo two-phase model, and the morphology resulting from unlike segment demixing was found to be closely related to the in vitro oxidative biostability of these segmented polyurethanes.