Microstructural organization of three-phase polydimethylsiloxane-based segmented polyurethanes

Microphase separation is investigated for segmented polyurethane copolymers synthesized from 4,4′-methylenediphenyl diisocyanate and 1,4-butanediol as the hard segments and poly(hexamethylene oxide diol) and hydroxyl-terminated polydimethylsiloxane as soft segments. The neat PDMS-based diol exhibits two segmental relaxations corresponding to the principal repeating unit, Si(CH ₃) ₂O, and to the hydroxyl end-group segments. When incorporated in the polyurethanes, the siloxane units form their own phase, while the end-group segments are mixed with the second macrodiol and some short hard segment sequences. This is demonstrated by the results of dynamic mechanical analysis and wide-angle X-ray diffraction experiments. The microdomain morphology was characterized principally by small-angle X-ray scattering, and the scattering data were analyzed with a pseudo-two-phase model as well as a modified three-phase core-shell model.