Segmented polyurethanes based on polytetramethylene glycol (PTMG) of 1000 g/mol were synthesized using a two-step polymerization procedure. Various hard segments were obtained using hexamethylene diisocyanate (HDI) or 4,4'-methylenebis(phenyl isocyanate) (MDI) as the diisocyanates and hydroquinone bis(2-hydroxyethyl)ether (HQEE) or triptycene-1,4-hydroquinone bis(2-hydroxyethyl)ether (TD) as the chain extenders. The effect of rigidity and bulkiness of the hard segments on morphology, thermal and mechanical properties were studied. Fourier transform infrared (FTIR) suggested that hydrogen bonding interactions were weakened in the presence of the bulky triptycene-containing hard segments. Variable temperature FTIR demonstrated that hydrogen bonds completely dissociate at around 170 degrees C for polyurethanes chain extended by HQEE compared to around 110 degrees C for their TD analogs. Polyurethanes from MDI and TD displayed microphase mixing behavior based on atomic force microscopy (AFM) and small angle X-ray scattering (SAXS). When HDI was used as the diisocyanate in the TD chain extended polyurethane, enhanced microphase separation was observed with comparable mechanical properties to those of the MDI analogs with HQEE. (C) 2013 Elsevier Ltd. All rights reserved.