A series of segmented polyurethanes (SPU), based on 4,4′-diphenylmethane diisocyanate and 1,4-butanediol as hard segments (HS) and poly(propylene glycol) (Mn = 1000) as soft segments, were synthesized. Relationships between microphase separation and the surface and adhesive properties were characterized by thermal analysis, X-ray diffraction, contact angle, electron spectroscopy for chemical analysis, T-peel and tensile test measurements. Microphase separation occurred for SPU with an HS content of more than 50 wt% and influenced not only the bulk properties, but also the surface properties. Young's modulus and tensile strength increased abruptly for SPU with an HS content of more than 50wt%. Surface free energy also increased in a stepwise manner at an HS content of about 50wt%. The optimum HS content of SPUs for adhesion, based on T-peel test results, also gave good thermal and mechanical properties.
