Structure–property relationships of thermoplastic polyurethane elastomers based on polycarbonate diols

Abstract The phase‐separation behavior and morphology of polycarbonate‐based polyurethanes were investigated as a function of the soft‐segment molecular weight and chemical structure and the 4,4′‐diphenylmethane diisocyanate/1,4‐butanediol based hard‐segment contents. Polarized optical microscopy and atomic force microscopy images showed that the surface morphologies changed as the soft‐segment molecular weight and hard‐segment content varied and also when the sample preparation conditions were modified. An increase in the soft‐ and hard‐segment lengths led to increased phase separation with respect to the lower molecular weight soft segment, and this showed an interlocked and connected morphology of intermixed soft and hard domains. The surface morphology of phase‐separated polyurethanes with hard segments composed of more than four to five 4,4′‐diphenylmethane diisocyanate units contained globular hard‐segment domains formed by spherulites, in which the size and connectivity between the branched lamellae changed with the hard‐segment size. Interlamellar areas related to the soft segment were seen in the spherulites. Variations in the hard‐segment spherulites were observed for polyurethanes based on soft segments of different molecular weights. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008