Thermoplastic urethane elastomers. I. Effects of soft-segment variations

A series of thermoplastic urethane elastomers with soft segments of varying sequence length was prepared and their dynamic mechanical properties were characterized over a wide temperature range. The polymers were prepared using various molecular weight polycaprolactone diols as the soft segment and 4,4′‐diphenylmethane diisocyanate and 1,4‐butanediol as the hard segment. The urethane elastomer exhibited soft‐segment crystallization when a polycaprolactone diol greater than 3000 M̄n was used. The glass transition temperature of these materials progressively shifted to lower temperatures as the chain length of the soft segment was increased. This dependence was interpreted in terms of a molecular weight relationship similar to that associated with amorphous homopolymers. The dynamic mechanical properties of these polyurethanes appear to be consistent with responses observed for compatible copolymers.