Transition behavior and phase segregation in TDI polyurethanes

Prior studies of two series of segmented polyurethanes based on 2, 4 toluene cliisocyanate (2, 4 TDI) or 2, 8 TDI, butanediol, and a 1000 molecular weight polytetramethyleneoxide (PTMO-1000) soft segment revealed a rapid increase in soft segment glass transition temperature (T_g) with increasing urethane content in the 2, 4 TDI series. The change in T_g couldbe correlated with estimates of hard segment-soft segment phase mixing obtained by infrared analysis of the urethane NH and carbonyl bands. In the present paper, the infrared data have been reevaluated using improved procedures for resolving the carbonyl band into H-bonded and nonbonded components, and the relation between the estimated extent of phase mixing and T_g has been reexamined. The transition behavior in an extensive series of related polymers has also been determined, including 2, 4 TDI arid 2, 6 TDI samples with PTMO2000 as well as polybutyleneadipate (PBA-1000 and PBA-2000) soft segments. The results indicate the effectiveness, of increased soft segment molecular weight in promoting phase segregation, imply that much greater phase mixing occurs in polyester than polyether samples, suggest that anchoring the ends of the soft segments has only a small effect on T_g, and provide some evidence that H-bonding not only increases T_g but can also impede soft segment crystallization.