The influence of composition ratio on the morphology of biomedical polyurethanes

Abstract

Two series of thermoplastic polyurethane elastomers were synthesized from 4,4′-methylenediphenyl diisocyanate (MDI), 1,4-butanediol (BDO) chain extender, and each of poly(tetramethylene oxide) (PTMO) and poly(hexamethylene oxide) (PHMO) macrodiols. The PTMO and PHMO molecular weights were kept constant at 993 and 852 g/mol, respectively. In the PTMO-based series, the composition ratio was varied between 48 and 58% (w/w) of macrodiol; 2 commercially available PTMO-based polymers were also included. These were Pellethane 2363 80A® and its harder counterpart, Pellethane 2363 55D®. In the PHMO-based series, the composition ratio was varied between 50 and 60% (w/w) of macrodiol. The materials were characterized by differential scanning calorimetry (DSC), dynamic mechanical thermal analysis (DMTA), wide-angle X-ray diffraction (WAXD), and small-angle X-ray scattering (SAXS). Mechanical performance was also assessed by tensile testing, stress hysteresis, and hardness testing. Altering the composition ratio had a similar effect on morphology and properties for both the PTMO and PHMO-based series. An increase in hard segment content was associated with increased hard microdomain crystallinity, hardness, and stiffness. In both series, he beginning of hard microdomain interconnectivity was observed at a composition ratio of 52% soft segment. That is to say, for the processing and annealing conditions employed, macrodiol contents of 52% and below began to produce continuous, rather than discrete, hard microdomains. Pellethane 80A® was shown to have a discrete hard microdomain morphology, while Pellethane 55D® was shown to incorporate interconnecting hard microdomains. It is suggested that the superior biostability performance of Pellethane 55D relative to Pellethane 80A may be related to its interconnecting hard microdomain texture. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 71: 937–952, 1999