Structure and relaxation dynamics of poly(amide urethane)s with bioactive transition metal acetyl acetonates in hard blocks

摘要

Structural characteristics, thermal transitions and molecular dynamics of selected poly(amide urethane)s with transition metal acetyl acetonates Me(AcAc)(2) (Me = Sn4+, Zn2+, Cu2+, Pb2+) as chain extenders, were comparatively investigated using small- and wide-angle X-ray scattering (SAXS, WAXS), differential scanning calorimetry (DSC), and dielectric techniques (dielectric relaxation spectroscopy, DRS; thermally stimulated currents, TSC). We studied the influence of metal chelates on the mixing of the soft-segment (SS) and hard-segment (HS) domains and the related degree of microphase separation (DMS). The reactivity of Me(AcAc)(2) with macrodiisocyanate was found to decrease in the order Sn(AcAc)(2)Cl-2 > Cu(AcAc)(2) > Zn(AcAc)(2) > Pb(AcAc)(2). While Pb(AcAc)(2) shows a higher tendency for crystallisation, both the dielectric and calorimetric results suggest that the corresponding polyurethane has comparatively low DMS. The type of the transition metal has moderate effect on the glass transition temperature and no influence on the shape of the dielectric alpha relaxation signal, indicating weak interactions between metal ions and SS domains. In contrast, structural parameters and the dielectric behaviour of the beta relaxation suggest preference for hydrogen-bonding interactions between Sn4+ and Cu2+ metal-chelates and HS domains. The temperature dependence of dc conductivity sigma(dc) is described by the Vogel-Tammann-Fulcher equation and signifies the coupling between the mobility of polymeric chains and charges' motion. It may be expected that the present combination of techniques and particular results with respect to DMS will contribute to the development and testing of novel biodegradation-resistant and antibacterial metal-polyurethanes for biotechnological and industrial applications.