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Molecular dynamics in selected novel linear/low-branched polyurethanes (PUs), based on oligo(oxytetramethylene glycol), 4,4'-diphenylmethanediisocyanate (MDI) or 2,6-toluenediisocyanate (TDI), and unsymmetrical dimethylhydrazine (I) and a derivative of that (II) as chain extenders (CE), were studied by dielectric techniques. Special attention was paid to the investigation of the α relaxation, associated to the glass transition, by dielectric relaxation spectroscopy (DRS) and thermally stimulated depolarization currents (TSDC). The TSDC method was used to study the interfacial Maxwell-Wagner-Sillars (MWS) relaxation, related to the accumulation of charges at the interfaces between soft-segment and hardsegment microdomains. The results obtained by DRS and TSDC were in good agreement with each other and in reasonable agreement with results for the microphase separation (MS) obtained by small-angle X-ray scattering and differential scanning calorimetry. TSDC proved to be an attractive complementary technique to DRS for the study of MS in PUs. The results suggest that the position of the MWS band, as well as its separation from the α band, is a good measure of the degree of MS. As regards the PUs studied here, the degree of MS enhances by increasing the mole ratio of CE, and by replacing MDI by TDI or CE I by CE II.

Structural characteristics, thermal transitions and molecular dynamics of selected poly(amide urethane)s with transition metal acetyl acetonates Me(AcAc)(2) (Me = Sn(4+), Zn(2+), Cu(2+), Pb(2+)) 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 Sn(4+) and Cu(2+) 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.

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