A Comparison of the Dielectric Behavior of Aromatic and Aliphatic Polyurethanes in Relation to Transitional Phenomena

The dielectric properties of two polyurethanes (PUs) with different hard segments, i.e., aromatic methylene di-p-phenyl diisocyanate (MDI) and aliphatic hexamethylene diisocyanate (HDI), were investigated in the temperature range of -100 to $100^{\circ}C$ and in the frequency range of 1 Hz to 3 kHz. The ${\alpha}$-relaxations induced by the glass transition of the equivalent soft segments in the two PUs occurred at relaxation times of ${\tau}=3.46{\times}10^{-3}s$ for MDI-PU and ${\tau}=3.39{\times}10^{-2}s$ for HDI-PU at $-20^{\circ}C$, in accord with the temperature-frequency superposition principle, resulting in similar shifting factors. However, different I-relaxations were observed for the two PUs. The I-relaxation of MDI-PU occurred due to the mobility of the chain extenders near $80^{\circ}C$ with a slower shifting rate than the ${\alpha}$-relaxation. On the other hand, I-relaxation arising from both the extender and the unconstrained hard segments of HDI-PU occurred at $70{\sim}100^{\circ}C$, indicating complicated dielectric behavior due to partial interaction with the ${\alpha}$-relaxation at high frequencies. Thus, the I-relaxation of HDI-PU did not follow the superposition principle. The dielectric behaviors of the PUs were mainly influenced by their phase transitions, which were affected by the structure and components of the materials.