Thermal Properties, Interactions, Morphologies, and Conductivity Behavior in Blends of Poly(vinylpyridine)s and Zinc Perchlorate

We have investigated the physical properties and specific interaction of two regioisomeric poly(vinylpyridine)sspoly(2-vinylpyridine) (P2VP) and poly(4-vinylpyridine) (P4VP)sblended with zinc perchlorate. Analyses by differential scanning calorimetry indicate that the values of Tg of the poly- (vinylpyridine)s increase significantly upon blending with zinc perchlorate. The values of Tg of P2VP and P4VP increase by 119 and 154 °C, respectively, relative to their corresponding pure polymers, upon blending with 40 and 30 wt %, respectively, zinc perchlorate. On the basis of the extended configuration entropy model equation, the interaction strength of the zinc salt/P4VP blend (3.60) is greater than that of the zinc salt/P2VP blend (3.55). The interaction between the polymer and the zinc ion was confirmed by infrared, X-ray photoelectron, and solid-state NMR spectroscopies, which suggest that the zinc cation coordinates to pyridine units in a metal-ligand bonding mode. In addition, the strength of the interaction between the polymer and the zinc ion is influenced by the different steric demands of the two polymer structures. A good correlation is found in the morphology of these polymer/zinc salt blends as determined by wide-angle X-ray diffraction and solid-state NMR T1F H measurements.