Miscibility with positive deviation in Tg–composition relationship in blends of poly(2-vinyl pyridine)-block-poly(ethylene oxide) and poly(p-vinyl phenol)

Phase behavior and miscibility with positive deviation from linear Tg–composition relationship in a copolymer/homopolymer blend system, poly(2-vinyl pyridine)-block-poly(ethylene oxide) (P2VP-b-PEO)/poly(p-vinyl phenol) (PVPh), were investigated by differential scanning calorimetry (DSC), Fourier-transform infrared spectroscopy (FT-IR) and solid-state 13C nuclear magnetic resonance (13C NMR), optical microscopy (OM), and scanning electron microscopy (SEM). Optical and electron microscopy results as well as NMR proton spin–lattice relaxation times in laboratory frame ( T 1 H ) all confirmed the miscibility as judged by the Tg criterion using DSC. In comparison to the literature result on a homopolymer/homopolymer blend of P2VP/PVPh, fitting with the Kwei equation on the Tg–composition relationship for the block-copolymer/homopolymer blend of P2VP-b-PEO/PVPh blend system yielded a smaller q value (q = 120) for P2VP-b-PEO/PVPh than that for P2VP/PVPh blend (q = 160). The FT-IR and 13C NMR results revealed hydrogen-bonding interactions between the pendant pyridine group of P2VP-b-PEO and phenol unit in PVPh, which is responsible for the noted positive deviation of the Tg–composition relationship. Comparison of the shifts of hydroxyl IR absorbance band, reflecting the average strength of H-bonding, indicates a decreasing order of P2VP/PVPh > P2VP-b-PEO/PVPh > PEO/PVPh blends. The PEO block in the copolymer segment tends to defray the interaction strength in the P2VP-b-PEO/PVPh blends because of relative weaker interaction between PEO and PVPh than that between P2VP and PVPh pairs. A comparative ternary (P2VP/PEO)/PVPh blend was also studied as the controlling experiments for comparison to the P2VP-b-PEO/PVPh blend. The thermal behavior and interaction strength in (P2VP/PEO)/PVPh ternary blends are discussed with those in the P2VP-b-PEO/PVPh copolymer/homopolymer blend.