Glass transitions in hydrogen-bonded polymer complexes

Mutual precipitates of poly (N, N‐dimethyl acrylamide) and poly (4‐hydroxystyrene) were collected from dioxane, methanol, or acetone. The glass transition (Tg) temperatures of the precipitates are higher than the weight‐average values. Clear films cast from dimethylformamide solutions have lower Tg values. Complexation also occurred between poly (ethyl oxazoline) and poly (4‐hydroxystyrene) in dioxane and between poly (vinyl pyrrolidone) and poly (4‐hydroxystyrene) in methanol. Again, the glass transition temperatures of the precipitates are higher than the values for the blend films. The ΔCp values associated with the glass transitions of the complexes are smaller than those of the blends having the same compositions. Negative excess heat capacities of mixing have been observed for several precipitates.