Phase behavior of (polyacrylamides + water) solutions: concentration, pressure and isotope effects

Phase diagrams of poly(N-isopropylacrylamide) (PNIPAAM) as well as of hydrophilically-modified copolymers in aqueous solution were determined. A high-accuracy He–Ne Laser scattering technique was used for the detection of operational spinodal (sp) and cloud-point (cp) curves. Polymer concentration was varied from 0.5 to 20 wt.%. In the case of copoly(PNIPAAM/vinylsaccharide) several different chain lengths were considered. Pressure (up to 400 bar) and solvent isotope effects were studied. We predict a closed-loop type phase diagram for the copolymers, which presents an estimated hypercritical point in H2O solutions at Mw∼0.5×105, although only lower critical solution temperature (LCST) is experimentally accessible. At lower molecular weights, the solutions are always in the one-phase region.