Cononsolvency of Poly[2-(methacryloyloxy)ethyl phosphorylcholine] in Ethanol-Water Mixtures: A Neutron Reflectivity...

Molecular mechanisms underlying the cononsolvency, a re-entrant coil-to-globule-to-coil conformational transition of polymer chains in mixtures of two good solvents, of poly[2-(methacryloyloxy)ethyl phosphorylcholine] (PMPC) in ethanol-water binary mixtures were complementarily investigated. This was accomplished by following a statistical mechanical model for competitive hydrogen bonding combined with the cooperative solvation concept as well as neutron reflectivity (NR) experiments employing contrast variation in the cononsolvents. The experimental re-entrant aggregation of the PMPC chains in ethanol-water mixed solvents, obtained on the basis of turbidity was accurately reproduced by theoretical calculations. The calculation proved the relatively strong cooperativity of ethanol and the preferential interaction of water, while the total coverage of solvents was the lowest at an ethanol volume fraction (f_ethanol) of 0.90. At this level, the cononsolvency was the most significant, and the collapsed PMPC chains were solvated with more water than the bulk mixed solvent. The ethanol-water cononsolvency for the PMPC brushes on a planar silicon wafer was investigated by NR experiments, and the solvent composition involved in the collapsed PMPC brush was addressed according to the contrast variation study with mixed solvents of water, deuterium oxide, ethanol-d₅, and ethanol-d₆. The collapsed PMPC brushes at f_ethanol = 0.90 contained more water than the bulk solvent. The preferential distribution of water in the collapsed PMPC brush was consistent with the simulation results. Therefore, the molecular mechanism for the cononsolvency of PMPC in ethanol-water mixed solvents based on competitive hydrogen bonding coupled with cooperative solvation was experimentally rationalized.