Reappearance of slow mode in mixtures of polyethylene glycol and poly(sodium methacrylate)

Abstract

Mixtures of an anionic polyelectrolyte, poly(sodium methacrylate), NaPMA, and a neutral polymer, polyethylene glycol, PEG, were investigated by dynamic and static light scattering techniques at different concentrations and chain-lengths of PEG. The NaPMA standard with a narrow molecular weight distribution was chosen for the study. The so called slow-mode behaviour, characteristic of salt-free NaPMA solutions, vanishes as the simple salt, NaCl in this case, is added in a sufficient amount. However, in NaPMA–NaCl–PEG mixtures, the slow-mode signal is observed again. We assume that the dielectric constant of the mixture with PEG, which is substantially lower than that of pure water, causes the reappearance of the slow-mode signal through reinforced electrostatic interactions between NaPMA polyions. Monte Carlo simulations of a coarse-grained model of the system confirm stronger correlations between NaPMA molecules and thus qualitatively agree with experimental results.