Viscometry of polyelectrolyte solutions: Star-like versus linear poly[[2-(methacryloyloxy)ethyl] trimethylammonium iodide] and specific salt effects

Abstract

The intrinsic viscosities, [η], of the 3-arm star polyelectrolyte in pure water are for a given molar mass considerably lower than for the linear product because of the higher monomer concentration and charge density in isolated coils. These effects are much more pronounced than in the case of uncharged macromolecules. Extra salt (NaCl, NaI, CaCl2) reduces the solution viscosities of the 3-arm star polymer less than of the linear product. The transition of [η] from the value in pure water to the minimum saturation value at high salt concentrations follows a Boltzmann sigmoid. In saline solvents the changes of the viscosities with rising polymer concentration depend strongly on the chemical nature of the salt and on the molecular architecture of the solute. The present findings demonstrate the necessity to account for thermodynamic interactions between all components of the mixture, in addition to the usual electrostatic considerations. These considerations should turn out helpful for a better understanding of salt induced topological transitions of charged biopolymers.