Structure and Properties of Polyelectrolyte−Surfactant Nonstoichiometric Complexes in Low-Polarity Solvents

Abstract

Solutions of complexes of poly(N-ethyl-4-vinylpyridinium) cations and dodecyl sulfate anions in chloroform are studied by viscometry, isothermal diffusion, flow birefringence, and dynamic light scattering techniques. Stoichiometric polyelectrolyte−surfactant complexes as well as nonstoichiometric ones with the compositions 0.55−1.0, expressed as the molar ratio of surfactant ions to the polycation chain units, neither form interchain associations nor dissociate into individual components in dilute solutions in chloroform. A decrease in the complexes' composition, i.e., a substitution of dodecyl anions with bromide anions, results in an increase of diffusion coefficients and a decrease in the intrinsic viscosity and in the absolute value of the negative segmental optical anisotropy of macromolecules of such complexes. Solubility of the studied complexes in low-polarity solvents increases in the order chloroform > chlorobenzene > benzene and decreases with decrease in the composition of complexes. Interchai...