Studies on dilute solutions of rodlike macroions. II. Electrostatic effects

Abstract

AbstractA group of rodlike polymers soluble only in strong protic acids was studied using light scattering and viscosity techniques. These include poly(1,4‐phenylene benzobisoxazole), poly(1,4‐phenylene benzobisthiazole) and poly(1,4‐phenylene terephthalamide). The solution properties were dependent on the ionic strength of the acid used as solvent. In a low ionic strength acid such as chlorosulfonic acid, the polymer solutions exhibited decreased unpolarized scattering, an extremely small translational diffusion coefficient, and high viscosity. All of these effects could be eliminated by the addition of a salt such as lithium chlorosulfonate, which increased the ionic strength of the solvent. The effects were attributed to a pseudo ordering of the polymer solvent system caused by electrostatic repulsions between protonated polymer chains effective over large distances (ca. 100 Å) in the low ionic strength solvent. This type of ordering is distinct from actual anisotropic phase formation, which occurs at higher concentrations in these systems. Analysis of data at infinite dilution gave a persistence length of at least 45 nm for poly(1,4‐phenylene terephthalamide), larger than previous experimental results, but in accord with recent rotational isomeric state calculations and similar to experimental data for poly(p‐benzamide).