SOLUTION VISCOSITY BEHAVIOR OF POLYSTYRENE-BASED CATIONIC IONOMERS - EFFECTS OF ION CONTENT AND SOLVENT

Dilute-solution viscosities of polystyrene-based cationic ionomers containing ammonio or phosphonio groups were measured in several solvents. In polar solvents with dielectric constant (epsilon(r)) beyond 10, the ionomers showed a typical polyelectrolyte behavior, indicating that a large part of ionic groups were dissociated into ions. In nonpolar solvents with low E,, the reduced viscosity of the ionomers linearly decreased with a decreasing ionomer concentration. At low polymer concentrations, every ionomer gave a reduced viscosity lower than that of the corresponding chloromethylated polystyrene. With an increasing ion content, the intrinsic viscosity progressively decreased if the nonpolar solvents had a low acceptor number (AN), such as toluene or tetrahydrofran (THF). In the halogenated solvents with high AN value, such as chloroform, however, the intrinsic viscosity was hardly dependent on the ion content. This indicates that the intramolecular aggregation among the ionic groups is inhibited in the halogenated solvents due to a strong anion solvation. An addition of a protic solvent to a nonpolar solvent eliminates the aggregation between ionic groups and leads to polyelectrolyte behavior. (C) 1994 John Wiley & Sons, Inc.