Control of Ionic Interactions in Sulfonated Polystyrene Ionomers by the Use of Alkyl- Substituted Ammonium Counterions

Polystyrenes containing up to about 20 mol % sulfonic acid are reproducibly and readily prepared by the sulfonation of polystyrene at 50°C with acetyl sulfate in 1,2-dichloroethane solution. The metal salts of sulfonated polystyrene possess extremely high melt viscosities and are soluble in single solvents such as toluene and THF only at very low sulfonate levels. Such properties are the result of the very strong ion-dipole interactions among the metal sulfonate groups. Such strong interactions can be substantially reduced through the neutralization of the sulfonic acid with ammonia and, most especially, relatively simple low molecular weight amines. Sulfonated polystyrenes varying in sulfonic acid content from about 1 mol % to about 20 mol % were neutralized with various mono-, di-, and tri-substituted alkyl amines ranging in alkyl chain length from H (ammonia) to Czo, and their rheological and thermal properties were measured. As the number of substituents on the nitrogen increased, the glass transition temperature and the melt viscosity decreased. The tributylamine sulfonates possessed viscosities almost as low as unsulfonated polystyrene and the longer chain amines behaved as if internally plasticized. The properties of amine neutralized sulfonated polystyrenes are concluded to be primarily a function of amine size. Increasing the size of the amine reduces the strength of the iondipole interaction by preventing close approach of the amine sulfonate groups.