Anionic polymerization of styrene sulfonic acid derivatives

Abstract As a preliminary to the preparation of block copolymers of p ‐styrene sulfonic acid and isoprene, anionic polymerization of several derivatives of the former was investigated. Radical anions of naphthalene were used as the initiator for this study, in which the effects of polymerization variables including counterion, temperature, monomer and initiator concentrations, and solvent were investigated. Synthesis techniques were modified to obtain monomers of sufficient purity for anionic polymerization of n ‐propyl, isopropyl, and methyl styrene sulfonates were successfully initiated, but only a limited degree of polymerization could be achieved under a wide variety of polymerization conditions. It is tentatively suggested that the living polymeric anions become dormant owing to a complexation between the anion and nearby sulfonate groups on the polymer coil.