The Effect of Monomer Aggregation in the Photopolymerization of Styrenesulfonate

The polymerization of styrenesulfonate photoinitiated with visible light in the presence of the dye safranine (λ max = 532 nm) has been studied at various monomer concentrations in aqueous solution (>0.1 M). The elemental photochemical and ground state steps involved in the initiation were studied individually in order to obtain a general mechanism for the photoinitiation. Two important facts were found: first, the photopolymerization proceeds in the presence of air, whereas co-initiators like amines, inhibit the reaction; second, several evidences obtained from ground state and excited-state interactions, as well as from the polymerization products suggest the aggregation of the monomer in clusters containing a dye molecule. Similar evidences were found when using the nonpolymerizable anion toluenesulfonate.