PHOTOPOLYMERIZATION OF MICELLE-FORMING MONOMERS .1. CHARACTERIZATION OF THE SYSTEMS BEFORE AND AFTER POLYMERIZATION

Cationic surfactants bearing a polymerizable styryl headgroup and a variable alkyl chain (Cn-STY with n = 8, 12, and 16) have been synthesized. Their aqueous solutions have been characterized by the surfactant critical micellar concentration (cmc) and aggregation number using electrical conductivity, spectrofluorimetry, and time-resolved fluorescence quenching. The photoinitiated polymerization of these surfactants in the micellar state led to stable and transparent or slightly bluish systems. The polymerized systems poly(Cn-STY) and the recovered polymers were characterized by means of several complementary techniques. The polymers have high molecular weights (3 X 10(5)-3 X 10(6)) which indicate that the initial micellar structure is not preserved upon polymerization. The structure of the polymerized systems depends on the alkyl chain length of the surfactant. The poly(C16-STY) systems exhibit a structure similar to that of a polysoap with intramolecular hydrophobic microdomains whereas the poly(C8-STY) and poly(C12-STY) systems behave like classical polyelectrolytes.