Reactive surfactants in heterophase polymerization. XXIV. Emulsion polymerization of styrene with maleate- and succinate-containing cationic surfactants

A series of alkyl pyridinium bromide maleate and succinate diester surfactants has been used as stabilizers in the free radical emulsion polymerization of styrene. High conversions of styrene were achieved readily with the maleate surfactants, but the succinates gave rise to varying levels of retardation. In two of the latter cases, use of the surfactant at a concentration below its crucial micelle concentration appears to be a key factor, but the other retardations are difficult to account for. Little difference in reactivity and latex properties was found with the maleate surfactants despite the position of the maleate group being very different in the series of molecules examined. Chemical incorporation of the maleate surfmers into the polymer particles appears to occur early on in the polymerizations, but a sufficiently high proportion of groups is on the surface to yield stable latex emulsions. The surface tensions of the final latices produced with both the maleate and succinate surfactants are high, suggesting a large proportion of succinate species are also surface adsorbed. However, the surface tensions of these latices are a little lower than those of latices produced with the maleates, suggesting the proportion of solubilized succinate surfactant is a little higher. This seems to be important in terms of the robustness of the stability of the latices to the addition of electrolytes, the succinate-stabilized species being consistently more tolerant. This suggests that while chemically bound surfactants can improve some of the properties of latices, e.g. the hydrophobicity of films, this might be at the expense of latex stability.