Polymerisation of styrene in microemulsion with catanionic surfactant mixtures

The use of aqueous catanionic surfactant mixtures in the oil-in-water (o/w) microemulsion polymerisation of styrene is reported. Catanionic surfactant mixtures of dodecyltrimethylammonium bromide 1 and sodium dodecylsulfate 3, or decanediyl-1,10-bis(dimethyldodecylammonium bromide) 2, a gemini surfactant, and the anionic surfactant 3 were used. Phase behaviour and polymerisation properties of the microemulsions were studied as a function of the total surfactant concentration and the cationic/anionic surfactant ratio. Single-phase o/w microemulsions were only formed if either the cationic or anionic surfactant were present in large excess. Upon -irradiation, polymer nanoparticles were obtained. Using dynamic light scattering, the particle radii were determined to be 10 to 20 nm, the size depending on the total surfactant concentration, the cationic/anionic surfactant ratio and the surfactant/styrene ratio. Size exclusion chromatography indicated molecular weights of polystyrene of between 3×10⁵ and 1.4×10⁶ Daltons. Catanionic 1/3 and 2/3 mixtures differ in their styrene solubilizations. In a 1- or 3-rich system, the solubilization efficiency can be improved by increasing the concentration of the oppositely charged minor surfactant component, while in a 2-rich system the addition of 3 only diminishes the efficiency. Possible reasons for the different behaviours are discussed.