Covalently closed microemulsions in presence of triblock terpolymers

This paper is focused on the influence of polystyrene (PS)-poly(1,4-butadiene) (PB)-poly(ethylene oxide) (PEO) triblock terpolymers on the w/o microemulsion of the pseudo-ternary system water/sodium dodecylsulfate (SDS)/xylene-pentanol. Despite the insolubility of the copolymer in water as well as in the xylene-pentanol mixture, it can be incorporated into the w/o microemulsion and interactions between the triblock terpolymer molecules and the anionic surfactant headgroups can be detected by differential scanning calorimetry (DSC) measurements. Furthermore, dynamic light scattering measurements were used to determine the aggregate diameter of the modified microemulsions. For lower polymer concentrations large aggregates between 100 and 500 nm can be observed. Surprisingly, at a higher terpolymer concentration of 5 wt%, significant smaller aggregate diameters can be identified by dynamic light scattering and Cryo-SEM. One can conclude that the copolymers are incorporated in the inverse microemulsion droplets, where the PB blocks cover the water droplets. The thermally induced radical cross-linking of the butadiene units in the presence of azobisisobutyronitrile (AIBN) leads then to covalently closed nanocapsules with an average size of 10 nm.