Surface-Functionalized Polystyrene Latexes Using Itaconate-Based Surfmers.

Itaconic acid was readily transformed to a series of amphiphilic diesters via stepwise esterification of itaconic anhydride; the diesters carry one alkyl (cetyl or octyl) group and either a PEG, glyceryl, or dopamine segment. These diesters were used as surfmers for the preparation of polystyrene (PS) emulsions, with the expectation that the surface of the emulsion particles would carry PEG, glyceryl or dopamine units. NMR spectroscopic studies revealed that the surfmers were covalently incorporated into the polystyrene chains; furthermore, NMR tube polymerization experiments also confirmed that when the PEG surfmer was used, the PEG segments are indeed present on the surface of the emulsion particles. The size of the PEGlyated PS emulsions was readily varied from 35 to 140 nm by changing the mole fraction of surfmer used. In the case of the glyceryl and dopamine carrying surfmers, an octyl unit was used as the hydrophobic segment to ensure appropriate hydrophobic-hydrophilic balance; it was noticed that significantly larger mole fractions of the surfmers were required (15-20 mol %) to generate stable emulsions with particle sizes of about 150 nm. The PS emulsions carrying dopamine units on the surface were found to adhere to glass surfaces; thus suggesting that such "sticky" emulsion particles could be used to functionalize different types of surfaces. Finally, itaconate diesters bearing cetyl and perfluorooctyl segments were also prepared and shown to copolymerize with styrene to generate fluoroalkyl-enriched PS copolymers; these were used to generate hydrophobic coatings, with water contact angles of over 120°. Thus, itaconate-based surfmers are readily accessible alternatives for the preparation of emulsions with tailored size and surface functionality.