Poly(dimethylamino)ethyl methacrylate for use as a surfactant in the miniemulsion polymerization of styrene

A novel Y-shaped macromonomer based on poly[(dimethylamino)ethyl methacrylate] (PDMAEMA) with a narrow molecular weight distribution was synthesized via oxyanion-initiated polymerization in which a potassium alcoholate of trimethylol propane allyl ether (2K-TMPAE) was used as a difunctional initiator. For the miniemulsion polymerization of styrene, this macromonomer acted well both as a comonomer carrying a reactive C=C double bond in its central section and as a pH-responsive polycationic surfactant in media with different pH values. The resulting microspheres composed of a hydrophobic polystyrene core and a hydrophilic PDMAEMA-protonated corona have shown spherical morphology and are quite stable. The nature of the reactive group, the amount of polymeric surfactant, and pH values in the aqueous medium have been systematically investigated during the miniemulsion polymerization by analyzing the evolution of the monomer conversions. The results of FTIR and (1)H NMR spectra demonstrated the generation of the functional particles. The analyses of TEM micrographs and dynamic light scattering (DLS) confirmed that the latices had a relatively narrow particle size distribution. The measurement of the zeta potential gave further evidence of the "hairy" particle structure. Because the reactive group is located in the central section of the macromonomer, the stabilization mechanism of the polymeric surfactant can be ascribed to (1) the absorption of two polycationic and hydrophilic tails that have electrostatic and steric stabilization to decrease the interface tension and (2) the copolymerization with the styrene monomer.