Kinetically Controlled Synthesis of Nonspherical Polystyrene Nanoparticles with Manipulatable Morphologies

The morphology of nanoparticles plays a critical role in determining their properties and applications. Herein, we report a versatile approach to the fabrication of nonspherical polystyrene (PS) nanoparticles with controlled morphologies on the basis of kinetically controlled seed-mediated polymerization. By manipulating parameters related to the reaction kinetics including the concentration of monomers, injection rate of reactants, and reaction temperature, the monomers could be directed to polymerize on the selective sites of PS seeds, and after the removal of the second polymer, nonspherical nanoparticles with a variety of thermodynamically unfavored morphologies could be synthesized. We systematically investigated the formation mechanism of these nonspherical nanoparticles by monitoring the evolution of seeds during the reaction. Moreover, we have also successfully extended this strategy to reaction systems containing monomers with different combinations and seeds with different sizes. We believe this work will provide a promising route to the fabrication of nonspherical polymer nanoparticles with controlled morphologies for various applications.