Synthesis of polymeric janus nanoparticles and their application in surfactant-free emulsion polymerizations

A robust and simple synthesis of nano-size oblate to dumbbell shaped polymeric anisotropic particles using RAFT mediated emulsion polymerization is presented. The particle synthesis relies on the property that monomer swollen cross-linked polymer seed particles shrink and expel some of the monomer when heated. Thus, upon heating for polymerization, some of the swelling monomer is expelled and sub-sequently polymerizes to form a bulge on the side of the original crosslinked seed particle. The shape of the bulge, and the degree of contact that the expelled monomer maintains with the original seed particle, is controlled by controlling the wettability of the seed surface by the expelled monomer. Very small monodisperse cross-linked polymer particles are initially prepared by RAFT mediated emulsion polymerization, then swollen with monomer and further polymerized to form anisotropic particles with a long dimension as little as 25 nm. Both the shape of the anisotropic bulge and the polymer composition, of each end of the final Janus nanoparticle can be finely controlled. The surface active properties of the Janus nanoparticles are demonstrated by their ability to contribute as stabilizers and influence particle formation in a surfactant free ab-initio emulsion polymerization. The method provides a simple and reproducible process for the production of Janus colloidal nanoparticles readily achievable in a normal latex plant where batch size would be limited only by the size of the reactor.