Exploration of the Mechanism for Self-Emulsion Polymerization of Amphiphilic Vinylpyridine

Abstract

A rare self-assembly behavior is observed in a hydrophilic monomer (4-vinylpyridine) (4VP) when polymerized in water with a hydrophilic initiator that results in the production of monodisperse polymeric nanoparticles in a single step. This behavior mimics the behavior obtained with the more commonly reported amphiphilic block copolymers. The synthesis and self-assembly of homopolymer nanoparticle from 4VP without the use of any cross-linker, stabilizing agent, surfactant, or polymeric emulsifier are described along with fundamental aspects of the mechanism of this polymerization. This facile and robust procedure enabled the production of highly monodisperse P4VP nanoparticle with a tunable size ranging from 80 to 445 nm. For the first time, we have investigated the growth mechanism of these polymeric nanoparticles to clarify the mechanism of polymeric nanoparticle formation. This work also provides direct visible evidence through transmission electron microscopy (TEM) images at the nanometer scale, which helps in obtaining a better understanding of the mechanism of self-assembly. The effect of temperature on the size of the polymeric nanoparticles was also examined along with the effect of initiator, monomer, and solvent concentrations. We therefore report a versatile and scalable process for the production of monodisperse polymeric nanoparticles, which we call self-emulsion polymerization (SEP).