The work described in this dissertation focuses on enhancing the polymer nanoparticle synthesis using RAFT (reversible-addition fragmentation chain transfer) in microemulsion polymerization in order to achieve predetermined molecular weight with narrow molecular weight polydispersity.

The hypothesis is that the use of an amphiphilic chain transfer agent (surface-active CTA) will confine the CTA to the surface of the particle and thermodynamically favor partitioning of the CTA between micelles and particles throughout the polymerization. Thus, the CTA diffusion from micelles to polymer particles would be minimized and the breadth of the CTA per particle distribution would remain low.

We report the successful improved synthesis of poly(butyl acrylate), poly(ethyl acrylate), and poly(styrene) nanoparticles using the RAFT microemulsion polymerization with surface-active CTA. The polymerization kinetics, polymer characteristics and latex size experimental data are presented. The data analysis indicates that the CTA remains partitioned between the micelles and particles by the end of the polymerization, as expected.

We also report the synthesis of well-defined core/shell poly(styrene)/poly(butyl acrylate) nanoparticle, having polydispersity index value of 1.1, using semi-continuous microemulsion polymerization with the surface-active CTA. The surface-active CTA restricts the polymerization growth to the surface of the particle, which facilitates the formation of a shell block co-polymers with each subsequent second monomer addition instead of discrete homopolymers. This synthesis method can be used to create a wide range of core/shell polymer nanoparticles with well-defined morphology, given the right feeding conditions.