Reactive Surfactants for Atom Transfer Radical Polymerization in Dispersed Media

This thesis describes the design and use of reactive surfactants for atom transfer radical polymerization (ATRP) in various dispersed media to generate stable, multiple functional polymeric nanostructures. Recent research progress on extension of ATRP to economically viable and environmentally benign disperse media is discussed in the introductory chapter. Chapter II described the synthesis of amphiphilic block copolymers and hydrophilic polymers with ATRP initiating sites at the chain end and use of these macroinitiators as stabilizers (inisurf) for miniemulsion ATRP. In Chapter III and IV, monomer based reactive surfactants (surfmer) were used for ATRP under either emulsion or dispersion polymerization conditions. Stable polymer particles with cationic charge or steric stabilizers covalently attached to the surfaces were obtained. Chapter V discussed the generation of cross-linked network structure through copolymerization of monomer and divinyl cross-linker under homogeneous conditions. The cross-linking chemistry was then extended in Chapter VI for the synthesis of functional polymeric nanocapsules through interfacial confined copolymerization of monomer and cross-linker. Chapter VII introduced a simple and general method for synthesis of uniform star polymers in aqueous dispersed media. Generation of a micelle-like structure is an important step for the formation of uniform star polymers. In Chapter VIII, ATRP was introduced to a new dispersed polymerization media, inverse microemulsion. Preparation of small hydrophilic polymer latexes and hydrogel nanoparticles with size below 100 nm was described. Chapter IX presented the use of high internal phase emulsion as a template for the preparation of porous materials with hydroxide groups on the interface and their potential application for capture and release of atmospheric CO2.