| Recent advances in polymer chemistry have been driven by new synthetic strategies and a growing demand for complex, functional, and well-defined materials for applications ranging from coatings to biomaterials. The discovery of controlled radical polymerization has considerably broadened the scope of the polymer chemist in recent years. This dissertation details the design, synthesis, and characterization of novel macromolecules prepared by reversible addition-fragmentation chain transfer (RAFT) polymerization. In Chapter 2, a facile synthesis route to thiol-functionalized alpha,o-telechelic polymers using difunctional chain transfer agents (CTAs) and RAFT polymerization is described. The synthetic methodology is generalized and potentially applicable to a range of monomers. These thiol telechelics were developed as a model system to study the formation of multiply bound polymer chains (MBPCs) or "polymer loops" on surfaces as a novel method for interfacial modification as discussed in Chapter 3. Various factors affecting the formation of the "looped" polymer conformation were elucidated including molecular weight. The presence of polymer loops on the surface greatly affected the adsorption kinetics and viscoelastic properties of the resulting films. In Chapter 4, the RAFT technique was utilized in the preparation of reactive telechelics or macromonomers containing norbornene, vinyl, and cinnamate functional groups at one terminus. These macromolecules represent important precursors for more complex polymeric architectures such as comb and network polymers. Finally, in Chapter 5, a new synthetic strategy for the preparation of dendritic-linear block copolymers is demonstrated using functional dendritic CTAs and RAFT polymerization. A series of dendritic CTAs were designed containing carbazole moieties at the periphery and a single dithioester functional group at the focal point. A detailed kinetic study was completed for the polymerization of various monomers in the presence of the dendritic CTAs. The resulting block copolymers undergo phase separation resulting in carbazole-rich domains which could be electropolymerized to give conjugated polymer networks. |
