Catalyst development in atom transfer radical polymerization from a thermodynamic perspective

Mechanistic innovations concerning catalyst development in atom transfer radical polymerization (ATRP) are discussed from a thermodynamic perspective. A thorough discussion of competitive equilibria that can affect catalyst performance is provided in the introductory chapter. In Chapter II, a model representing ATRP catalyst activity as the product of three distinct thermodynamic contributions is rigorously evaluated, including the reduction/oxidation of both the metal complex and the halogen atom, as well as the affinity of the catalyst for halide anions (or "halidophilicity"). Rules for catalyst selection at low catalyst concentrations are a major focus of the third chapter, and several new highly active and highly stable catalysts are developed for use in such systems. In Chapter IV, several Os complexes are developed as exceptionally halidophilic and active/powerful ATRP catalysts. Significant attention is also provided to the interplay of Os catalyzed ATRP and Os mediated organometallic radical polymerization. Several strategies are implemented in Chapter V to enhance control of ATRP in protic media for the basic/coordinating monomer 4-vinylpyridine, the neutral but protic monomer 2-hydroxethyl methacrylate, and the acidic monomers acrylic and methacrylic acid. The final Chapter is an investigation of how relative propagation rates of several polar and non-polar monomers are affected through it-coordination of the vinyl monomer with Cu 1 complexes. The effect monomer coordination has on ATRP catalyst performance is also examined.