Synthesis, Characterization, and Polymerization of Tetrakis(dialkylamino)phosphonium Cations

Precise macromolecular engineering has led to tremendous advances in the design of nextgeneration materials. This has been largely due to significant synthetic efforts controlling the polymerization process to afford polymers with predictable molecular weights, compositions, narrow molecular weight distributions, high chain-end fidelity, and unique architectures. Polyelectrolytes and ionomers are a unique class of polymers that bear formal charges either
directly within or tethered to the polymer backbone. Combining controlled/living polymer design principles with tunable electrostatic interactions provides access to a wide range of functional materials. One area these polymers are used in are for solid-state ion conducting membranes, which
are essential components in electrochemical devices such as fuel cells. Frontiers of fuel cell development involves crafting stable anion exchange membranes that
have high hydroxide conductivity and resist chemical decomposition due to the highly caustic nature of hydroxide. Understanding the fundamental decomposition pathways of the tethered cations is crucial for obtaining durable, long-lifetime materials. This dissertation details some of
our efforts towards elucidating the degradation pathways of one class of organophosphorus cation and its incorporation into well-defined polymers using controlled/living polymerization methods.