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Author ORCID Identifier


Open Access Dissertation

Document Type


Degree Name

Doctor of Philosophy (PhD)

Degree Program

Polymer Science and Engineering

Year Degree Awarded


Month Degree Awarded


First Advisor

Todd Emrick

Subject Categories

Polymer Chemistry


This dissertation encompasses the synthesis, characterization and application of novel polymer zwitterions that significantly expand the library of available zwitterionic polymers. Their facile synthesis is facilitated by the preparation of a novel functional sultone precursor molecule, which can be ring-opened by commercially available phosphine, amine and sulfide nucleophiles, affording phosphonium, ammonium or sulfonium sulfonate monomers, respectively. Most notably, this work describes the invention of phosphonium-based polymer zwitterions, establishing a new class of zwitterionic polymer structures with unique solution and interfacial properties. Furthermore, the incorporation of these phosphonium sulfonates into block copolymer architectures with conventional polymer zwitterions, and the resulting switchable solution assemblies, are described. Additionally, this work compares the novel phosphonium and ammonium sulfonate polymers, elucidating key structure-property relationship information on the effect of the identity of the cation-bearing atom on material properties, such as solution behavior and surface activity. Finally, the novel sulfonium sulfonate polymers, compared to analogous, ix previously established sulfothetin polymer zwitterions, display significant differences in their solubility, surface activity and stability, which may be attributed to their respective strength of inter-zwitterion interactions.