Off-campus UMass Amherst users: To download campus access dissertations, please use the following link to log into our proxy server with your UMass Amherst user name and password.

Non-UMass Amherst users: Please talk to your librarian about requesting this dissertation through interlibrary loan.

Dissertations that have an embargo placed on them will not be available to anyone until the embargo expires.

Author ORCID Identifier

https://orcid.org/0000-0002-9946-3923

AccessType

Open Access Dissertation

Document Type

dissertation

Degree Name

Doctor of Philosophy (PhD)

Degree Program

Polymer Science and Engineering

Year Degree Awarded

2022

Month Degree Awarded

September

First Advisor

Todd Emrick

Subject Categories

Polymer Chemistry

Abstract

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.

DOI

https://doi.org/10.7275/31043730

Share

COinS