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Document Type

Open Access Dissertation

Degree Name

Doctor of Philosophy (PhD)

Degree Program

Polymer Science and Engineering

Year Degree Awarded

2017

Month Degree Awarded

February

First Advisor

Todd Emrick

Subject Categories

Polymer and Organic Materials

Abstract

This thesis describes new synthetic platforms for a series of functional polymeric materials containing hydrophilic and/or zwitterionic moieties as pendent groups. The hydrophilicity, biocompatibility, and degradability of these polymers hinged on innovative monomer designs and adaption of appropriate polymerization strategies including controlled radical polymerization, metathesis polymerization, and ring-opening polymerization. Novel, functional sulfobetaine polymers having functional groups (i.e, alkenes and alkynes) directly attached to the zwitterionic moieties were prepared and shown to stabilize oil-water interfaces, allowing for interfacial crosslinking to afford robust polymer capsules. This represents the first example of inserting functionality directly into the zwitterionic moieties of polymer zwitterions, allowing one to achieve a much greater extent of functionality than is possible in zwitterion-containing copolymers. Functional oil-in-water droplets presenting reactive functionalities at the oil-water interface were realized by inserting reactive functional groups (i.e, activated ester and catechol) into amphiphilic polymer surfactants containing a hydrophobic polyolefin backbone and pendent hydrophilic phosphorylcholine groups by ring-opening metathesis polymerization (ROMP). Efforts in manipulating polymer backbone structures led to the development of electronically active polymer zwitterions, affording first examples of polymer zwitterions with conjugated polyacetylene-like backbones synthesized by metathesis cyclopolymerization. Redox-responsive disulfides and hydrolyzable phosphoesters were integrated successfully into polyolefins by ROMP with cyclic olefins containing degradable groups, while functional copolyesters featuring pendent alkene and alkyne groups amendable for post-polymerization modification were synthesized by organocatalyzed ring-opening polymerization. Finally, a simple method to immobilize poly(phosphorylcholine methacrylate) onto various surfaces was developed by catecholamine chemistry, which afforded a versatile and robust route to antifouling coating that successfully resisted bacterial and oil fouling.

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