Date of Award

5-2024

Degree Type

Dissertation

Degree Name

Doctor of Philosophy (PhD)

School

Polymer Science and Engineering

Committee Chair

Yoan C. Simon

Committee Chair School

Polymer Science and Engineering

Committee Member 2

Tristan D. Clemons

Committee Member 2 School

Polymer Science and Engineering

Committee Member 3

Sarah E. Morgan

Committee Member 3 School

Polymer Science and Engineering

Committee Member 4

Sergei I. Nazarenko

Committee Member 4 School

Polymer Science and Engineering

Committee Member 5

Derek L. Patton

Committee Member 5 School

Polymer Science and Engineering

Abstract

Dynamically bonded polymers are a class of materials which have garnered significant interest in recent years for their unique properties and potential applications. These polymers contain exchangeable linkages, thereby allowing for the long-range reorganization of polymer architectures within a given material. Extensive work has been done to develop novel strategies for incorporating covalent and non-covalent dynamic linkages into polymeric materials. This dissertation examines both dynamic covalent and non-covalently bound polymers, with a focus on understanding the emergent material properties that arise through dynamic exchange. A general overview of dynamic chemistries and their applications to polymer science is given in Chapter I. Chapter II discusses the design and synthesis of morpholin-2-one functionalized poly(norbornenes) and their application as reactive handles for single and double polymer modification. We provide in-depth kinetics studies to demonstrate the selective reactivity of morpholin-2-one with primary aliphatic amines, and further show that the latent alcohol group can be used as a second reactive site to for double modification of polymer chains. Finally, we present a one-pot approach to synthesize doubly grafted polymer architectures from monomeric starting materials. Chapter III focuses on the use of imidazolium sulfonate zwitterions as a non-covalent binding motif for supramolecular polymer networks. Herein, we report a trifunctional zwitterion, which form low molecular weight supramolecular glasses due to strong dipole-dipole interactions between zwitterionic dipoles. In chapter IV, we present photopolymerizable diketoenamine vitrimers utilizing bis-hydroxyamine crosslinkers as a model system to explore the role of crosslinker choice in controlling the topology- iii freezing temperature of triketone-based vitrimers. Finally, Chapter V provides a concise summary of our work and offers some future directions to pursue.

ORCID ID

0000-0002-7333-9182

Available for download on Monday, December 31, 2029

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