Date of Award

Spring 3-2023

Degree Type

Dissertation

Degree Name

Doctor of Philosophy (PhD)

School

Polymer Science and Engineering

Committee Chair

Yoan Simon

Committee Chair School

Polymer Science and Engineering

Committee Member 2

Derek Patton

Committee Member 2 School

Polymer Science and Engineering

Committee Member 3

Sarah Morgan

Committee Member 3 School

Polymer Science and Engineering

Committee Member 4

Robson Storey

Committee Member 4 School

Polymer Science and Engineering

Committee Member 5

Xiaodan Gu

Committee Member 5 School

Polymer Science and Engineering

Abstract

Bottlebrush polymers have garnered interest in many disciplines for their unique structure-property characteristics and potential applications. These polymers typically exhibit extended rodlike conformations as a result of sterically crowded side-chains. Further, extensive work has focused on expanding the synthetic toolbox for these systems, resulting in excellent molecular weight control, diverse functional group utility and corresponding stimuli-responsive behaviors. This dissertation examines both synthetic and stimuli-responsive tools in the context of bottlebrush systems.

A broad overview of bottlebrush characteristics, synthesis, and applications is discussed in CHAPTER I. CHAPTER II focuses on the use of a chain-transfer agent in the ring-opening metathesis polymerization of bottlebrush polymers to generate novel α, ω-telechelic bottlebrushes. In-depth kinetic studies showed bottlebrushes exhibit slightly slower chain transfer than linear analogues and chain-transfer agent sterics play a significant role in reaching quantitative conversion. Further, bottlebrushes with polymerizable end-groups were chain extended with atom transfer radical polymerization to generate linear-block-bottlebrush-block-linear copolymers. In CHAPTER III, three different systems of bottlebrushes with o-nitrobenzene-based, photocleavable side-chains were explored to elucidate the backbone molecular weight after photoscission to mixed success. In CHAPTER IV, an amphiphilic, diblock bottlebrush system with photocleavable side-chains demonstrated spatiotemporal control after aqueous self-assembly. Finally, in CHAPTER V, a brief overview and future outlook of the dissertation is presented.

ORCID ID

0000-0002-0607-8664

Available for download on Friday, March 07, 2025

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