Date of Award

Summer 6-2023

Degree Type


Degree Name

Doctor of Philosophy (PhD)


Polymer Science and Engineering

Committee Chair

Dr. Derek L Patton

Committee Chair School

Polymer Science and Engineering

Committee Member 2

Dr. Zhe Qiang

Committee Member 2 School

Polymer Science and Engineering

Committee Member 3

Dr. Yoan C Simon

Committee Member 3 School

Polymer Science and Engineering

Committee Member 4

Dr. Tristan Clemons

Committee Member 4 School

Polymer Science and Engineering

Committee Member 5

Dr. Jeffrey S. Wiggins

Committee Member 5 School

Polymer Science and Engineering


Polymer modification is crucial for developing new properties and materials from recalcitrant waste polymers. Synthetically, polymers possess a chemical inertness that renders their functionalization challenging. Specifically, the omnipresence of C–H bonds in all commercial polymers endows their chemical resistance. Thus, developments in C–H activation chemistry are crucial to polymer diversification processes and allow for fundamental insight into the role of material processing conditions on novel chemical reactions. Au(I)-chemistry has recently come to the fore owing to a unique chemical reactivity nonexistent with other transition metals. The alkynophilicity of Au(I), in tandem with their insensitivity to common polymer processing conditions (air, water, functional group tolerance, wide temperature range, etc.), renders Au(I) a particularly potent polymer modification catalyst. Despite the utility of Au(I), few reports take advantage of its utility.

The work reported in this dissertation outlines the design principles for Au(I) catalysis in polymer modification and the subsequent limitations and advantages engendered. The development of novel Au(I) catalyzed hydoarylation, hydroamination, and hydroalkoxylation reactions described herein enable the synthesis of novel aromatic polymers, polyimines, and polyethers while providing fundamental insight into the role of catalyst, cocatalyst, and reaction medium. Chapter I details the overall objectives and principles of polymer modification, the chemical concepts of C–H activation and how they apply to polymer modification, and the fundamental aspects of Au(I) catalysis. Chapter II describes the synthetic methodologies, materials, and methods discovered during the course of this work. Chapter III describes the hydorarylation of aromatic polymers with non-activated alkynes, the subsequent side-reactions, limitations of Au(I)-catalyzed hydroarylation, and the new polymer methodologies. Chapter IV describes the novel Au(I)-catalyzed hydroarylation of α-olefins, the key limitation to commercial catalysts, surprising regiochemistry with PSU and PET, and the unexpected leaving group-assisted Heck-type reactivity towards fully CH crosslinked PS.



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