Date of Award

7-2024

Degree Type

Dissertation

Degree Name

Doctor of Philosophy (PhD)

School

Polymer Science and Engineering

Committee Chair

Derek L. Patton

Committee Chair School

Polymer Science and Engineering

Committee Member 2

Jeffrey S. Wiggins

Committee Member 2 School

Polymer Science and Engineering

Committee Member 3

Olivia D. McNair

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

Xiaodan Gu

Committee Member 5 School

Polymer Science and Engineering

Committee Member 6

Yoan C. Simon

Abstract

Photodegradable polymer networks are attractive due to the precise spatiotemporal control and large-area applicability of light. Chemical linkages that enable these polymer networks to be photo-responsive, also hinder their applicability in ambient light. Photostable and photodegradable networks have recently been reported to overcome this challenge by combining other stimuli with light for degradation. We report the design of a network that responds to a simultaneous, dual stimulus for photodegradation. We design poly(thioether acetal) networks with benzylidene acetal moieties that are known to undergo β-scission in the presence of free thiols. By blocking these free thiols with a thermally labile protecting group, we harness the photostability of polymer networks with no free thiols at room temperature and the photodegradability of free thiols at elevated temperatures. In the process, we discover a transthioacetalization side-reaction with a previously unreported isocyanate catalyst that interferes with both the photopolymerization and photodegradation pathways. We propose and execute strategies to successfully overcome this side-reaction. Thus, reporting the synthesis of photopolymerized, photostable, photo-processable and photodegradable polymer networks.

ORCID ID

https://orcid.org/0000-0003-0343-0754

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