Polymer Backbone Metamorphosis Through Sigmatropic Rearrangements
Abstract
Post-synthetic modification is a powerful strategy to access a broad scope of materials properties from a small number of polymer scaffolds. Thus far, the paradigm in this field has been to append a moiety to the polymer or modify its side-chains or end-groups Ñprocesses, whose effects are inherently limited by the chemical fragments to be installed. On the other hand, relatively little attention has been devoted to altering the very core of the polymerÑits backbone composition. Yet, the ability to carry out such polymer backbone metamorphosis (PBM)Ñe.g., conversion of a polyester to a polyolefinÑwould produce dramatic changes in materialsÕ properties (e.g., glass transition temperature, crystallinity, ion-conductivity, degradability) with little chemical input beyond a desired stimulus. Moreover, PBM can grant entry to entirely new, previously inaccessible polymer scaffolds and, conversely, advance the sophistication of retrosynthetic analysis practiced in polymer chemistry. Thus, the central objective of the proposed research is to advance PBM as a novel and powerful strategy to modify polymer properties on demand. To that end, we aim to take advantage of a class of reactions called sigmatropic rearrangementsÑa vast set of transformations well-studied in the context of small molecules, but virtually unexplored in the context of polymer scaffolds. By gating the PBM with an orthogonal chemical or physical trigger, we also aim to demonstrate that PBM can serve as a versatile mechanism of stimulus responseÑa feature with fundamental significance for such applications as sensors and artificial actuators. Lastly, we aim to demonstrate that PBM can be applied to commodity polymers, eliciting unprecedented properties from classical materials.
Document Details
- Document Type
- DoD Grant Award
- Publication Date
- Jul 27, 2023
- Source ID
- W911NF2310265
Entities
People
- Aleksandr V Zhukhovitskiy
Organizations
- Army Contracting Command
- United States Army
- University of North Carolina at Chapel Hill