Defining Reactivity–Deconstructability Relationships for Copolymerizations Involving Cleavable Comonomer Additives
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Description
Accepted version
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1.16 MB
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Author(s)
Lundberg, David J
Ko, Kwangwook
Kilgallon, Landon J
Johnson, Jeremiah A
Date Issued
April 16, 2024
Journal
ACS Macro Letters
Publisher
American Chemical Society
Citation
David J. Lundberg, Kwangwook Ko, Landon J. Kilgallon, Jeremiah A. Johnson; Defining Reactivity–Deconstructability Relationships for Copolymerizations Involving Cleavable Comonomer Additives. ACS Macro Lett. 21 May 2024; 13 (5): 521–527.
Version
Author's final manuscript
Abstract
The incorporation of cleavable comonomers as additives into polymers can imbue traditional polymers with controlled deconstructability and expanded end-of-life options. The efficiency with which cleavable comonomer additives (CCAs) can enable deconstruction is sensitive to their local distribution within a copolymer backbone, which is dictated by their copolymerization behavior. While qualitative heuristics exist that describe deconstructability, comprehensive quantitative connections between CCA loadings, reactivity ratios, polymerization mechanisms, and deconstruction reactions on the deconstruction efficiency of copolymers containing CCAs have not been established. Here, we broadly define these relationships using stochastic simulations characterizing various polymerization mechanisms (e.g., coltrolled/living, free-radical, and reversible ring-opening polymerizations), reactivity ratio pairs (spanning 2 orders of magnitude between 0.01 and 100), CCA loadings (2.5% to 20%), and deconstruction reactions (e.g., comonomer sequence-dependent deconstruction behavior). We show general agreement between simulated and experimentally observed deconstruction fragment sizes from the literature, demonstrating the predictive power of the methods used herein. These results will guide the development of more efficient CCAs and inform the formulation of deconstructable materials.
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DOI of Published Version
https://doi.org/10.1021/acsmacrolett.4c00106
