Thiol-triggered deconstruction of bifunctional silyl ether terpolymers via an SNAr-triggered cascade
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d3sc02868b.pdf
Description
Published version
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3.15 MB
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Author(s)
Brown, Christopher M
Husted, Keith EL
Wang, Yuyan
Kilgallon, Landon J
Shieh, Peyton
Zafar, Hadiqa
Lundberg, David J
Johnson, Jeremiah A
Date Issued
August 2, 2023
Journal
Chemical Science
Publisher
Royal Society of Chemistry
Citation
Christopher M. Brown, Keith E. L. Husted, Yuyan Wang, Landon J. Kilgallon, Peyton Shieh, Hadiqa Zafar, David J. Lundberg, Jeremiah A. Johnson; Thiol-triggered deconstruction of bifunctional silyl ether terpolymers via an SNAr-triggered cascade. Chem. Sci. 2023; 14 (33): 8869–8877.
Version
Final published version
Abstract
While Si-containing polymers can often be deconstructed using chemical triggers such as fluoride, acids, and bases, they are resistant to cleavage by mild reagents such as biological nucleophiles, thus limiting their end-of-life options and potential environmental degradability. Here, using ring-opening metathesis polymerization, we synthesize terpolymers of (1) a “functional” monomer (e.g., a polyethylene glycol macromonomer or dicyclopentadiene); (2) a monomer containing an electrophilic pentafluorophenyl (PFP) substituent; and (3) a cleavable monomer based on a bifunctional silyl ether ðSiR2ðOR0
2ÞÞ. Exposing these polymers to thiols under basic conditions triggers a cascade of nucleophilic aromatic substitution (SNAr) at the PFP groups, which liberates fluoride ions, followed by cleavage of the backbone Si–O bonds, inducing polymer backbone deconstruction. This method is shown to be effective for deconstruction of polyethylene glycol (PEG) based graft terpolymers in organic or aqueous conditions as well as polydicyclopentadiene (pDCPD) thermosets, significantly expanding upon the versatility of bifunctional silyl ether based functional polymers.
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DOI of Published Version
https://doi.org/10.1039/d3sc02868b
