Issue 33, 2023

Thiol-triggered deconstruction of bifunctional silyl ether terpolymers via an SNAr-triggered cascade

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 Image ID:d3sc02868b-t1.gif. 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.

Graphical abstract: Thiol-triggered deconstruction of bifunctional silyl ether terpolymers via an SNAr-triggered cascade

Supplementary files

Article information

Article type
Edge Article
Submitted
06 Jun 2023
Accepted
12 Jul 2023
First published
02 Aug 2023
This article is Open Access

All publication charges for this article have been paid for by the Royal Society of Chemistry
Creative Commons BY-NC license

Chem. Sci., 2023,14, 8869-8877

Thiol-triggered deconstruction of bifunctional silyl ether terpolymers via an SNAr-triggered cascade

C. M. Brown, K. E. L. Husted, Y. Wang, L. J. Kilgallon, P. Shieh, H. Zafar, D. J. Lundberg and J. A. Johnson, Chem. Sci., 2023, 14, 8869 DOI: 10.1039/D3SC02868B

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