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Hydrogen fluoride (HF) is a versatile reagent for material transformation, with applications in self-immolative polymers, remodeled siloxanes, and degradable polymers. The responsive in situ generation of HF in materials therefore holds promise for new classes of adaptive material systems. Here, we report the mechanochemically coupled generation of HF from alkoxy-gem-difluorocyclopropane (gDFC) mechanophores derived from the addition of difluorocarbene to enol ethers. Production of HF involves an initial mechanochemically assisted rearrangement of gDFC mechanophore to α-fluoro allyl ether whose regiochemistry involves preferential migration of fluoride to the alkoxy-substituted carbon, and ab initio steered molecular dynamics simulations reproduce the observed selectivity and offer insights into the mechanism. When the alkoxy gDFC mechanophore is derived from poly(dihydrofuran), the α-fluoro allyl ether undergoes subsequent hydrolysis to generate 1 equiv of HF and cleave the polymer chain. The hydrolysis is accelerated via acid catalysis, leading to self-amplifying HF generation and concomitant polymer degradation. The mechanically generated HF can be used in combination with fluoride indicators to generate an optical response and to degrade polybutadiene with embedded HF-cleavable silyl ethers (11 mol %). The alkoxy-gDFC mechanophore thus provides a mechanically coupled mechanism of releasing HF for polymer remodeling pathways that complements previous thermally driven mechanisms.
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Selective Electrocatalytic Degradation of Ether‐Containing Polymers
Abstract Leveraging electrochemistry to degrade robust polymeric materials has the potential to impact society's growing issue of plastic waste. Herein, we develop an electrocatalytic oxidative degradation of polyethers and poly(vinyl ethers) via electrochemically mediated hydrogen atom transfer (HAT) followed by oxidative polymer degradation promoted by molecular oxygen. We investigated the selectivity and efficiency of this method, finding our conditions to be highly selective for polymers with hydridic, electron‐rich C−H bonds. We leveraged this reactivity to degrade polyethers and poly(vinyl ethers) in the presence of polymethacrylates and polyacrylates with complete selectivity. Furthermore, this method made polyacrylates degradable by incorporation of ether units into the polymer backbone. We quantified degradation products, identifying up to 36 mol % of defined oxidation products, including acetic acid, formic acid, and acetaldehyde, and we extended this method to degrade a polyether‐based polyurethane in a green solvent. This work demonstrates a facile, electrochemically‐driven route to degrade polymers containing ether functionalities.
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- Award ID(s):
- 2203758
- PAR ID:
- 10479553
- Publisher / Repository:
- Wiley Blackwell (John Wiley & Sons)
- Date Published:
- Journal Name:
- Angewandte Chemie International Edition
- Volume:
- 63
- Issue:
- 3
- ISSN:
- 1433-7851
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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