Mechanically Triggered Polymer Deconstruction through Mechanoacid Generation and Catalytic Enol Ether Hydrolysis

Hu, Yixin; Lin, Yangju; Craig, Stephen L.

doi:10.1021/jacs.3c10153

Cited by 6 publications

(2 citation statements)

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“…Schematic representation of previously reported mechanophores ,,,, and the mechanical release of hydrogen fluoride reported in this work.…”

Section: Introductionmentioning

confidence: 99%

“…Mechanochemistry has been widely applied in various contexts, including mechanochromic materials, − mechanocatalysis, , unlocking otherwise inaccessible reactions, − small molecule release, − and to enhance the mechanical properties of networks integrated with mechanophores. , Among these applications, the mechanically triggered release of acid is useful for a rich range of responses, including acid-induced polymer degradation, − polymerization, and hydrogel actuators. − The concept of a mechanochemically generated acid was first reported by Diesendruck et al using a gem -dichlorocyclopropanated ( g DCC) indene (Figure ), which was followed by a more thermally stable, but scissile, design based on an oxime sulfonate mechanophore . More recently, some of us reported easily synthesized alkoxy-substituted g DCC mechanophores that readily release hydrochloric acid in a nonscissile fashion similar to the indene, but with improved thermal stabilitycombining some of the more attractive attributes of previous designs. , …”

Section: Introductionmentioning

confidence: 99%

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Self-Amplified HF Release and Polymer Deconstruction Cascades Triggered by Mechanical Force

Hu,

Wang,

Kevlishvili

et al. 2024

J. Am. Chem. Soc.

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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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“…Schematic representation of previously reported mechanophores ,,,, and the mechanical release of hydrogen fluoride reported in this work.…”

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Self-Amplified HF Release and Polymer Deconstruction Cascades Triggered by Mechanical Force

Hu,

Wang,

Kevlishvili

et al. 2024

J. Am. Chem. Soc.

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Polymer Degradation via a Mechanochemical Gating Strategy

Liang,

Qian

2024

Chin. J. Chem.

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The extensive use of plastics, valued for their lightweight, durability, and cost‐effectiveness, has led to severe environmental pollution, with 72% of plastic waste ending up in landfills or natural habitats. Traditional methods for plastic decomposition, including both mechanical and chemical approaches, often face challenges such as incomplete degradation and stability concerns. The innovative concept of mechanical gating presents a promising solution by incorporating mechanophores into polymer structures, enabling controlled degradation. Recent advancements have focused on utilizing mechanophores, such as cyclobutane, as "door locks" to regulate the degradation process. This perspective highlights recent progress in this field, demonstrating the potential of mechanophore‐based strategies for achieving on‐demand polymer degradation. It addresses the limitations of conventional recycling methods and explores how this approach can balance polymer stability with environmental degradability, paving the way for more sustainable plastic management solutions.Early Day Record

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Notizen aus der Chemie

Calvino,

Dierkes,

Heine

et al. 2024

Nachr Chem

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Notizen aus der ChemieKunststoffadditive im Hausstaub | | Hindered Amine Light Stabilizers (HALSs) sind wichtige, aber toxische Kunststoffadditive. Ihr Einsatz in Kunststoffprodukten mit direktem Lebensmittel-oder Menschenkontakt ist stark reguliert. Über indirekte Expositionsrisiken, beispielsweise durch Hausstaub oder Luft, ist bisher jedoch wenig bekannt.Deng und Team haben Staub-und Luftproben aus Südchina mit LC-MS/MS auf neun monomere HALSs untersucht. Sie wiesen sieben der neun nach. Am häufigsten detektiert wurden Sebacinsäure-bis(2,2,6,6-tetramethyl-4-piperidyl)ester (Tinuvin 770) und 1,2,2,6,6-Pentamethyl-4-piperidyl-Sebacinsäuremethylester (HS-508).Die Mediane der Gehalte lagen im Staub bei 417 bis 8 830 ng•g -1 und in der Luft bei 28,6 bis 70,9 pg•m -3 . Die Gehalte im Staub lagen somit signifikant über denen von UV-Filtern, beispielsweise Benzotriazolen. HALSs werden demnach für künftige Umweltstudien bedeutend sein. GeD

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Mechanically Triggered Polymer Deconstruction through Mechanoacid Generation and Catalytic Enol Ether Hydrolysis

Cited by 6 publications

References 46 publications

Self-Amplified HF Release and Polymer Deconstruction Cascades Triggered by Mechanical Force

Self-Amplified HF Release and Polymer Deconstruction Cascades Triggered by Mechanical Force

Polymer Degradation via a Mechanochemical Gating Strategy

Notizen aus der Chemie

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