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

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.

Ionically Cross-Linked Polymers as Asymmetric Gel Polymer Electrolytes for Enhanced Cycle Performance of Lithium-Sulfur Batteries.

Two thermoplastic triblock copolymers of poly(ε-caprolactone)-based acidic (PCL-A) and basic (PCL-B) polymers are synthesized by atom transfer radical polymerization. PCL-A and PCL-B are sequentially electrospun on a sulfur electrode and then ionically cross-linked by an acid-base reaction via hot pressing at 70 °C, which is confirmed by infrared (IR) spectroscopy. The cross-linked PCL-A/PCL-B-electrospun sulfur electrode is assembled as a lithium-sulfur battery with an asymmetric gel polymer electrolyte. The cross-linked polymer is swollen by a liquid electrolyte to form an asymmetric gel polymer electrolyte. The cyclic voltammetry results indicate that the asymmetric gel polymer electrolyte can suppress the dissolution of lithium polysulfides (Li2Sn) into the electrolyte. Furthermore, the lithium-sulfur battery with the asymmetric gel polymer electrolyte exhibits enhanced cycle-life performance.