Titanium-Catalyzed Defluorination of Poly(Vinyl Fluoride) and Poly(Vinylidene Fluoride) Under Friedel-Crafts Conditions.

Authors

Louis Le Moigne, Marie Sircoglou, Quentin Bonnin, Marie-José Penouilh, Joan Vignolle, Etienne Grau, Cédric Le Coz, Mélanie Bousquet, Paul Fleurat-Lessard, Adrien T Normand

Published in

Angewandte Chemie (International ed. in English). Pages e4183926. Aug 23, 2026. Epub Aug 23, 2026.

Abstract

The defluorination of poly(vinyl fluoride) (PVF) and poly(vinylidene fluoride) (PVDF) fluoropolymers catalyzed by titanium species in the presence of triethylsilane (Et₃SiH) and aromatic solvents is reported. Commercially available Ti complexes (e.g., [Cp₂TiCl₂] (Ti3) or [CpTiCl₃] (Ti5); Cp = η⁵-C₅H₅) activated by the silylium reagent [(Et₃Si)₂H](B(C₆F₅)₄) (Si⁺) defluorinate PVF and PVDF with turnover frequencies (TOF) of up to 3.7 h^-1, affording copolymers with low residual fluorine content (down to 0.8%). The obtained polymers were characterized by multiple techniques including solid-state nuclear magnetic resonance (NMR) and Fourier-transform Infrared (FTIR) spectroscopies, combustion ion chromatography (CIC), differential scanning calorimetry (DSC) and gel permeation chromatography (GPC). Density functional theory (DFT) calculations conducted in bromobenzene on 2-fluoropropane as a model indicate that the turnover-limiting step is the concerted fluoride abstraction (by Ti)/hydride transfer (by Et₃SiH).

PMID:
42633661
Bibliographic data and abstract were imported from PubMed on 24 Aug 2026.

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