A Versatile Strategy to Synthesize Perfluoropolyether-Based Thermoplastic Fluoropolymers by Alkyne-Azide Step-Growth Polymerization

Perfluoropolyether (PFPE)‐based thermoplastic fluoropolymers are synthesized by A2 + B2 step‐growth polymerization between PFPE‐diyne and fluorinated diazides. This versatile method allows synthesizing PFPE‐based materials with tunable physicochemical properties depending on the exact nature of the fluorinated segment of the diazide precursor. Semicrystalline or amorphous materials endowed with high thermostability (≈300 °C under air) and low glass transition temperature (≈−100 °C) are obtained, as confirmed by differential scanning calorimetry, thermogravimetry, and rheometry. Step‐growth polymerizations can be copper‐catalyzed but also thermally activated in some cases, thus avoiding the presence of copper residues in the final materials. This strategy opens up new opportunities to easily access PFPE‐based materials on an industrial scale. Furthermore, a plethora of developments can be envisioned (e.g., by adding a third trifunctional component to the formulations for the synthesis of PFPE‐based elastomers). Perfluoropolyether‐based thermoplastic polymers exhibiting low glass transition temperature (≈−100 °C) are synthesized either by copper‐catalyzed or by thermally‐activated A2 + B2 alkyne‐azide step‐growth polymerization. By tuning the structure of the fluorinated segment of the diazide precursor, semicrystalline or amorphous materials endowed with high thermostability (≈300 °C under air) can be obtained.