Frontally Fabricated Fluoropolymers

Abstract Fluoropolymers are ubiquitous in modern technologies owing to their exceptional thermal, chemical, and environmental durability. However, these properties often come at the expense of synthetic severity and recyclability. Here, we report the preparation of semi-fluorinated thermosets and thermoplastics via frontal ring-opening metathesis polymerization (FROMP), enabling rapid synthesis with minimal external energy input and no post-polymerization processing. Fluorinated monomers were prepared from pentafluoropyridine (PFP), whose activated heteroaromatic scaffold enables regioselective nucleophilic aromatic substitution with norbornene-derived nucleophiles. Alcohol-derived monomers intrinsically favored multifunctional reactivity and network formation, whereas 5-norbornene-2-methylamine formed a resonance-stabilized anilide adduct that suppressed further substitution. The resulting amine-linked fluoropolymers displayed linear architectures, favorable mechanical properties despite lacking covalent crosslinks, and improved prospects for reprocessability. Collectively, these studies position FROMP as a promising platform for more sustainable fluoropolymer manufacturing and end-of-life management.