Modular and Processable Fluoropolymers Prepared via a Safe, Mild, Iodo–Ene Polymerization

[Image: see text] Fluoropolymers have infiltrated society as coatings and insulators. However, low processability, few opportunities for polymer functionalization, and explosive monomers hampering academic investigation of these materials have precluded the extension of the unique properties of perfluorocarbons to the cutting edge of material science. Here, we present semifluorinated iodo–ene polymers as a scaffold to overcome fluoropolymer limitations. A sodium dithionate initiated polymerization of perfluorodiiodides and dienes allows for high-molecular-weight polymers (>100 kDa) to be prepared in the presence of oxygen and water with up to 59 wt % fluorine content. These conditions are sufficiently mild to enable the polymerization of functional dienes, leading to biodegradable fluoropolymers. The iodo–ene polymerization results in the addition of polarizable iodine atoms, which improve polymer processability; yet, these atoms can be removed after processing for enhanced stability. Displacement of the iodine atoms with thiols or azides facilitates covalent surface modification and cross-linking. Finally, the low bond dissociation energy of the C–I bond allows allyl group addition as well as photo-cross-linking. Collectively, the simple synthesis and modular nature of the semifluorinated iodo–ene polymers will enable the convergence of perfluorocarbons and advanced materials.