Controlled Radical Copolymerization toward Tailored F/N Hybrid Polymers by Using Light‐Driven Organocatalysis

Abstract Controlled radical copolymerizations present attractive avenues to obtain polymers with complicated compositions and sequences. In this work, we report the development of a visible‐light‐driven organocatalyzed controlled copolymerization of fluoroalkenes and acyclic N ‐vinylamides for the first time. The approach enables the on‐demand synthesis of a broad scope of amide‐functionalized main‐chain fluoropolymers via novel fluorinated thiocarbamates, facilitating regulations over chemical compositions and alternating fractions by rationally selecting comonomer pairs and ratios. This method allows temporally controlled chain‐growth by external light, and maintains high chain‐end fidelity that promotes facile preparation of block sequences. Notably, the obtained F/N hybrid polymers, upon hydrolysis, afford free amino‐substituted fluoropolymers versatile for post modifications toward various functionalities (e.g., amide, sulfonamide, carbamide, thiocarbamide). We further demonstrate the in situ formation of polymer networks with desirable properties as protective layers on lithium metal anodes, presenting a promising avenue for advancing lithium metal batteries.