Controlled Radical Copolymerization of Hydrofluoroolefin 2,3,3,3‐Tetrafluroropropene (R1234yf) via Thermally Activated Delayed Fluorescence Catalysis

Abstract The transformation of hydrofluoroolefins (HFOs) into value‐added materials represents an important strategy for sustainable fluorocarbon utilization. Here, we designed a thermally activated delayed fluorescence (TADF) photocatalyst based on 3,5‐difluorobenzonitrile core, which has presented high reduction potential (−1.86 V versus SCE), prolonged lifetime ( τ TADF = 31.02 µs) and high quantum yield after excitation. The TADF catalyst facilitated oxidative quenching with a xanthate chain‐transfer agent, enabling visible‐light controlled radical copolymerization of 2,3,3,3‐tetrafluoropropene ( R1234yf ) at ppm levels of catalyst usage under ambient conditions. The copolymerization furnished good control across various unconjugated comonomers (vinyl esters, vinyl amides), yielding HFO‐embedded chains with tunable molecular weights, controlled dispersities and good chain‐end fidelity. Furthermore, this versatile synthetic approach promoted on‐demand construction of complex block architectures through chain‐extension polymerization. After hydrolysis, the obtained amphiphilic chains exhibited outstanding performance as superhydrophobic coatings on diverse substrates, and surfactants in emulsion polymerization, supporting practical potentials of HFO‐based copolymers. This work establishes a versatile platform to access well‐defined R1234yf copolymers, creating opportunities to address both HFO‐transformation concern and growing demand for high‐performance fluoropolymers.