Photoorganocatalyzed Divergent Reversible‐Deactivation Radical Polymerization towards Linear and Branched Fluoropolymers

Topology influences the properties and applications of polymers. Consequently, considerable efforts have been made to control topological structures. In this work, we have developed a photoorganocatalyzed divergent synthetic approach based on reversible-deactivation radical polymerization (RDRP) that enables the preparation of both linear and branched fluoropolymers of low dispersity (Ð), a tunable degree of branching and high chain-end fidelity by exposure to LED light irradiation under metal-free conditions. This method promotes the generation of complicated structures (e.g., necklace-like and mop-like fluoropolymers) via chain-extension photo-RDRP, and provides a novel and versatile platform to access fluoropolymer electrolytes with high Li-ion transference number and good ionic conductivity, which should create improved opportunities for advanced material engineering.