Radical promoted cationic RAFT polymerization by photo electron transfer reaction†

The application of cationic RAFT polymerization in photocuring has enabled the fabrication of stimuli-responsive materials. However, these systems mainly rely on UV light, limiting their broader application. Herein, we developed a radical promoted cationic RAFT (RPC-RAFT) polymerization system utilizing a photoredox catalyst via a photo electron transfer reaction, extending the usable light wavelength to blue and red light. The well-defined polymerization of various vinyl ethers was achieved with controlled molecular weights and narrow molecular weight distributions. Moreover, we achieved successful photocuring using this system for the polymerization of a bifunctional vinyl ether monomer, offering a convenient approach for in-depth photocuring.