Chemiluminescence‐Induced Free Radical–Promoted Cationic Polymerization

Chemiluminescence (CL) has recently been featured as a new external light source for various photoinduced reactions with attractive features such as eliminating continuous energy supply and advanced light source setups. In the present study, the free‐radical‐promoted cationic polymerization of cyclohexene oxide, n‐butyl vinyl ether, and N‐vinyl carbazole under CL irradiation is described. The method is based on the visible‐light‐induced generation of electron donor radicals from bis‐(4‐methoxybenzoyl)diethyl germane (BAG), bis(2,4,6‐trimethylbenzoyl) phenyl phosphinate, and camphorquinone by CL illumination followed by electron transfer to diphenyl iodonium hexafluorophosphate (Ph2I+PF6−) to form corresponding cations capable of initiating cationic polymerization. The applicability of the process to network formation is also demonstrated by using a bifunctional monomer, tri(ethylene glycol) divinyl ether. A novel method for cationic polymerization initiated by the visible light emitted from a chemical reaction that uses inexpensive chemicals while overcoming continuous energy supply and advanced light source setups is developed. Visible light absorbed by the photoinitiators generates radicals that are oxidized to cations capable of initiating cationic polymerization of various monomers.