Metal-Free Photoinitiated, Controlled Cationic Polymerization of Vinyl Ethers Using Organic Iodides

Metal-free cationic polymerization enables the preparation of polymers without residual metal contamination, eliminating the need for additional purification. Here, a metal-free photoinitiating polymerization of isobutyl vinyl ether (IBVE) was developed using organic iodide as the initiator precursor. PIBVE with controlled molecular weight and narrow molecular weight distribution (Đ < 1.10) was successfully obtained. The polymerization kinetics demonstrated a controlled reaction, and in situ chain extension was demonstrated. In addition, we introduced a latent initiator strategy, allowing to control the generation process of the initiator through adjustment of the light source and providing a facile way to tune the MWD of the obtained polymer.