Metal-Free\nPhotoinitiated, Controlled Cationic Polymerization\nof Vinyl Ethers Using Organic Iodides

Metal-free cationic polymerization enables the preparation\nof polymers\nwithout residual metal contamination, eliminating the need for additional\npurification. Here, a metal-free photoinitiating polymerization of\nisobutyl vinyl ether (IBVE) was developed using organic iodide as\nthe initiator precursor. PIBVE with controlled molecular weight and\nnarrow molecular weight distribution (<i>Đ</i> <\n1.10) was successfully obtained. The polymerization kinetics demonstrated\na controlled reaction, and <i>in situ</i> chain extension\nwas demonstrated. In addition, we introduced a latent initiator strategy,\nallowing to control the generation process of the initiator through\nadjustment of the light source and providing a facile way to tune\nthe MWD of the obtained polymer.