Near-Infrared, Light-Induced Cationic and Radical RAFT Polymerization Catalyzed by Iron Complex

A near-infrared (NIR) light induced controlled cationic polymerization is presented here. The halide abstraction reaction between the cyclo-pentadienyl iron dicarbonyl dimer (Fe-2(Cp)(2)(CO)(4)) and an organic halide is utilized to generate initial radicals or cations under mild conditions, which can be further combined with both radical and cationic reversible addition-fragmentation chain transfer (RAFT) polymerization. Well-defined poly(vinyl ether)s and polyacrylates are prepared successfully under NIR light by this method. The excellent penetration ability of NIR light through thick barriers has been verified by polymerization in the presence of an A4 paper. In addition, iron-based radical polymerization has been used for three-dimensional (3D) printing to fabricate materials with different thicknesses.