Nat Commun. 2022 Jun 24;13(1):3621. doi: 10.1038/s41467-022-31359-4.
Photo-controlled living polymerization has received great attention in recent years. However, despite the great success therein, the report on photo-controlled living cationic polymerization has been greatly limited. We demonstrate here a novel decolorable, metal-free and visible light-controlled living cationic polymerization system by using tris(2,4-dimethoxyphenyl)methylium tetrafluoroborate as the photocatalyst and phosphate as the chain transfer agent (CTA) for polymerization of 4-methoxystyrene. This polymerization reaction under green LED light irradiation shows clear living characteristics including predictable molar mass, low molar-mass dispersity (Đ = 1.25), and sequential polymerization capability. In addition, the photocatalytic system exits excellent “on-off” photo switchability and shows the longest “off period” of 36 h up to now for photo-controlled cationic polymerization. Furthermore, the residual photo-catalyst is easily deactivated and decolored with addition of a base after the polymerization. The present study has extended the photo-controlled living cationic polymerization systems with new organic photocatalysts, phosphate CTA and polymerizable monomer as well as the new properties of excellent photostability and in-situ decolored capacity.