Construction of Well-Defined Redox-Responsive CO₂ -Based Polycarbonates: Combination of Immortal Copolymerization and Prereaction Approach

Due to the axial group initiation in traditional (salen)CoX/quaternary ammonium catalyst system, it is difficult to construct single active center propagating polycarbonates for copolymerization of CO₂ /epoxides. Here a redox-responsive poly(vinyl cyclohexene carbonate) (PVCHC) with detachable disulfide-bond backbone is synthesized in a controllable manner using (salen)CoTFA/[bis(triphenylphosphine)iminium, [PPN]TFA binary catalyst, where the axial group initiation is depressed by judiciously choosing 3,3'-dithiodipropionic acid as starter. While for those comonomers failing to obtain polycarbonate with unimodal gel permeation chromatography (GPC) curve, a versatile method is developed by combination of immortal copolymerization and prereaction approach, and functional aliphatic polycarbonates having well-defined architecture and narrow polydispersity can be prepared. The resulting PVCHC can be further functionalized with alkenes by versatile cross-metathesis reaction to tune the physicochemical properties. The combination of immortal polymerization and prereaction approach creates a powerful platform for controllable synthesis of functional CO₂ -based polycarbonates.