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.
Department Key Laboratory of Polymer Ecomaterials, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun, 130022, P. R. China.
Shunjie
S
Liu
Department Key Laboratory of Polymer Ecomaterials, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun, 130022, P. R. China.
Xun
X
Zhao
Department Key Laboratory of Polymer Ecomaterials, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun, 130022, P. R. China.
Hongchen
H
Guo
Department Key Laboratory of Polymer Ecomaterials, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun, 130022, P. R. China.
Yusheng
Y
Qin
Department Key Laboratory of Polymer Ecomaterials, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun, 130022, P. R. China.
Xianhong
X
Wang
Department Key Laboratory of Polymer Ecomaterials, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun, 130022, P. R. China.
Fosong
F
Wang
D002245:Carbon Dioxide / Q000737:chemistry*; D002623:Chemistry Techniques, Analytical / Q000379:methods*; D010084:Oxidation-Reduction; D011076:Polycarboxylate Cement / Q000138:chemical synthesis* / Q000737:chemistry; D058105:Polymerization
D011076:Polycarboxylate Cement; D002245:Carbon Dioxide; C005506:polycarbonate
carbon dioxide fixation; copolymerization; cross metathesis; polycarbonates; redox chemistry