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Construction of Well‐Defined Redox‐Responsive CO 2 ‐Based Polycarbonates: Combination of Immortal Copolymerization and Prereaction Approach
Author(s) -
Liu Shunjie,
Zhao Xun,
Guo Hongchen,
Qin Yusheng,
Wang Xianhong,
Wang Fosong
Publication year - 2017
Publication title -
macromolecular rapid communications
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.348
H-Index - 154
eISSN - 1521-3927
pISSN - 1022-1336
DOI - 10.1002/marc.201600754
Subject(s) - copolymer , iminium , polymer chemistry , dispersity , polycarbonate , triphenylphosphine , metathesis , cyclohexene oxide , polymerization , materials science , cyclohexene , catalysis , chemistry , polymer , organic chemistry
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 CO 2 /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 CO 2 ‐based polycarbonates.