Affiliation:
1. Department of Macromolecular Science, State Key Laboratory of Molecular Engineering of Polymers Fudan University Shanghai 200433 China
2. School of Chemistry and Chemical Engineering, Chongqing Key Laboratory of Theoretical and Computational Chemistry Chongqing University Chongqing 401331 China
Abstract
AbstractOrganocatalyzed reversible‐deactivation radical polymerizations (RDRPs) are attractive for many applications. Here, we developed photoredox‐mediated RDRP by activating (hetero)aryl sulfonyl chloride (ArSO2Cl) initiators with pyridines and designing a novel bis(phenothiazine)arene catalyst. The in situ formed sulfonyl pyridinium intermediates effectively promote controlled chain‐growth from ArSO2Cl, enabling access to various well‐defined polymers with high initiation efficiencies and controlled dispersities under mild conditions. This versatile method allows “ON/OFF” temporal control, chain‐extension, facile synthesis of different polymer brushes via organocatalyzed grafting reactions from linear chains. Time‐resolved fluorescence decay studies and calculations support the reaction mechanism. This work provides a transition‐metal‐free RDRP to tailor polymers with readily available aromatic initiators, and will promote the design of polymerization leveraged from photoredox catalysis.
Funder
National Natural Science Foundation of China
State Key Laboratory of Molecular Engineering of Polymers
Subject
General Chemistry,Catalysis
Cited by
6 articles.
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