Controlling Thiyl Radical Polymerization via In Situ Desulfurization

Controlling the thiyl radical polymerizations is highly desirable for synthesizing polymers with precisely controlled main-chain structures yet remains challenging due to the difficulty of reversibly controlling propagating thiyl radicals with existing methods. Here, we present a new strategy in whi...

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Bibliographic Details
Published in:Polymer chemistry 2024-11
Main Authors: Hu, Huajuan, Yi, Ping, He, Jiayang, Cao, Derong, Huang, Hanchu
Format: Article
Language:English
Online Access:Get full text
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Summary:Controlling the thiyl radical polymerizations is highly desirable for synthesizing polymers with precisely controlled main-chain structures yet remains challenging due to the difficulty of reversibly controlling propagating thiyl radicals with existing methods. Here, we present a new strategy in which the propagating thiyl radical undergoes desulfurization with trivalent phosphorus, generating a stabilized carbon radical for reversible control. This approach enables the radical ring-opening polymerization of macrocyclic allylic sulfides to be effectively regulated by reversible addition-fragmentation chain transfer (RAFT) agents, resulting in polymers with well-defined architectures, which was exemplified by the successful incorporation of sequence-defined segments into the polymer backbone, along with diblock copolymerization of macrocyclic allylic sulfides. This work will further advance thiyl radical polymerizations toward polymers with controlled main-chain functionalities.
ISSN:1759-9954
1759-9962
DOI:10.1039/D4PY01140F