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- Title
Controlled switching thiocarbonylthio end-groups enables interconvertible radical and cationic single-unit monomer insertions and RAFT polymerizations.
- Authors
He, Wei; Tao, Wei; Wei, Ze; Tong, Guoming; Liu, Xiaojuan; Tan, Jiajia; Yang, Sheng; Hu, Jinming; Liu, Guhuan; Yang, Ronghua
- Abstract
To emulate the ordered arrangement of monomer units found in natural macromolecules, single-unit monomer insertion (SUMI) have emerged as a potent technique for synthesizing sequence-controlled vinyl polymers. Specifically, numerous applications necessitate vinyl polymers encompassing both radically and cationically polymerizable monomers, posing a formidable challenge due to the distinct thiocarbonylthio end-groups required for efficient control over radical and cationic SUMIs. Herein, we present a breakthrough in the form of interconvertible radical and cationic SUMIs achieved through the manipulation of thiocarbonylthio end-groups. The transition from a trithiocarbonate (for radical SUMI) to a dithiocarbamate (for cationic SUMI) is successfully accomplished via a radical-promoted reaction with bis(thiocarbonyl) disulfide. Conversely, the reverse transformation utilizes the reaction between dithiocarbamate and bistrithiocarbonate disulfide under a cationic mechanism. Employing this strategy, we demonstrate a series of synthetic examples featuring discrete oligomers containing acrylate, maleimide, vinyl ether, and styrene, compositions unattainable through the SUMI of a single mechanism alone. To emulate the ordered arrangement of radically and cationically polymerizable monomers using single-unit monomer insertion (SUMI) remians challenging. Here the authors demonstrate sequence-defined vinyl polymers via SUMI by manipulating thiocarbonylthio end-groups.
- Subjects
SUMY (Ukraine); RADICALS (Chemistry); VINYL polymers; MONOMERS; VINYL ethers; DITHIOCARBAMATES; POLYMERIZATION; OLIGOMERS; DIARYLETHENE; STYRENE
- Publication
Nature Communications, 2024, Vol 15, Issue 1, p1
- ISSN
2041-1723
- Publication type
Article
- DOI
10.1038/s41467-024-49463-y