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Controlled switching thiocarbonylthio end-groups enables interconvertible radical and cationic single-unit monomer insertions and RAFT polymerizations.
- Source :
- Nature Communications; 6/13/2024, Vol. 15 Issue 1, p1-9, 9p
- Publication Year :
- 2024
-
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. [ABSTRACT FROM AUTHOR]
Details
- Language :
- English
- ISSN :
- 20411723
- Volume :
- 15
- Issue :
- 1
- Database :
- Complementary Index
- Journal :
- Nature Communications
- Publication Type :
- Academic Journal
- Accession number :
- 177898152
- Full Text :
- https://doi.org/10.1038/s41467-024-49463-y