Journal
MACROMOLECULAR RAPID COMMUNICATIONS
Volume 37, Issue 10, Pages 833-839Publisher
WILEY-V C H VERLAG GMBH
DOI: 10.1002/marc.201600092
Keywords
anionic polymerization; aziridines; copolymerization; ring-opening polymerization; sequence-controlled polymers
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Funding
- Deutsche Forschungsgemeinschaft [DFG WU/750 7-1]
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Natural macromolecules, i.e., sequence-controlled polymers, build the basis for life. In synthetic macromolecular chemistry, reliable tools for the formation of sequence-controlled macromolecules are rare. A robust and efficient chain-growth approach based on the simultaneous living anionic polymerization of sulfonamide-activated aziridines for sequence control of up to five competing monomers resulting in gradient copolymers is presented. The simultaneous azaanionic copolymerization is monitored by real-time H-1 NMR spectroscopy for each monomer at any time during the reaction. The monomer sequence can be adjusted by the monomer reactivity, depending on the electron-withdrawing effect by the sulfonamide (nosyl-, brosyl-, tosyl-, mesyl-, busyl) groups. This method offers unique opportunities for sequence control by competing copolymerization: a step forward to well-engineered synthetic polymers with defined microstructures.
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