Light-induced RAFT single unit monomer insertion in aqueous solution—toward sequence-controlled polymers
| Autor: | Reece W. Lewis, Almar Postma, Graeme Moad, Nino Malic, Yanyan Zhou, Annelore Aerts |
|---|---|
| Přispěvatelé: | Macromolecular and Organic Chemistry |
| Jazyk: | angličtina |
| Rok vydání: | 2018 |
| Předmět: |
Polymers and Plastics
Light Radical polymerization Thio 02 engineering and technology 010402 general chemistry Photochemistry 01 natural sciences Oligomer Polymerization Reaction rate chemistry.chemical_compound Materials Chemistry Pentanoic Acids/chemistry Pentanoic Acids single unit monomer insertion Acrylamides/chemistry Acrylamides Aqueous solution Organic Chemistry Chain transfer Raft sequence defined polymers 021001 nanoscience & nanotechnology Photochemical Processes radical polymerization 0104 chemical sciences Kinetics Monomer chemistry 0210 nano-technology RAFT |
| Zdroj: | Macromolecular Rapid Communications, 39(19):1800240. Wiley-VCH Verlag |
| ISSN: | 1022-1336 |
| Popis: | First report on the sequential, visible light-initiated, single unit monomer insertion (SUMI) of N,N-dimethylacrylamide (DMAm) into the reversible addition fragmentation chain transfer (RAFT) agent, 4-((((2-carboxyethyl)thio)carbonothioyl)thio)-4-cyanopentanoic acid (CTA1), in aqueous solution is provided. The specificity for SUMI over formation of higher oligomers and/or RAFT agent-derived by-products is higher for longer irradiation wavelengths. Red light provides the cleanest product (selective SUMI), showing a linear pseudo-first order kinetic profile to high (>80%) conversion, but also the slowest reaction rate. Blue light provides a relatively rapid reaction, but also gives some by-products (65% conversion. Higher specificity with red light is attributed to CTA1 absorbing at longer wavelengths than the SUMI product, which allows selective excitation of CTA1. The use of a higher reaction temperature (65 °C vs ambient) results in a higher reaction rate and a reduction in oligomer formation. |
| Databáze: | OpenAIRE |
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