Smart Control of Nitroxide-Mediated Polymerization Initiators’ Reactivity by pH, Complexation with Metals, and Chemical Transformations
| Autor: | Mariya Edeleva, Gerard Audran, Sylvain Marque, Elena Bagryanskaya |
|---|---|
| Jazyk: | angličtina |
| Rok vydání: | 2019 |
| Předmět: |
nitroxide mediated polymerization
alkoxyamine tunable rate constants protonation complexation Technology Electrical engineering. Electronics. Nuclear engineering TK1-9971 Engineering (General). Civil engineering (General) TA1-2040 Microscopy QH201-278.5 Descriptive and experimental mechanics QC120-168.85 |
| Zdroj: | Materials, Vol 12, Iss 5, p 688 (2019) |
| Druh dokumentu: | article |
| ISSN: | 1996-1944 |
| DOI: | 10.3390/ma12050688 |
| Popis: | Because alkoxyamines are employed in a number of important applications, such as nitroxide-mediated polymerization, radical chemistry, redox chemistry, and catalysis, research into their reactivity is especially important. Typically, the rate of alkoxyamine homolysis is strongly dependent on temperature. Nonetheless, thermal regulation of such reactions is not always optimal. This review describes various ways to reversibly change the rate of C⁻ON bond homolysis of alkoxyamines at constant temperature. The major methods influencing C⁻ON bond homolysis without alteration of temperature are protonation of functional groups in an alkoxyamine, formation of metal⁻alkoxyamine complexes, and chemical transformation of alkoxyamines. Depending on the structure of an alkoxyamine, these approaches can have a significant effect on the homolysis rate constant, by a factor of up to 30, and can shorten the half-lifetime from days to seconds. These methods open new prospects for the application of alkoxyamines in biology and increase the safety of (and control over) the nitroxide-mediated polymerization method. |
| Databáze: | Directory of Open Access Journals |
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