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Oxygen tolerant copper-mediated reversible deactivation radical polymerization
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Liarou, Evelina (2020) Oxygen tolerant copper-mediated reversible deactivation radical polymerization. PhD thesis, University of Warwick.
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WRAP_Theses_Liarou_2020.pdf - Submitted Version - Requires a PDF viewer. Download (8Mb) | Preview |
Official URL: http://webcat.warwick.ac.uk/record=b3492782~S15
Abstract
The focus of this Ph.D. thesis is to develop Cu-RDRP and render it a more user-friendly and versatile platform. For this purpose, three different Cu-RDRP methodologies, Cu(0)-wire mediated RDRP (Chapter 2), photoinduced Cu-RDRP (Chapter 3) and aqueous Cu-RDRP with the pre-disproportionation of Cu(I) (Chapter 4), are studied in the absence of conventional deoxygenation. Without the use of extrinsic oxygen scavengers and reducing agents, a range of well-defined polymers (i.e. poly(acrylates), poly(methacrylates), poly(styrene) and poly(acrylamides)) are synthesized under various conditions (temperatures, solvents, reaction scale). In all the different oxygen tolerant approaches, high end-group fidelity is maintained, leading to well-defined block copolymers in-situ.
In each of the three different approaches, the concentration of oxygen in the polymerization reactions is monitored in-situ with the use of an oxygen probe, and the mechanism of oxygen consumption is investigated and discussed. Furthermore, the role of the polymerization reagents on the evolution of oxygen consumption is elucidated, highlighting the importance of each component.
Apart from the oxygen tolerant nature of these platforms, the effect of UV-irradiation on Cu-based complexes is investigated (Chapter 5), providing insights into the excited state dynamics and the photo-redox behaviour of Cu(II)-based complexes, and the effect of different aliphatic amines on photoinduced Cu-RDRP.
| Item Type: | Thesis (PhD) | ||||
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| Subjects: | Q Science > QD Chemistry | ||||
| Library of Congress Subject Headings (LCSH): | Addition polymerization | ||||
| Official Date: | February 2020 | ||||
| Dates: |
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| Institution: | University of Warwick | ||||
| Theses Department: | Department of Chemistry | ||||
| Thesis Type: | PhD | ||||
| Publication Status: | Unpublished | ||||
| Supervisor(s)/Advisor: | Haddleton, David M. | ||||
| Format of File: | |||||
| Extent: | xxii, 238 leaves : illustrations (some colour) | ||||
| Language: | eng |
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