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Exploitation of living polymerization and polymer derivatization for the functional materials
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Zhang, Jirui (2022) Exploitation of living polymerization and polymer derivatization for the functional materials. PhD thesis, University of Warwick.
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Official URL: http://webcat.warwick.ac.uk/record=b3910170
Abstract
The objective of this work is to provide new perspectives on the exploitation of controlled living polymerization and functionalization in synthetic polymer chemistry, thus, the versatile approaches were selected for fabrications and the physical and chemical properties of the products were investigated for the potential applications.
The synthesis of end-functional polymyrcene (PMy) was investigated and examined for the synthesis of end-functional polymers in Chapter 2. The end-functional PMy was successfully synthesized via anionic polymerization in THF. A library of epoxides was selected to terminate the propagating PMy chain to induce hydroxyl and other functional groups to the ω-terminus of the polymer, which were examined by different techniques. Subsequently, polymers were fully hydrogenated, which result in improving the thermal and oxidative stability of the end-functional products.
In Chapter 3, the stereochemistry and functionalization of PMy were discussed. PMy with ordered microstructure, has been successfully synthesized by both radical and anionic polymerization in different solvents and subsequently post-modified via photo-induced thiol-ene click chemistry. Two key points were highlighted: (1). The polarity of solvent has a significant impact on the microstructure of the PMy to quantitative stereoisomers. (2). Regioselective functionalization of PMy with a library of thiols to induce hydrophilic/polar groups in different conditions. Subsequently, hydrogenation of PMy and derivatized PMy was carried out so that improve the thermal stability of the products which is desirable for many applications.
Finally, derivatized polyether amine initiated homo- and block copolymer with thermoresponsive behaviour was studied (in Chapter 4). Both hydrophilic and hydrophobic modified polyether amine (Jeffamine) macroinitiators were utilized in copper-mediated reversible deactivation radical polymerization (Cu-RDRP) in aqueous media. Well-defined homopolymer or copolymer of acrylamides (including N-isopropyl acrylamide and N,N-dimethyl acrylamide) were characterized. The thermoresponsive behaviour was confirmed by DLS and UV-Vis, Moreover, thermal analysis provided an insight studies into the effect for the thermoresponsive behaviour.
Item Type: | Thesis (PhD) | ||||
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Subjects: | Q Science > QD Chemistry | ||||
Library of Congress Subject Headings (LCSH): | Polymerization, Polymers, Polymers -- Microstructure, Thermoresponsive polymers, Stereochemistry, Functional groups, Copper catalysts, Biodegradable plastics | ||||
Official Date: | October 2022 | ||||
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. | ||||
Sponsors: | Lubrizol Corporation | ||||
Format of File: | |||||
Extent: | xxxiii, 252 pages : illustrations, charts | ||||
Language: | eng |
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