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Synthesis and properties of novel semi-fluorinated block copolymers via Cu(II)-mediated photo-induced RDRP
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Li, Yongguang (2023) Synthesis and properties of novel semi-fluorinated block copolymers via Cu(II)-mediated photo-induced RDRP. PhD thesis, University of Warwick.
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Official URL: http://webcat.warwick.ac.uk/record=b3980923
Abstract
The focus of this thesis is to develop the Cu(II)-mediated photo-induced reversible deactivation radical polymerisation (RDRP) system to synthesise well-defined semi-fluorinated polymers for studying their self-assembly in the bulk state via microphase separation. Semi-fluorinated polymers feature plenty of unique characteristics attributed to the properties of fluorine and the research on these prospective materials is gaining increasing attention and academic interest for many industrial applications.
As a starting point the conditions of the polymerisation of fluorinated monomer using the photo-induced technique were optimised; yielding a process capable to produce semi-fluorinated di-block copolymers as compatibilizers in hundred-gram scales which has been seen as highly challenging conventionally. “Reactive compatibilizers” were also produced with same procedure utilising a hydroxy-functionalised alkyl halide initiator (2-hydroxyethyl 2-bromoisobutyrate). The thermal stability of these materials was investigated, and polymer nanoscale morphologies were studied using transmission electron microscopy (TEM). In collaboration with Warwick Manufacturing Group (WMG) and industry sponsors, Lubrizol, these compatibilizers were blended with fluoroelastomer and thermoplastic polyurethane in order to evaluate their properties.
In the second part a large group of semi-fluorinated di-block copolymers with different molecular weights, mass fractions and functionalities were synthesised to further explore the potential and the limitations of Cu(II)-mediated photo-induced RDRP system. The resulting materials were conducted with comprehensive thermal analysis. Small-angle X-ray scattering (SAXS) was utilised to study the domain sizes and nanoscale morphologies of these semi-fluorinated di-block copolymers.
Finally, a novel strategy for the surface-modification of emulsion-templated highly porous (polyHIPE) materials via surface-initiated Cu(II)-mediated photo-induced RDRP was demonstrated. 2-Hydroxyethyl 2-bromoisobutyrate modified polyHIPEs (HEBiB-polyHIPEs) were fabricated and decorated on the surfaces with a range of acrylate and acrylamide polymer brushes by the “grafting-from” method. Various surface properties were achieved utilising different monomers including fluorescence, wettability and hydrophobicity.
Item Type: | Thesis (PhD) | ||||
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Subjects: | Q Science > QD Chemistry | ||||
Library of Congress Subject Headings (LCSH): | Block copolymers -- Synthesis, Addition polymerization, Fluoropolymers | ||||
Official Date: | January 2023 | ||||
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: | xxi, 194 pages : illustrations | ||||
Language: | eng |
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