Nikolaou, Vasiliki (2015) Copper-mediated living radical polymerisation of acrylates and acrylamides : utilising light as an external stimuli. PhD thesis, University of Warwick.

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Abstract

The main focus of this thesis is to expand the scope of the newly developed copper-mediated photo-induced reversible deactivation radical polymerisation (RDRP) system. The synthesis of α,ω-telechelic multiblock copolymers will be attempted utilising a wide range of bi-functional initiators and acrylic monomers targeting different chain lengths. The compatibility of this system with special solvents and catalysts will also be investigated. Moreover, the limitations of this technique will be highlighted including the necessity to employ various components that require multiple optimisation studies and the challenge in efficiently storing many reactants (e.g. ligands, copper catalyst). Two novel discrete complexes that incorporate both precatalyst and ligand will be synthesised to address the aforementioned issues while advanced characteristics and advantages over the previous approach will be demonstrated.

In the second part the polymerisation of acrylamides will be demonstrated utilising aqueous Cu(0)-mediated RDRP since the light system is not applicable for the controlled polymerisation of this monomeric family. The high end-group fidelity of the resulted polyacrylamides will also be exemplified via sequential monomer addition with both acrylamide and acrylate monomers, yielding well-defined hydrophilic materials.

In the last chapter the synthesis of semifluorinated triblock copolymers in a multigram scale utilising the photo-induced RDRP will be demonstrated. This is an ongoing work with the Lubrizol Corporation and constitutes only a few initial studies towards developing materials with interesting properties or applications and basically sets the scene for future work.

Item Type:	Thesis (PhD)
Subjects:	Q Science > QD Chemistry
Library of Congress Subject Headings (LCSH):	Addition polymerization
Official Date:	October 2015
Dates:	Date Event October 2015 Submitted
Institution:	University of Warwick
Theses Department:	Department of Chemistry
Thesis Type:	PhD
Publication Status:	Unpublished
Supervisor(s)/Advisor:	Haddleton, David M.
Extent:	xxvi, 227 leaves : illustrations, charts
Language:	eng

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