Simula, Alexandre (2015) Synthesis of α,ω-telechelics by Cu(0)-mediated reversible deactivation radical polymerisation. PhD thesis, University of Warwick.

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Abstract

The objective of this thesis is to explore the versatility of Cu(0)-mediated reversible deactivation radical polymerisation (RDRP) in organic and aqueous media, towards the design of functional telechelic polymers.

The interest in telechelic macromolecules, i.e. “prepolymer capable of entering into further polymerisation or other reaction through its reactive end groups” arises from their use as chain extenders, precursors for block-, graft-copolymers and networks by reaction with appropriate reagents. The design of telechelic polymers has stemmed from the development of sophisticated polymerisation tools, to achieve good control over the polymer architecture, molecular weight distribution and perhaps more importantly, chain end fidelity.

The limitations and potential of Cu(0)-mediated RDRP technique are tested towards different monomer moieties, solvents and chain end functionalities, with the ultimate goal to expand the scope of functional telechelic polymers. Firstly, the reactivity of the halide end groups is exploited to yield functional telechelic poly(acrylates) with α,ω-hydroxyl groups upon post polymerisation modifications. The macro-diols can be further reacted, via isocyanate end-capping or ring-opening polymerisation. Then, the versatility of the synthetic tool is further tested towards the design of thermo-responsive polymers in water. Acrylamides and acrylates can be copolymerised with good control over the molecular weight distributions and predominantly, chain end fidelity. The typically unwanted hydrolysis of the halide chain ends is further exploited to yield tailor-made diols. Subsequently, the scope of telechelic materials accessible is expanded by careful selection of monomer, ligand, copper source and solvent, yielding well-defined poly(methacrylates) in organic and aqueous media. In the end, the introduction of external halide salts in aqueous media is exploited to generate functional block copolymers with hydrophilic and/or zwitterionic methacrylates in aqueous media.

Item Type:	Thesis or Dissertation (PhD)
Subjects:	Q Science > QD Chemistry
Library of Congress Subject Headings (LCSH):	Telechelic polymers, Polymerization
Official Date:	September 2015
Dates:	Date Event September 2015 Submitted
Institution:	University of Warwick
Theses Department:	Department of Chemistry
Thesis Type:	PhD
Publication Status:	Unpublished
Supervisor(s)/Advisor:	Haddleton, Dave
Sponsors:	Lubrizol Corporation
Extent:	xxxvii, 237 leaves : illustrations (colour), chart
Language:	eng

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