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Title: Synthesis and polymerization of thioester containing compounds
Author: Aksakal, Suzan
ISNI:       0000 0004 7962 4886
Awarding Body: Queen Mary, University of London
Current Institution: Queen Mary, University of London
Date of Award: 2019
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The objective of this thesis was to investigate the controlled radical polymerisation of thioester compounds and explore their potential with the goal to use the functional group for post-polymerisation modifications. The thesis describes the utilisation of thioester containing monomers in CRP. Firstly, the synthesis and RAFT polymerisation of various thio (meth)acrylates are presented. Investigation of polymerisation parameters affecting the apparent rate constant (e.g. temperature, initiator concentration and different degree of polymerisation), thermal properties and hydrophobicity are elaborated. Furthermore, examples to obtain well-defined poly(thioacrylates) are given by exploring possible reaction conditions for NMP. In addition, modification reactions on poly(ethyl thioacrylate) with primary amines and alcohols were investigated. As well as the copolymerisation with a second functional monomer (PFS). In order to investigate polymerisation conditions for Cu-mediated RDRP, polymerisation parameters were systematically varied and optimised. Ideal reaction conditions were found to utilise a bimetallic system of iron and copper. Chain extension with acrylate and subsequent modification led to a copolymer containing all three types of acrylic monomers. The utilisation of a 4-arm star initiator has also proven to be compatible. Finally, analogues ester, amide and thioester based ATRP initiators have been synthesised and their kinetics were compared to the homopolymerisation of EA. The 4-arm thioester based initiator allowed a rapid and direct access to a thioester based star shaped polymer, whereby the post modification with a protected amino acid resulted in its disassembly to linear polymers. Furthermore, the bifunctional property of ETA monomers has been shown in an aza-Michael addition on the double bond and a catalysed reaction on the thioester moiety, to mimic an amide functionality. In a combination with thiolactone chemistry, a range of sequence-defined oligomers have been obtained on solid phase.
Supervisor: Not available Sponsor: European Union (EuroSequences)
Qualification Name: Thesis (Ph.D.) Qualification Level: Doctoral
EThOS ID:  DOI: Not available
Keywords: Engineering and Materials Science ; Polymerization