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Title: Design, Synthesis andCharacterisation of Reactive StarPolymers
Author: Cauet, Solene
ISNI:       0000 0004 2672 3442
Awarding Body: The University of Warwick
Current Institution: University of Warwick
Date of Award: 2008
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The objective of this thesis was to prepare well-defined succinimide-functional star polymers by copper(I) catalysed living radical polymerisation. Atom transfer radical polymerisation (ATRP) was used to prepare copolymers incorporating the activated ester methacrylate monomer Nmethacryloxysuccinimide (NMS) and butyl methacrylate (BMA). First, welldefined pure 5-arm star block copolymers were prepared by polymerisation of BMA from a glucose-core initiator to produce star homopolymers which were then used as macroinitiators for the polymerisation of NMS. Thereafter, welldefined pure 5-arm star statistical copolymers and copolymers with a pure BMA block and a statistical block were produced. Good control over the kinetics and molecular weights was achieved. The molecular weights of the copolymers were confirmed by gel permeation chromatography with low-angle laser light scattering detection (GPC-LALLS) and their compositions via IH NMR and elemental analysis. Well-defined styrene 5-arm star polymers were synthesised via ATRP from a glucose core. 'Click chemistry' was used to end-functionalise two star polymers of different molecular weights by converting the chain-ends to azide groups after which the resulting polymers were clicked with three alkyne compounds with biotin, coumarin and succinimide functionality. IH NMR, FTIR, GPC, GPCLALLS and MALDI-TOF analyses confirmed the success of the click reactions. Finally, the reaction of poly(BMA-co-NMS) copolymers with amines was studied by FTIR, GPC and IH NMR. It was observed that the reactions followed first-order kinetics with respect to the quantity of succinimidyl groups. The presence of ring-opened side product was shown by IH NMR and signs of this side reaction were also observed with GPC-UV analysis. The results of this study were used to prepare derivates of a 5-arm statistical BMA-NMS star copolymer precursor with 5 different amines. The final products were analysed by IH NMR to measure conversion of succinimidyl groups and amount of side-product and by GPC-LALLS to obtain molecular weights. The solubility of the derived polymers was also assessed in a number of different solvents.
Supervisor: Not available Sponsor: Not available
Qualification Name: Thesis (Ph.D.) Qualification Level: Doctoral
EThOS ID:  DOI: Not available