Synthesis of Novel Star Copolymers via Living Radical Polymerisations for Application as Dispersants

The mam objective of this thesis was to prepare poly(methacrylate) based dispersants via copper(D catalysed living radical polymerisation. In particular, attention was focused on the synthesis of amphiphilic asymmetric star copolymers and conjugates formed between poly(methacrylate)s and poly(ethyle...

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Bibliographic Details
Main Author: MacCreath, Ben
Published: University of Warwick 2007
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Online Access:http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.491515
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Summary:The mam objective of this thesis was to prepare poly(methacrylate) based dispersants via copper(D catalysed living radical polymerisation. In particular, attention was focused on the synthesis of amphiphilic asymmetric star copolymers and conjugates formed between poly(methacrylate)s and poly(ethylene imine). Miktoarm star copolymers were of particular interest as the macromolecular structure afforded by these polymers will not only be effective as a dispersant, but allow an insight into the structure-property relationship of the different dispersant components. Miktoarm star copolymers were synthesised from initiators bearing protected hydroxyl groups by 'living radical polymerisation and post-polymerisation deprotection with subsequent functionalisation and a further polymerisation. The polymers obtained were well-defined and of narrow molecular weight distribution with monomodal SEC traces and PDi <1.4. They were tested as dispersants and a structure-property relationship was sought. Conjugates ofpoly(methacrylate)sand poly(ethylene imine) were formed via afunctionalised polymer. Hydrophobic poly(BMA), which can react with primary amines to form a stable amide linkage, has been synthesised from N-succinimidyl ester functionalised initiators by living radical polymerisation with M. Wt. 5,000 - 15,000 g.mor! and PDi <1.2. The reaction of these with PEl was then investigated. Poly(methacrylates) containing a-carboxyl functionality were also prepared by employing a post-polymerisation functionalisation protocol starting from functionalised polymers or by using a I-butyl protected initiator for the polymerisation followed by a deprotection step. The conjugation of these to PEl via both salt and amide linkages was then investigated. Conjugates fanned by both methods were tested for dispersant ability.