Malins, Edward L. (2015) Synthetic routes to terminal and backbone functionalised copolymer materials. PhD thesis, University of Warwick.

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Abstract

The main objective of this thesis was to design and synthesise, via a combination of controlled radical polymerisation and post-polymerisation modification, functional copolymers with a potential application as automotive additives. Pursuit of this objective resulted in the development of four novel syntheses of copolymers.

Block copolymers of polyisobutylene (PIB) and poly(2-(dimethylamino)ethyl methacrylate) (PDMAEMA) were prepared via two different synthetic pathways that exploited alternative end group modifications of olefin terminated PIB. A PIB macroinitiator was utilised for the single-electron transfer living radical polymerisation of DMAEMA as well as macromolecular coupling of a primary amine bearing PDMAEMA and a succinic anhydride terminated PIB.

Friedel-Crafts alkylation of phenol with olefin terminated PIB and subsequent esterification of the phenolic end group with acryloyl chloride furnished polyisobutylene functionalised with an acrylate end group (PIBA). PIBA was then successfully copolymerised with N,N-dimethylacrylamide (DMA), via reversible addition fragmentation chain transfer (RAFT) polymerisation, to synthesise random and block copolymers of PIBA and DMA.

Alternating copolymers were synthesised by the free radical copolymerisation of alkyl-functional α-methyl styrene (AMS) monomers and maleic anhydride (MalA). These copolymers could then be modified post-polymerisation, via imidisation of the MalA repeat units with a primary amine, to prepare alternating difunctional copolymers.

In the last Chapter original modifications and block copolymers of poly(2,3,4,5,6- pentafluorostyrene) (P(PFS)) were developed. Functionalisation of P(PFS) with a para-azide moiety by substitution of the para-fluorine with sodium azide was demonstrated. This substitution was then performed in combination with a parafluoro thiol "click" reaction and a [4+2] azide-alkyne cycloaddition to subsequently modify a P(PFS) backbone multiple times. A P(PFS) macroRAFT agent, prepared by RAFT polymerisation, was successfully chain extended with DMA and 2-isopropenyl-2-oxazoline to prepare functional amphiphilic block copolymers.

Item Type:	Thesis or Dissertation (PhD)
Subjects:	Q Science > QD Chemistry
Library of Congress Subject Headings (LCSH):	Copolymers -- Synthesis
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, David M. ; Becer, C. Remzi
Extent:	xxvi, 304 leaves : charts
Language:	eng

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