The Introductory chapter of this Thesis covers the historical development, synthesis, modification chemistry, and applications of aromatic poly(ether ketone)s, and surveys their potential in technologies for renewable energy generation. The scientific problems which must be solved before such technologies can become commercially viable are highlighted. Chapter 2 describes the development of a "microblock" poly(ether ketone) ionomer (with strictly alternating ionic and neutral chain segments) for use as a proton exchange membrane in water electrolysis, for the production of high purity hydrogen. The ionomer achieves high mechanical strength in an aqueous environment as a result of its designed biphasic morphology. It shows good proton conductivity whilst retaining mechanical integrity under high-temperature, hydrated conditions. Testing in electrolysis has demonstrated good energy efficiency, very low hydrogen crossover, and a stable, reproducible level of power consumption over prolonged periods of time.

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The aims of this project were firstly to develop a protocol for the iterative synthesis of polyethers on a polymeric support, using suitably protected monomers. The synthesis of cyclic ethers by an intramolecular cyclisation/cleavage from the polymeric support, utilising a sulfonyl chloride linker, was also desired. The final aim was to develop a method for reductive amination on a polymeric support, with a view to forming mixed amine/ether oligomers. Chapter 1 is a review of the range of polymers that have been used as supports in organic synthesis, various linkers that have been used to immobilise molecules onto supports, the synthesis of polyethers and cyclic ethers in solution and on polymeric supports, and reductive amination in solution and on polymeric supports. Chapter 2 describes the protecting group strategies that were developed for the synthesis of linear, singly branched and dibranched monomers. These strategies gave monomers in very high yields, which were suitably protected for use in the synthesis of oligomers and cyclic ethers in later chapters. Chapter 3 describes the synthesis of novel linkers on a soluble PEG support PEG sulfonyl chloride and PEG Wang trichloroacetimidate. Both linkers were synthesised in high yields, and were successfully utilised in the PEG supported reactions described in later chapters. Chapter 4 describes the synthesis of oxetanes by mono-activation of a branched diol as a sulfonate ester in solution, on cross-linked polystyrene and on PEG, followed by intramolecular cyclisation/cleavage. Oxetanes were afforded in good yields, under mild conditions, with rapid purification. Chapter 5 describes the development of an iterative polyether synthesis, initially on cross-linked polystyrene, and then on a PEG support. This provided access to a range of structurally defined oligoethers and avoided the laborious purification techniques associated with classical solution based methods. Chapter 6 describes the mild and selective oxidation of an immobilised alcohol to an aldehyde on a PEG support, followed by reductive amination with secondary amines. A strategy is also proposed for the synthesis of mixed amine/ether oligomers. The final chapter describes the experimental techniques employed.

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Polyethylene(oxide) (PEO) is an intriguing polymer, it is water-soluble but exhibits surface-active properties. When capped hydrophobically at one end by a fluorocarbon group, a novel polymeric surfactant is generated. This has been synthesised by combining anionic polymerisation and an end-capping reaction using isophorone diisocyanate. Three molecular weight polymers were generated, for each of which a hydrogenous and a deuterated version were required, hi aqueous solution, these polymeric surfactants formed surface excess layers at the air-water interface and their surface organisation and dynamic behaviour has been investigated. Surface tension data was obtained using a digital tensiometer and the surface tension isotherm is dependent on both solution concentration and polymer molecular weight. Using neutron reflectometry, the organisation of such adsorbed polymer films at the air-water interface has been obtained over a range of solution concentrations for each polymer molecular weight. Neutron reflectometry data was analysed by both optical matrix and kinematic approximation methods. Both analyses yield the same description, i.e. a two-layer organisation is observed at the air-water interface for all three molecular weight polymers. The PEO layer thickness and the surface organisation are found to be dependent on both solution concentration and molecular weight. The PEO chains are totally immersed in the subphase and strongly anchored at the surface via the fluorocarbon end group. The dynamic behaviour of each PEO adsorbed surface excess at the air-water interface has been studied using surface quasi-elastic light scattering. A resonance between the capillary and dilational waves is observed and the maximum in damping is independent on surface organisation but is molecular weight and solution concentration dependent. The viscoelastic behaviour of the dilational modulus can be described using a simple Maxwell fluid model, from which a relaxation time has been obtained assuming a single relaxational process.

The slip-spring model introduced by Likhtman (Macromolecules 38, 6128-6139 (2005)) simulates a single chain entangled within a polymer melt. Single-chain models such as the slip-spring model allow the rheology of polymers to be studied without requiring the use of expensive multiple-chain molecular dynamics simulations. This study investigates the slip-spring model in the context of a single entanglement and compares it to a two-chain entanglement model. A better understanding of the mechanisms involved in an entanglement is obtained, through the properties of stress relaxation and mean squared displacement, but also through analysis of the bead positions and bond vectors involved. Flaws are identified within the slip-spring model, for which modifications to the model are suggested, including the addition of a non-isotropic spring-constant and the replacement of the slip-spring by a slip-chain. This examination of the simple case is carried out, so that the knowledge gained may be later applied to the multiple-entanglement slip-spring model. During the course of this study, the generic polymer simulation (GPS) package was con- structed by the Reading Theoretical Polymer Physics Group. GPS provides an object-orientated simulation framework, designed to keep simulations organised and make new simulations faster to create. An overview of the concepts involved is included in this thesis. Another tool encountered within this study is maximum likelihood estimation, a statistical technique that, when applied to polymer models such as the slip-spring model, allows the estimation of model parameters. Such a fitting is not only useful for finding the best parameters, but also prevents the model flaws from being obscured by incorrect parameter fitting.

Modifiers are incorporated routinely into adhesive formulations to impart favourable chemical and physical properties to the adhesive bond. Control over such properties, such as structure, attractive forces and morphology, can be utilised to enhance key physical properties, e.g., phase separation, hydrophobicity, glass transition temperature, adhesion and cohesion.

This research has shown that biodegradable monomer (5,6-benzo-2- methylene-1,3-dioxepane) (BMOO) can be achieved. Also its homo-and-eo- polymerisation can be successfully realised via RAFT and ROP polymerisation techniques. BMOO was synthesised with the modification via the dehydrobrornination of 5,6-benzo-2-(bromomethyl)-1,3-dioxepane in a good yield (95% yields). The homopolymerisation of BMOO were designed to produce a target OP of 200 via living "polymerisation" and complete ring-opening polymerisation. A narrow POI (1.09) and an M n= 4,697 g mol' were observed after 24 hours for the reaction in the presence of the CT A(MCPDB)' The copolymerisation of MMA and BMOO in the presence of the CT A(CPDB) gave better control over the polymerisation than that achieved using the CT A(MCPDB) and the CTA(ETSPE), at 120 "C. A narrow POI (1.36) and an Mn= 16,662 g mol' were observed after 24 hours. The copolymer was shown to be results of a combination of 1,2-addition polymerisation and of ring-opening copolymerisation. The reactivity ratio of the monomers was calculated using the Kelen- Tudos method (rMMA= 1.12 and rBMDO= 0.43). The copolymerisation of styrene with BMOO in the presence of the CTA(cPDB) gave the better control than that given by the CT A(MCPDB) and the CTA(ETSPE), at 120aC (Sty:BMOO, with an initial feed of 33%:67%). A narrow POI (1.18) and M n= 9,684 g rnol' were obtained after 24 hours. The % ratio of BMOO that was incorporated into the final polymeric chain was Sty:BMOO= 64.3%:35.7% and the copolymer was formed from ring-opening polymerisation only. The reactivity ratio of the monomers was calculated using the Kelen-TOdos method (rsty= 2',56 and rBMDO= 0.64). NMR, FTIR and UVlVis spectroscopy provided further evidence that the final polymers were the product of a ring-opening polymerisation. As required, thermal analysis techniques were used to ascertain the consequences of the copolymerisation, with respect to thermal consequences (decomposition) and compositional features.