Studies of the cationic polymerisation of vinylic and energetic cyclic ether monomers

The cationic polymerisation of various monomers, including cyclic ethers bearing energetic nitrate ester (-ON02) groups, substituted styrenes and isobutylene has been investigated. The main reaction studied has been the ring-opening polymerisation of 3- (nitratomethyl)-3-methyl oxetane (NIMMO) using the alcohol/BF3.0Et2 binary initiator system. A series of di-, tri- and tetrafunctional telechelic polymers has been synthesised. In order to optimise the system, achieve controlled molecular weight polymers and understand the mechanism of polymerisation the effects of certain parameters on the molecular weight distribution, as determined by Size Exclusion Chromatography, have been examined. This shows the molecular weight achieved depends on a combination of factors including -OH concentration, addition rate of monomer and, most importantly, temperature. A lower temperature and OH concentration tends to produce higher molecular weight, whereas, slower addition rates of monomer, either have no significant effect or produce a lower molecular weight polymer. These factors were used to increase the formation of a cyclic oligomer, by a side reaction, and suggest, that the polymerisation of NIMMO is complicated with endbiting and back biting reactions, along with other transfer/termination processes. These observations appear to fit the model of an active-chain end mechanism. Another cyclic monomer, glycidyl nitrate (GLYN), has been polymerised by the activated monomer mechanism. Various other monomers have been used to end-cap the polymer chains to produce hydroxy ends which are expected to form more stable urethane links, than the glycidyl nitrate ends, when cured with isocyanates. A novel monomer, butadiene oxide dinitrate (BODN), has been prepared and its homopolymerisation and copolymerisation with GL YN studied. In concurrent work the carbocationic polymerisations of isobutylene or substituted styrenes have been studied. Materials with narrow molecular weight distributions have been prepared using the diphenyl phosphate/BCl3 initiator. These systems and monomers are expected to be used in the synthesis of thermoplastic elastomers.

Hydrogels containing linear and cyclic polyethers

Hydrogels are a unique class of polymer which swell, but do not dissolve in, water. A range of 2-hydroxyethyl methacrylate based copolymer hydrogels containing both cyclic and linear polyethers have been synthesised and are described in this thesis. Initially, cyclic polyethers were occluded within the polymer matrix and the transport properties investigated. The results indicated that the presence of an ionophore can be used to modulate ion transport and that ion transport is described by a dual-sorption mechanism. However, these studies were limited due to ionophore loss during hydration. Hence, the synthesis of a range of acrylate based crown ether monomers was considered. A pure sample of 4-acryolylaminobenzo-15-crown-5 was obtained and a terpolymer containing this monomer was prepared. Transport studies illustrated that the presence of a `bound' ionophore modulates ion transport in a similar way to the occluded systems. The transport properties of a series of terpolymers containing linear polyethers were then investigated. The results indicated that the dual-sorption mechanism is observed for these systems with group II metal cations while the transport of group I metal cations, with the exception of sodium, is enhanced. Finally, the equilibrium water contents (EWC) surface and mechanical properties of these terpolymers containing linear polyethers were examined. Although subtle variations in EWC are observed as the structure of the polyether side chain varies, generally EWC is enhanced due to the hydrophilicity of the polyether side chain. The macroscopic surface properties were investigated using a sessile drop technique and FTIR spectroscopy. At a molecular level surface properties were probed using an in vitro ocular spoilation model and preliminary cell adhesion studies. The results indicate that the polyethylene oxide side chains are expressed at the polymer surface thus reducing the adhesion of biological species.

Cyclic and acyclic modifications of 5-aminoimidazole-4-carboxamide

The Introduction gives a brief resume' of the biologically important aspects of 5 -aminoimidazole -4 -carbozamide (1) and explores., in-depth, the synthetic routes to this imidazole. All documented reactions of 5 -aninoimidanole-4 -carboxamide are reviewed in detail, with particular emphasis on the preparation and subsequent coupling reactions of 5 –diazo-imidazole-4 -carboxamide (6). A series of thirteen novel amide 5-amino-2-arylazoimidazole-4-carboxamide derivatives (117-129) were prepared by the coupling of aryldiazonium salts with 5-aminoimidazole-4-carboxamide. Chemical modification of these azo-dyes resulted in the preparation of eight previously unknown acyl derivatives (136-143) Interaction of 5-amino-2-arylazoimidazole-4-carboxides with ethyl formate in sodium ethoxide effected pyrimidine ring closure to the novel 8-arylazohypoxanthines (144 and 145). Several reductive techniques were employed in an effort to obtain the elusive 2,5-diaminoimidazole-4-carboxamide (71),a candidate chemotherapeutic agent, from the arylazoiridazoles. No success can be reported although 5-amino-2-(3-aminoindazol-2-yl) imidazole-4-carboxamide (151) was isolated due to a partial reduction and intramolecular cyclisation of 5-amino72-(2-cyanaphenylazo)imidazole-4-carboxamide (122) .Further possible synthetic approaches to the diaminoimidazole are discussed in Chapter 4. An interesting degradation of a known unstable nitrohydrazone is described in Chapter 5.This resulted in formation of 1, 1-bis(pyrazol--3-ylazo)-1-nitroethane (164) instead of the expected cyclisation to a bicyclic tetrazine N-oxide. An improved preparation of 5-diazoinidazole-4-carboxamide has been achieved, and the diazo-azole formed cycloadducts with isocyanates to yield the hitherto unknown imidazo[5,1-d][1,2,3,5]tetrazin-7(6H)-ones. Eleven derivatives (167-177) of this new ring-system were prepared and characterised. Chemical and spectroscopic investigation showed this ring-system to be unstable under certain conditions, and a comparative study of stability within the group has been made. "Retro-cycloaddition" under protic and photolytic conditions was an unexpected property of 6-substituted imidazo[5,1-d][1,2,3,5]tetrazin--7(0)-ones.Selected examples of the imidazotetrazinone ring-system were tested for antitumour activity. The results of biological evaluation are given in Chapter 7, and have culminated in a Patent application by the collaborating body, May and Baker Ltd. One compound,3-carbamoyl-6-(2-chloro-ethyl)imidazo[5,1-d][1,2,3,5jtetrazin-7(6H)-one (175),shows striking anti-tumour activity in rodent test systems.

Polymer PCF Bragg grating sensors based on poly(methyl methacrylate) and TOPAS cyclic olefin copolymer

Fibre Bragg grating (FBG) sensors have been fabricated in polymer photonic crystal fibre (PCF). Results are presented using two different types of polymer optical fibre (POF); first multimode PCF with a core diameter of 50µm based on poly(methyl methacrylate) (PMMA) and second, endlessly single mode PCF with a core diameter of 6µm based on TOPAS cyclic olefin copolymer. Bragg grating inscription was achieved using a 30mW continuous wave 325nm helium cadmium laser. Both TOPAS and PMMA fibre have a large attenuation of around 1dB/cm in the 1550nm spectral region, limiting fibre lengths to no longer than 10cm. However, both have improved attenuation of under 10dB/m in the 800nm spectral region, thus allowing for fibre lengths to be much longer. The focus of current research is to utilise the increased fibre length, widening the range of sensor applications. The Bragg wavelength shift of a grating fabricated in PMMA fibre at 827nm has been monitored whilst the POF is thermally annealed at 80°C for 7 hours. The large length of POF enables real time monitoring of the grating, which demonstrates a permanent negative Bragg wavelength shift of 24nm during the 7 hours. This creates the possibility to manufacture multiplexed Bragg sensors in POF using a single phase mask in the UV inscription manufacturing. TOPAS holds certain advantages over PMMA including a much lower affinity for water, this should allow for the elimination of cross-sensitivity to humidity when monitoring temperature changes or axial strain, which is a significant concern when using PMMA fibre.

The formation and properties of some cyclic compounds of silicon an dtin

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