Alternating copolymers represent a special class of copolymers in which the two comonomers copolymerize in a regular alternating sequence along the polymer chain. Of particular interest in our group are the stilbene-maleic anhydride/maleimide alternating copolymers. These copolymers possess sterically congested backbones and precisely placed functional groups arising from the strictly alternating copolymerization. The research in this dissertation is focused on the synthesis, characterization, and potential application of functionalized copolymers that contain semi-rigid alternating copolymer sequences. The fluorescence properties of a series of non-conjugated, tert-butyl carboxylate functionalized alternating copolymers were investigated. Extraordinarily high fluorescent intensity with excellent linearity was observed for the di-tert-butyl group-containing stilbene and maleic anhydride alternating copolymer in THF. We attributed the origin of the strong fluorescence to the “through space” π – π interactions between the phenyl rings from the stilbene and C=O groups from the anhydride. The fluorescence was maintained when the copolymer was deprotected and hydrolyzed and the resulting carboxylic acid-functionalized copolymer was dissolved in water at neutral pH. The tert-butyl carboxylate functionalized alternating copolymer sequences were incorporated into highly crosslinked polymer networks using suspension polymerization. After removing the tert-butyl groups by acidic hydrolysis, the surface area of the networks increased significantly. Using this facile two-step strategy, we were able to achieve nanoporous polymers with BET surface area up to 817 m2/g and carboxylic acid-functionalized surfaces. The BET surface area of deprotected polymers increased with increasing crosslinking density, and the stilbene-containing polymers showed systematically higher BET surface area than the styrene-containing polymers due to the stiffness of the alternating sequences. The resulting nanoporous polymers have potential to be employed as solid sorbents for CO2. The same tert-butyl carboxylate functionalized alternating copolymer sequences were also incorporated into microgels via miniemulsion polymerization. The miniemulsion technique ensured the successful synthesis of microgels with ~100 nm diameter using solid stilbene and maleimide monomers. The resulting tert-butyl carboxylate-containing microgels were converted into carboxylic acid-containing aqueous microgels by acid hydrolysis. These aqueous microgels showed good and reversible lead and copper ion adsorption capacities. Amine-functionalized nanoporous polymers were synthesized by the post-modification of highly-crosslinked divinylbenzene-maleic anhydride polymers. High amine-contents were achieved by covalently attaching multiamines to the acid-chloride functionalized polymer surface. The resulting polymers showed medium to high BET surface areas (up to 500 m2/g) and high CO2 capture capacities. / PHD

The normal operation of the endocrine (hormonal) system can be disrupted by a number of man-made and naturally-occurring chemicals, thereby affecting those physiological processes that are under hormonal control. Such substances are called endocrine disrupting compounds (EDCs). The endocrine disruption issue has alarmed the environmental authorities since the substances involved can hinder hormonal processes causing far-reaching effects on reproduction and development in current and future human and wildlife generations. Effects on some species of fish triggered worldwide concern and initiated a research scheme which is being undertaken by various organisations e.g. United States Environmental Protection Agency (USEPA), United Kingdom Environment Agency (UKEA), Oslo and Paris Commission (OSPAR), Japan Environment Agency (JEA) and World Wildlife Fund (WWF) in order to assess the effects (present and potential), point of generation, levels of contamination and exposure limits. The findings showed that most of the oestrogens are produced by humans and animals and get discharged into river streams mainly through sewage effluents. Fish in particular have been found to be affected the most even when the oestrogenic levels in water are very low. The probability of future European legislation to eliminate hormonally active compounds from wastewaters suggests that new and alternative methods should be developed for their removal. In this work, the adsorption of 17ß-oestradiol (E2) and 17a-ethinyl oestradiol (EE2) onto several granular activated carbons and Hypersol-Macronet hypercrosslinked polymers was investigated by batch experiments after a low level detection system had been developed using Gas Chromatography Mass Spectrometry (GC/MS). Equilibrium experiments were carried out for all adsorbents to quantify the sorption capacity for E2 and EE2. For better assessment of the sorbents performance, their physical properties such as surface area, average pore diameter and micropore volume and chemical structure were characterised by N2 adsorption experiments, scanning electron microscopy (SEM), FTIR spectroscopy, elemental analysis, sodium capacity determination, pH titration, proton binding curves and zeta potential measurements. Adsorption isotherm data were fitted to the Langmuir and Freundlich equations. Activated carbons were found to be preferable to Hypersol-Macronet hypercrosslinked polymers for adsorption purposes. The adsorption of oestrogens appears to be controlled by hydrophobic interactions. Kinetic experiments were performed with different size ranges of adsorbents at different concentrations and the results were analysed by a particle diffusion model. It was found that concentration did not seem to influence the kinetics of the oestrogen sorption whereas the particle size of the adsorbents influenced the adsorption rate of both molecules. The particle diffusion model seemed to fit the data collected for the adsorption rate of 17B-oestradiool onto the adsorbents but gave a poor fit for most of the data collected for 17a-ethinyl oestradiol.