Trifluorovinylsulfur pentafluoride dimerizes to (SF5CFCF2)2 in the presence of cesium fluoride. Two derivatives of trifluorovinylsulfur pentafluoride, SF5CF(CF3)C(O)F and SF5CF(CF3)C(O)NH2, were used to prepare the new compounds, SF5CF(CF3)CO2H and SF5CF(CF3)CN, respectively. The first was prepared by reacting the SF5-acid fluoride with water, while the second involved the abstraction of water from the SF5-amide using P4O10. The attempted preparation of a bis-pentafluorosulfur ketone and a pentafluorosulfur containing acid anhydride were unsuccessful. Selected transition and post transition metal chlorides and elements undergo oxidative displacement and oxidative addition reactions with F-(tert-butyl) hypochlorite, (CF3)3COCl, to form new F-(tert-butoxides). Preliminary studies with selected aromatic systems were also carried out.

Mycobacterium vaccae JOB5 and Graphium sp. were studied to evaluate their ability to cometabolize methyl tert-butyl ether (MTBE) and its metabolites after growth on two different alkanes, propane and iso-pentane. Both cultures were capable of cometabolizing MTBE and the metabolites, tert-butyl formate (TBF) and tert-butyl alcohol (TBA). MTBE, TBF, and TBA did not support growth of either microbe. Higher degradation rates were obtained in the bacterial system when the cultures were grown on iso-pentane. Nonlinear least squares regression and direct linear plot methods were used to estimate kinetic coefficients and provided comparable results. The enzymes from Mycobacterium vaccae JOB5 and Graphium sp. that promote the cometabolism of MTBE and its metabolites exhibited similar kinetics and substrate inhibition. The presence of the substrate decreased the degradation rate of MTBE and TBA suggesting competitive inhibition and preference for the substrate. Blockage experiment with acetylene suggested the presence of an alkane monooxygenase for the metabolism of MTBE and TBA, and a hydrolytic enzyme for the degradation of TBF. The presence of a hydrolase enzyme was supported by the fact that TBF was degraded to TBA under either aerobic or anaerobic conditions and was not inhibited by the presence of acetylene, propane, or isopentane. Measured rates of abiotic hydrolysis of TBF were significantly less than biodegradation rates. Acetylene acted as a reversible inhibitor for both cultures when tested in the presence of the growth media and as an inactivator when tested in the presence of a phosphate solution for the bacterial system. Growth-batch reactor experiments were conducted to compare the degradation of iso-pentane and MTBE with the predicted degradation rates based upon kinetic constants determined from single and dual-compound experiments. Experimental data was modeled with Monod kinetics and STELLA�� software. Reasonable predictions of reactor performance were achieved when Monod maximum utilization rates were increased compared to single and dual-compound experiments. / Graduation date: 2002

Macromonomers bearing oligomerizable C=C functionality have been prepared by the nucleophilic displacement of allylic bromide functionality on brominated poly(isobutylene-co-isoprene) (BIIR). Whereas commercial grades of isobutylene-rich elastomers do not cure under the action of peroxides, these materials undergo simultaneous cross-linking and degradation when activated by radical initiators, with the competitive balance dictated by the reactivity of the oligomerizable group. Vinyl benzoate, vinyl imidazolium, and acrylate functionalities cure rapidly to high cross-link density whereas the maleimide graft is too reactive and unstable for any utility. Methacrylate and itaconate macromonomers cure to moderate extent while maleate esters and unactivated terminally unsaturated groups are unable to significantly counteract the degradation mechanism and do not afford any appreciable cross-link density to BIIR. The most reactive macromonomers display the potential for scorch, an effect that is efficiently mitigated with the introduction of (2,2,6,6-tetramethyl-piperidin-1-yl)oxyl (TEMPO) to quench free radical cure activity. Furthermore, an acrylated adduct, AOTEMPO, is able to recover more of the cross-link density that would otherwise be lost to irreversible free radical coupling. These nitroxyls display longer than expected induction times, likely due to the catalytic nature of TEMPO when alkoxyamine decomposition is significant. A suite of elastomeric ionomers bearing N-functional imidazolium bromide functionality have been prepared in order to investigate the N-alkylation dynamics with brominated poly(isobutylene-co-para-methylstyrene) (BIMS) as well as the subsequent peroxide cure activity of the reactive ionomer. A functional imidazole bearing a methacrylate group displayed moderate alkylation rate and good cure activity whereas a 4-vinylbenzyl analogue provides fast alkylation at the expense of storage stability. N-Allylimidazole is rapidly alkylated by BIMS in both solution and solvent free processes and the resulting ionomer displays unique cure dynamics. This phenomenon is investigated by model compound polymerization and is likely due to the unique free radical reactivity of allyl imidazolium moieties. The cross-linked ionomer displays many of the beneficial physical properties associated with a hybrid ionic/covalent network including good resistance to stress relaxation and thermal stability. / Thesis (Master, Chemical Engineering) -- Queen's University, 2014-01-29 17:09:42.428

Thesis (Ph. D.)--University of Hong Kong, 2005. / Title proper from title frame. Also available in printed format.

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No description available.

Th.--Sci.--Bordeaux 1, 1979. N°: 645.

published_or_final_version / abstract / Ecology and Biodiversity / Doctoral / Doctor of Philosophy

Tertiary butyl alcohol (TBA) is used as a fuel oxygenate and is the main breakdown component of methyl tert butyl ether (MTBE). As such, TBA is found in water systems through storage leaks and spills, presence of MTBE in the water, and as an impure byproduct of MTBE-blended fuels. It presents several health hazards and is a suspected carcinogen. Studies involving aquatic life, mice and rats indicate that TBA is a concern at low concentrations. Wastewater removal of tert butyl alcohol (TBA) has been limited to methodology used by MTBE or by anaerobic or aerobic methods. Neither set of techniques is applicable to TBA due to its long biological degradation period, its very specific conditions for anerobic or aerobic treatment, and its low Henry's law constant, low transformation rate, and its high mobility. The main goal of this project was to determine the adsorption capabilities of different zeolites for TBA. A comparison to previous work done with powdered zeolites and MTBE is shown in the following Chapters. Batch systems of TBA and several different zeolites were examined to determine the best zeolites for TBA adsorption. As shown in Chapter 3, the best zeolites for TBA adsorption over an equilibrium time of 48 hours were silicalite and HiSiv 3000 pellets. Using the two chosen zeolites, silicalite and HiSiv 3000, adsorption isotherms were created and compared against MTBE data using the same data. The final portion of this project included a continuous system consisting of a zeolite column and a steady flow rate of TBA. The zeolite columns consisted of sole silicalite, sole HiSiv 3000, and different proportions of the two zeolites in the same column. All column experiments were run at similar conditions with variation in the adsorbent bed lengths for easy comparison between the resulting breakthrough curves. At the 3-cm bed length, the zeolite columns outperformed the activated carbon column; however, there was no distinct difference between the zeolite columns. In the 6-cm bed length experiments, there were apparent differences between the two zeolite breakthrough curves. The 9-cm column did not differentiate between the zeolites.