Thesis (Ph.D.)--University of Delaware, 2009. / Principal faculty advisors: Michael H. Santare and Anette M. Karlsson, Dept. of Mechanical Engineering. Includes bibliographical references.

Thesis (Ph. D.)--University of Pittsburgh, 1922. / Vita. Bibliography: [1] p. following p. 14.

Monomeric and polymeric fluoroalkyl sulfonyl fluorides, sulfonate salts and sulfonic acids have qualities desirable for use as electrolytes in alternative energy sources such as fuel cells and solid polymer electrolyte lithium batteries. Since the nature of the fluoroalkyl group affects the properties of these compounds, new monomeric and polymeric fluoroalkyl sulfonyl fluorides, sulfonate salts and sulfonic acids were prepared in this work. Simple compounds prepared in this work were: the fluoroalkyl sulfonyl fluorides, sulfonate salts and sulfonic acid CHF (OCF₂CF2SO₂ F)₂ CF₂(OCF₂CF₂SO₂F) ₂ CH₂(OCF₂CF₂SO3Na) ₂ CF₂(OCF₂CF₂SO3 ) ₂Ca , CF₂(OCF₂CF₂SO3H) ₂ prepared by means of electrochemical fluorination; FC (CF3 ) ₂OCH₂CH₂OCF₂CF₂SO₂F prepared using the adduct of hexafluoroacetone and silver fluoride; CH₃OCF₂CF₂SO₂F prepared as a substrate for free-radical substitution reactions of fluorinated species; and the pentafluorosulfur lithium sulfonate salts SFsCHFSO₃Li and SFsCF₂SO₃Li. Novel compounds containing both alcohol and fluoroalkyl sulfonyl functional groups were prepared: the chlorohydrin ClCH₂CH (OH) CH₂OCF₂CF₂SO₂F; the benzyl ethers HOCH₂CH (OCH₂C6Hs) CH₂OCF₂CF₂SO₂F and C6HsCH₂OCH₂CH (OH) CH₂OCF₂CF₂SO₂F as a product mixture; and the diol HOCH₂CH (OH) CH₂OCF₂CF₂SO₂F. The diol was found to be a useful synthon for the preparation of two polymeric fluoroalkyl sulfonyl fluorides: the polyester [C (O)CF₂CF₂CF₂ C (O) OCH₂CH (CH₂OCF₂) CF₂SO₂F] O]n by reaction with perfluoroglutaric anhydride and a polyurethane formed with 1,6-diisocyanohexane. Other polymeric compounds prepared were: the sulfonyl fluoride, sulfonate salt and sulfonic acid [OCH₂CH (CH₂OCF₂CF₂SO₂F)]n, [OCH₂CH (CH₂OCF₂CF₂SO₃Na)]n, and [OCH₂CH (CH₂OCF₂CF₂SO₃H)]n prepared by homopolymerization of the epoxide OCH₂CHCH₂OCF₂CF₂SO₂F; a cross-linked copolymer of the same epoxide; and the fluoroalkyl sulfonyl fluoride polyacrylat [-CH₂-CH-(CO₂CH₂CH₂CF₂CF₂OCF₂CF₂SO₂F)]n prepared from the acrylate ester H₂C=CHC (O) OCH₂CH₂CF₂SO₂F. ¹H, ¹⁹F and ¹³C nuclear magnetic resonance spectroscopy, infrared spectroscopy, mass spectrometry, melting point or boiling point, elemental analysis, contact angles, optical clarity, refractive index, and specific conductivity were among the techniques used to characterize the compounds.

Sulfur trioxide (SO₃) adds to fluoroolefins of the form RCF=CF₂, (where R = F, SF₅, CF₃, CF₃OCF₂, CF₂=CF(CF₂)₂, CF₃(CF₂)₃O, CF₃O(CF₂)₂OCF₂, or CH₂ClCHClCH₂), yielding the fluorinated [beta]-sultones, RCFCF₂OSO₂. In the case of CF₃(CF₂)₃OCF=CF₂, a reverse addition occurs, giving the sultone, CF₃(CF₂)₃CF₂2OCFCF₂SO₂O. The fluoro [beta]-sultones are capable of undergoing different reactions, such as rearrangement, hydrolysis, esterification, and polymerization. These reactions, will result in the formation of compounds containing the fluorosulfonyl grouping (SO₂F); it is this group that yields the corresponding sulfonic acid upon base/acid treatment. The addition of sodium bisulfite to CF₃CF= CF₂ and CF₃(CF₂)₄CF=CF₂ in the presence of (C₆H₅CO)₂O₂ and Na₂B₄O₇·10H₂O was also studied to produce the corresponding sulfonic acid hydrates of the general formula, R[subscript f]CFHCF₂SO₃H·nH₂O. These acids were prepared, and thus, tested as possible fuel cell electrolytes. Infrared, ¹H and ¹⁹F nuclear magnetic resonance and mass spectra, as well as elemental analyses, will be presented in order to support the proposed structures for the resulted compounds.

Thesis (doctoral)--Technische Hochschule Karisruhe, 1904. / Includes bibliographical references.

Thesis (M.S.)--Rutgers University, 2008. / "Graduate Program in Chemistry and Chemical Biology." Includes bibliographical references (p. 23-24).

Thesis (doctoral)--Technische Hochschule Karisruhe, 1904. / Includes bibliographical references.

Pentafluorosulfur (VI) bromide (SF5Br) adds to olefins of the form CX2=CX2, where X= H or F, with the pentafluorosulfur group usually adding to the carbon with more hydrogens attached to it. This series of compounds was used in an attempt to prepare the corresponding sulfonic acid hydrates of the general formula SF5CX2CX2SO3H·nH2O, in order to have these compounds tested as possible fuel cell electrolytes. The reaction scheme involved reflux of the SF5Br adduct with an equimolar amount of sodium sulfite in 50% ethanol for two days, followed by acidification of the recovered solid material using HCl or H2SO4.

Part I describes the preparation of a number of useful intermediates from the sultone F5SCHCF2OSO2 (1). These intermediates include the following: the ketene F5SC(SO2)=C=O (21), the unique sultone F4S=CCF2OSO2 (23), and various ionic intermediates of the form Y+ [F5SC(SO2F) COX]-. These intermediates play an important role in providing new pathways for preparing fluorosulfonic acid precursors. Fluorosulfonic acids are excellent candidates to improve the efficiency of environmentally safe fuel cells. It was possible to obtain new derivatives of 1 by various reactions of 21, 23 and the ionic intermediates, but it was not possible to introduce an alkyl substituent with either of the intermediates. Part II is concerned with the synthesis of SF5 containing epoxides as possible monomers. When polymerized, materials of high dielectric strength and high chemical resistance should be obtained. The reaction chemistry of one of the epoxides was investigated and it was found that all reactions studied were accompanied by the loss of the SF5 group. Thus, it was not possible to obtain any polymeric materials. Part III deals with the synthetic accessibility of SF$\sb5$ malonic esters and thence of SF$\sb5$ acrylic esters. These compounds should serve as building blocks in the synthesis of SF$\sb5$ containing pyrimidines. The CF3 analogue, 5-trifluoromethyl uracil, is used as an antiviral drug. In order to synthesize either SF5 malonic ester or 2-SF5 acrylic ester an SF5 group has to be introduced at a secondary carbon. A secondary SF$\sb5$ compound could be synthesized (F5SCH (COOC2H5) (CHBrOAc)) but could not be converted to the respective malonic ester F5SCH (COOC2H5) compound. Part IV describes the reactions and preparations of Parts I-III.

An experimental investigation of the high pressure synthesis of water soluble, self doping conducting polymers is presented. 2- And 3-aminobenzenesulfonic acid and the respective sodium sulfonates have been polymerised. Optimal polymerisation conditions have been determined with respect to yield, conductivity and molecular weight. Reaction parameters such as oxidant, pressure, catalysts, reaction time and temperature and the use of additives were investigated. The minimum pressure required for polymerisation was 7 kbar. An increase in pressure had a negligible effect on polymer characteristics. The polymers were generated in aqueous, non-acidic media, to ensure they were selfdoping when characterised. Conductivities of between 10-6 Scm-1 and 10-3 Scm-1 were measured. The sulfonate salts reacted faster than the sulfonic acids and for both a longer reaction time resulted in higher yields and conductivities. These polymers were completely water soluble, of high molecular weight and able to be cast as thin films. The arylamines 5- and 8-aminonaphthalene-2-sulfonic acid and their respective sodium sulfonates were polymerised at elevated pressure. The naphthalene sulfonate salts polymerised at atmospheric pressure, but displayed a higher molecular weight when reacted under pressure. Generally the naphthalene monomers reacted similarly to the benzene monomers, although there were some differences. Conductivity and yield decreased with increased reaction times and the use of 0.1M equivalents of ferrous sulfate had an negligible effect on the polymers. The polynaphthalenes were highly water soluble, self doping and had conductivities in the order 10-5 to 10-3 Scm-1. A measurement of the activation volume for the polymerisation of 2-methoxyaniline and sodium 8-aminonaphthalene-2-sulfonate was performed. These were determined to be -44 ± 3 cm3mol-1 and -62 ± 10 cm3mol-1 respectively. These large negative values are consistent with rate limiting monomer oxidation.