Fluorination sulfonate

Fluorinated sulfonic acid, registered trademark of E. 1. du Pont de Nemours Co., Inc. 

Polymer Electrolyte Fuel Cell. The electrolyte in a PEFC is an ion-exchange (qv) membrane, a fluorinated sulfonic acid polymer, which is a proton conductor (see Membrane technology). The only Hquid present in this fuel cell is the product water thus corrosion problems are minimal. Water management in the membrane is critical for efficient performance. The fuel cell must operate under conditions where the by-product water does not evaporate faster than it is produced because the membrane must be hydrated to maintain acceptable proton conductivity. Because of the limitation on the operating temperature, usually less than 120°C, H2-rich gas having Htde or no (

Fluorinated and Ghlorfluorinated Sulfonic Acids. The synthesis of chlorinated and fluorinated sulfonic acids has been extensively reviewed (91,92). The Hterature discusses the reaction of dialkyl sulfides and disulfides, sulfoxides and sulfones, alkanesulfonyl haHdes, alkanesulfonic acids and alkanethiols with oxygen, hydrogen chloride, hydrogen fluoride, and oxygen—chloride—hydrogen fluoride mixtures over metal haHde catalysts, such as... 

All lation. In alkylation, the dialkyl sulfates react much faster than do the alkyl haHdes, because the monoalkyl sulfate anion (ROSO ) is more effective as a leaving group than a haHde ion. The high rate is most apparent with small primary alkyl groups, eg, methyl and ethyl. Some leaving groups, such as the fluorinated sulfonate anion, eg, the triflate anion, CF SO, react even faster in ester form (4). Against phenoxide anion, the reaction rate is methyl triflate [333-27-7] dimethyl sulfate methyl toluenesulfonate [23373-38-8] (5). Dialkyl sulfates, as compared to alkyl chlorides, lack chloride ions in their products chloride corrodes and requires the use of a gas instead of a Hquid. The lower sulfates are much less expensive than lower bromides or iodides, and they also alkylate quickly. 

In general, fluorinated sulfonic acids can be used as eatalysts for various cationic cyclizations Typical examples are the triflic acid catalysis in the double cyclization of A,VV-dibenzylpropynylamine [82] (equation 30) and the fluorosulfonic acid catalyzed condensation of phenylacetaldehyde [<5J] (equation 31)... 

A variety of ionomers have been described in the research literature, including copolymers of a) styrene with acrylic acid, b) ethyl acrylate with methacrylic acid, and (c) ethylene with methacrylic acid. A relatively recent development has been that of fluorinated sulfonate ionomers known as Nafions, a trade name of the Du Pont company. These ionomers have the general structure illustrated (10.1) and are used commercially as membranes. These ionomers are made by copolymerisation of the hydrocarbon or fluorocarbon monomers with minor amounts of the appropriate acid or ester. Copolymerisation is followed by either neutralisation or hydrolysis with a base, a process that may be carried out either in solution or in the melt. 

Sondheimer, S. J., Bunce, N. Y. and Fyfe, C. A. 1986. Structure and chemistry of Nafion-H A fluorinated sulfonic acid polymer. Journal of Macromolecular Science—Reviews in Macromolecular Chemistry and Physics C26 353-413. 

From the correlation of Hammett s constant and P, we might expect the fluorinated sulfone to be a more effective acceptor than the nitro group (Gp(N02)=0.78 vs Gp(S02CF3)= 0.93) (JJJ. A comparison between 4-N, N-dimethylamino-nitrobenzene,6, with 4-N,N-diethylaminophenylperfluoropro-pyl sulfone,5, as indicated in Table II suggests that the use of the fluorinated sulfone leads to comparable values of p (9.0 x 10-30 esu vs 12 x 10 30 esu in this case). More... 

The benzene derivatives containing the fluorinated sulfone have been prepared either by nucleophilic substitution of the 4-fluorophenyl derivative (e.g. 1) or by starting with the appropriately substituted sodium thiophenoxide and reacting with perfluoroalkyl iodide follow by oxidation with either MCPBA or chromium oxide (12. li.) The biphenyl derivatives have been prepared by palladium catalyzed cross coupling chemistry of the 4-bromophenyl derivative (e.g. 2) with substituted phenyl boronic acid (yields 37-84%) (JLH, .). Compound 16 has been prepared by palladium catalyzed cross coupling of (4-bromophenyl)perfluorohexyl sulfone with vinyl anisole in 37 % yield (JJL). The vinyl sulfones, 7 and 9, have been prepared by condensation of CH3S02Rf (JJL) with the appropriate aldehyde (yields 70,and 73%) following a literature procedure (1 ). Yields were not optimized. 

We have found that use of fluorinated sulfone and SSI acceptors leads to materials with better nonlinearity for their transparency compared with materials containing the conventional acceptors. Figure 3 summarizes our findings, and is a plot of jlp vs Xmax for donor-acceptor CT molecules of benzene, styrene, biphenyl, fluorene, and stil-bene derivatives with fluorinted sulfone, SSI, and other common acceptors (SC>2Me, CN, COH, COMe, and NO2) groups. 

Fluorine, proton, and carbon NMR spectral data of some fluorinated sulfonic acids, sulfonyl chlorides and fluorides, and esters are given in Scheme 4.54. 

The PEFC was first developed for the Gemini space vehicle by General Electric, USA. In this fuel cell type, the electrolyte is an ion-exchange membrane, specifically, a fluorinated sulfonic acid polymer or other similar solid polymer. In general, the polymer consists of a polytetrafluoroethylene (Teflon) backbone with a perfluorinated side chain that is terminated with a sulfonic acid group, which is an outstanding proton conductor. Hydration of the membrane yields dissociation and solvation of the proton of the acid group, since the solvated protons are mobile within the polymer. Subsequently, the only liquid necessary for the operation of this fuel cell type is water [7,8],... 

Abbreviations PFSA, partially fluorinated sulfonic acid PK, polyketone-type sulfonic acid. 

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