Hydrocarbons from sulfones

Sulfinic acids and hydrocarbons from sulfones SO2R -> SOgH + HR... 

Hydrocarbons from sulfonic acid esters OSOgR -> H... 

Sodium amalgam Hydrocarbons from sulfones Reductive cleavage... 

Hydrocarbons from sulfonic acid amides Deamination... 

Sulfolane A process for removing aromatic hydrocarbons from petroleum fractions by liquid-liquid extraction using sulfolane (tetramethylene sulfone tetrahydrothiophene-1,1-dioxide) at approximately 190°C. Developed by Shell Development Company in 1959 and first commercialized in 1962 now licensed through UOP. It replaced the Udex process. Sulfolane is used for another purpose in the Sulfinol process. 

A spirothietane sulfone-oxetane is a comonomer in the preparation of polyethers. A polymer obtained from this sulfone in a solution of bis(3,3-chloromethyl) oxetane with phosphorus pentafluoride can be spun to drawable filaments. Thietane sulfone spirocyclic carbonates may be polymerized via the carbonate group to high-molecular-weight solids said to be useful in laminating. Thietane 1,1-dioxide improves the dye receptivity of poly (acrylonitrile), viscose, cellulose acetate, and poly(vinyl chloride). It is also reported to be a stabilizer for nitric acid in oxidizer mixtures for rocket motors. 2-Methylthietane 1,1-dioxide is claimed to be superior to sulfolane (thiolane 1,1-dioxide) in the liquid extraction of aromatic hydrocarbons from mixtures with saturated hydrocarbons. " A number of bis(3,3-alkoxy) thietane 1,1-dioxides have been proposed as intermediates in the preparation of cyanine dyes useful as photographic sensitizers. " ... 

When SO3 itself is employed, the concentration is at a maximum and the initial stage of the sulfonation is completed easily and rapidly. However, the sulfonic acid formed in the initial stage easily reacts with a second mole of SO3 to form a complex which may be much less reactive than SO3 itself. Thus, when reacting a hydrocarbon with SO3 on an equimolar basis, one half of the hydrocarbon is sulfonated with SO3 and the other half is sulfonated by the less reactive complex (see the section on Kinetics). Likewise, when sulfonating organic acids with SO3, the initial reaction product is an acyl sulfate which is next converted to the desired sulfonate under considerably more drastic conditions. The second half of these reactions is the slower, and the rate and reaction conditions are determined by the stability of the initial complex, which varies greatly. The benzene-sulfonic acid-S03 complex is quite reactive, while that from naphthalene-disulfonic acid is comparatively unreactive. When SO3 is used for sulfation, the reaction appears simpler ... 

Chang, J.H., Park, J.H., Park, G.G., Kim, C.S. and Park, 0.0. 2003. E roton-conducting composite membrane derived from sulfonated hydrocarbon and inorganic materials. 

J. H. Chang, J. H. Park, G. G. Park, C. S. Kim and O. O. Park, Proton conducting composite membranes derived from sulfonated hydrocarbon and inorganic materials, J. Power Sources 124, 18-25 (2003). 

Because of good thermal and hydrolytic stability, excellent mechanical and chemical stability, low cost, and commercial availability of sulfonated aromatic hydrocarbon polymers, recent research has focused on the synthesis and development of sulfonated aromatic hydrocarbon polymers specifically for high-temperature PEMFCs. Typical examples include sulfonated poly(ether ether ketone) (SPEEK) or poly(ether ketone ketone) (SPEKK) [1,2], sulfonated poly(ether sulfone) (SPSE) [3], alkyl sulfonated polybenzimidazole (PBI), sulfonated naphthalenic polyinrides (sNPl) [4-6], sulfonated polyCphenylene sulfide) [7,8]. Both post- and pre-sulfona-tion methods have been used in the past. Other than the post-sulfonation modification of aromatic polymers, recently, efforts have been dedicated to direct polycondensation from sulfonic acid containing monomers to synthesize sulfonated polymers [9]. The latter approach, namely pre-sulfonation, is widely applied because of the ease of controlling sulfonation degree and deactivated sites in the arylene backbones, which further avoid side reactions such as decomposition and hydrolysis of polymers resulted from the post-sulfonation method. 

Fig. 15.2 Methanol permeability in Nafion 115 and composite membranes [9]. (This figure was published in Journal of Power Sources, Vol. 124, J. H. Chang, J. H. Park, C-S. Kim, O-Ok Park, Proton-Conducting Composite Membranes Derived from Sulfonated Hydrocarbon and Inorganic Materials, page 22, Copyright Elsevier, 2003)...

Materials that are related through the sulfonate group include the aliphatic paraffin sulfonates produced by the photochemical sulfonation of rehnery hydrocarbons, petroleum sulfonates derived from selected petroleum distillate fractions, olehn sulfonates, A -acyl-A -alkyltaurines, sulfosuccinate esters and related compounds, alkylaryl sulfonates, and ligninsulfonates, which are a byproduct of the paper manufacturing process. While complete coverage of the class would be prohibitive, some of the most important types are described below. 

To overcome these difficulties, drilling fluids are treated with a variety of mud lubricants available from various suppHers. They are mostly general-purpose, low toxicity, nonfluorescent types that are blends of several anionic or nonionic surfactants and products such as glycols and glycerols, fatty acid esters, synthetic hydrocarbons, and vegetable oil derivatives. Extreme pressure lubricants containing sulfurized or sulfonated derivatives of natural fatty acid products or petroleum-base hydrocarbons can be quite toxic to marine life and are rarely used for environmental reasons. Diesel and mineral oils were once used as lubricants at levels of 3 to 10 vol % but this practice has been curtailed significantly for environmental reasons. 

The single-monomer route (eq. 5) is preferred as it proves to give more linear and para-linked repeat unit stmctures than the two-monomer route. Other sulfone-based polymers can be similarly produced from sulfonyl haUdes with aromatic hydrocarbons. The key step in these polymerisations is the formation of the carbon—sulfur bond. High polymers are achievable via this synthesis route although the resulting polymers are not always completely linear. 

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