Perfluorocarbons

The reactivity of fluorine compounds varies from extremely stable, eg, compounds such as sulfur hexafluoride [2551-62 ] nitrogen trifluoride [7783-54-2] and the perfluorocarbons (see Fluorine compounds, organic) to extremely reactive, eg, the halogen fluorides. Another unique property of nonionic metal fluorides is great volatiUty. Volatile compounds such as tungsten hexafluoride [7783-82-6] molybdenum hexafluoride [7783-77-9] ... 

Carbon and Graphite. Fluorine reacts with amorphous forms of carbon, such as wood charcoal, to form carbon tetrafluoride [75-73-0], CF, and small amounts of other perfluorocarbons. The reaction initiates at ambient conditions, but proceeds to elevated temperatures as the charcoal bums ia fluoriae. 

Disposal. Fluorine can be disposed of by conversion to gaseous perfluorocarbons or fluoride salts. Because of the long atmospheric lifetimes of gaseous perfluorocarbons (see Atmospheric models), disposal by conversion to fluoride salts is preferred. The following methods are recommended scmbbing with caustic solutions (115,116) reaction with soHd disposal agents such as alumina, limestone, lime, and soda lime (117,118) and reaction with superheated steam (119). Scmbbing with caustic solution and, for dilute streams, reaction with limestone, are practiced on an industrial scale. 

Aerosol-Based Direct Fluorination. A technology that works on Hter and half-Hter quantities has been introduced (40—42). This new aerosol technique, which functions on principles similar to LaMar direct fluorination (Fig. 5), uses fine aerosol particle surfaces rather than copper filings to maintain a high surface area for direct fluorination. The aerosol direct fluorination technique has been shown to be effective for the synthesis of bicycHc perfluorocarbon such as perfluoroadamantane, perfluoroketones, perfluoroethers, and highly branched perfluorocarbons. 

Simple and Complex Organic Molecules. Using modem direct fluorination technology, the synthesis of even the most complex perfluorocarbon stmctures from hydrocarbon precursors is now possible. For example, syntheses of the first perfluoro crown ethers, perfluoro 18-crown-6, perfluoro 15-crown-5, and perfluoro 12-crown-4 (54) have been reported. Perfluoro crown ethers (54,55) are becoming important as the molecules of choice for many F-nmr imaging appHcations (56) in humans and are particularly effective in brain and spinal diagnostics when... 

Hydrocarbon Polymers. It is difficult to produce perfluorocarbon polymers by the usual methods. Many monomers, such as hexafluoropropylene, polymerize only slowly because of the steric hindrance of fluorine. Furthermore, some monomers are not very stable and are difficult to synthesize. Direct fluorination can be used for the direct synthesis of fluorocarbon polymers (68—70) and for producing fluorocarbon coatings on the surfaces of hydrocarbon polymers (8,29,44—47,49,68—71). 

The extremely nonpolar character of PFCs and very low forces of attraction between PFC molecules account for their special properties. Perfluorocarbons bod only slightly higher than noble gases of similar molecular weight, and their solvent properties are much more like those of argon and krypton than hydrocarbons (2). The physical properties of some PFCs are Hsted in Table 1. 

Table 1. Physical Properties of Aliphatic Perfluorocarbons (PFCs) ...

The surface of PTFE articles is sHppery and smooth. Liquids with surface tensions below 18 mN/m(=dyn/cm) are spread completely on the PTFE surface hence, solutions of various perfluorocarbon acids in water wet the polymer (78). Treatment with alkafl metals promotes the adhesion between PTFE and other substances (79) but increases the coefficient of friction (80). 

The sorption behavior of perfluorocarbon polymers is typical for nonpolar partially crystalline polymers (89). The weight gain strongly depends on the solubihty parameter. Litde sorption of substances such as hydrocarbons and polar compounds occurs. 

Polymer Solvent. Sulfolane is a solvent for a variety of polymers, including polyacrylonitrile (PAN), poly(vinyhdene cyanide), poly(vinyl chloride) (PVC), poly(vinyl fluoride), and polysulfones (124—129). Sulfolane solutions of PAN, poly(vinyhdene cyanide), and PVC have been patented for fiber-spinning processes, in which the relatively low solution viscosity, good thermal stabiUty, and comparatively low solvent toxicity of sulfolane are advantageous. Powdered perfluorocarbon copolymers bearing sulfo or carboxy groups have been prepared by precipitation from sulfolane solution with toluene at temperatures below 300°C. Particle sizes of 0.5—100 p.m result. 

For pure nonhydrocarbon organics, the most accurate method for predic tion of critical temperature for all compound groups is also the Ambrose" method. Equation (2-1) applies to all nonhydrocarbon compounds except perfluorocarbons, where the constant 1.242 is replaced by 1.570. For compounds containing any of C, H, O, N, S, or halogens up to C13 and ranging in critical temperature from 228-790 K, the average error is about 6 K. 

Attention should also be directed to the growing number of perfluorocarbon-sulfur species which feature single, double or even triple C-S bonds, e.g. ... 

Another important argument for the use of the organic solvent is the reverse hydrolytic reactions that become feasible [61,75]. The inhibition of the biocatalyst can be reduced, since the substrate is initially concentrated in the organic phase and inhibitory products can be removed from the aqueous phase. This transfer can shift the apparent reaction equilibrium [28,62] and facilitates the product recovery from the organic phase [20,29,33]. A wide range of organic solvents can be used in bioreactors, such as alkanes, alkenes, esters, alcohols, ethers, perfluorocarbons, etc. (Table 1). 

The use of thermomorphic systems has recently been studied as a way of achieving catalyst separation in homogeneous catalysis. For example, a biphasic hydroformylation catalyst system was developed to take advantage of the unusual solvent characteristics of perfluorocarbons combined with typical organic solvents (4). Fluorous/organic mixtures such as perfiuoromethylcyclohexane... 

The remarkable strength of some XBs allows them to prevail over HBs in identifying the modules to be involved in self-assembly. For instance, in experiments of competitive co-crystal formation, a dipyridyl derivative prefers to co-crystallize with XB donors rather than HB donors and the same occurs for NjNjN jN -lclramclhylclhylcncdiaminc (TMEDA) [36]. In solution, solute-solute intermolecular HBs are considerably diminished if a strong XB donor co-solute is added. If haloperfluorocarbons (halo-PFCs) are used, the HB breaking potency increases moving from perfluorocarbons to chloro-, bromo-, and iodoperfluorocarbons [37-43], perfectly consistent with the order of the increasing XB donor ability of the halo-PFCs co-solutes, hi aque-... 

Very powerful greenhouse gases that are not naturally occurring include hydrofluorocarbons (HFCs), perfluorocarbons (PFCs), and sulfur hexafluoride (SF6), which are generated in a variety of industrial processes. 

The chemical shifts of secondary CF2 groups within perfluorocarbons decrease modestly (less shielding) as the neighboring fluorocarbon groups become more branched, i.e., change from CF3 to CF2Rf to CF(Rf)2, as exemplified by the examples in Scheme 6.24. 

Scheme 6.26 provides chemical shifts for all of the fluorines in a representative group of perfluorocarbons. The various environments exhibited should allow one to estimate the chemical shift for almost any fluorine in a perfluorocarbon system. The fluorine chemical shifts of four-, five- and six-membered ring perfluoroalicyclics are quite consistently in the range of -133 to -134 ppm, but as usual, fluorines on a cyclopropane ring appear at a much higher field than those of other fluorinated alicyclics, perfluorocyclopropane having a chemical shift of -159 ppm. 

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