Perfluorinated Polymer Resin Acids

Perfluorinated Polymer Resin Acids. A convenient solid perfluori- 

Nafion membrane materials were originally developed for electrochemical applications.155 The acid strength (—Ho) is estimated to be between 11 and 13156 that is, the acidity of Nafion is comparable to that of concentrated sulfuric acid. In these systems, the sulfonic acid group is attached to a CF2 or CF group in a perfluorinated backbone. 

Other perfluorinated ionomer membranes, chemically very similar to Nafion, are also available commercially. Aciplex, manufactured by the Asahi Chemical Company, is very similar to Nafion, except that it has perfluoropropanesulfonic acid side chains. Flemion (Asahi Glass Company), in contrast, possesses perfluorobutanoic acid functions. 

Two significant drawbacks of Nafion-H in catalytic applications are its very low surface area (0.02 m2 g ) and the hindered accessibility of the active sites (sulfonic acid groups) located inside the pockets of the polymeric backbone. Consequently, the specific activity of Nafion, namely, the number of reacting molecules per unit weight, 

The high acidity of the unique sulfonic acid function of Nafion can also be utilized by tethering perfluoroalkanesulfonic acid groups to the surface of various silicas. Two approaches have been described to prepare such hybrid organic-inorganic materials. The grafted materials 3 have been prepared by reacting preformed silica materials (MCM-41, SBA-15) with sultone 2 [Eq. (2.31)].165 Co-condensation of tetraethoxy-silane with 4 in the presence of dodecylamine template, in turn, furnished the HMS-based material 5 [Eq. (2.32)].166,167 

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Polymeric resin sulfonic acids including sulfonic acid resins complexed with Lewis acids and perfluorinated polymer resin acids (Nafion-H and Nafion-silica nanocomposites). 

A.2.2. Perfluorinated Polymer Resin Acids. A convenient solid perfluori-... 

Chemical Properties. A combination of excellent chemical and mechanical properties at elevated temperatures result in high performance service in the chemical processing industry. Teflon PEA resins have been exposed to a variety of organic and inorganic compounds commonly encountered in chemical service (26). They are not attacked by inorganic acids, bases, halogens, metal salt solutions, organic acids, and anhydrides. Aromatic and ahphatic hydrocarbons, alcohols, aldehydes, ketones, ethers, amines, esters, chlorinated compounds, and other polymer solvents have Httle effect. However, like other perfluorinated polymers,they react with alkah metals and elemental fluorine. 

Nafion, a perfluorinated sulfonated polymer, is a typical example of an ion-exchangeable resin with high promise as a catalyst support. Its properties are significantly different from those of common polymers (stability towards strong bases, and strong oxidizing and reducing acids and thermal stability up to at least 120 °C if the counter ion is a proton, and up to 200-235 °C if it is a... 

Nafion-H, a perfluorinated sulfonic acid resin, is another strongly acidic solid that has been explored as alkylation catalyst. Rprvik et al. (204) examined unsupported Nafion-H with a nominal surface area of 0.2 m2/g (surface area of a swellable polymer is difficult to define) in isobutane/2-butene alkylation at 353 K and compared it with a CeY zeolite. The zeolite gave a better alkylate and higher conversion than Nafion-H, which produced significant amounts of octenes and heavy-end products. The low surface area of the resin and questions about the accessibility of the sulfonic acid groups probably make the comparison inadequate. 

Major areas of application are in the field of aqueous electrochemistry. The most important application for perfluorinated ionomers is as a membrane separator in chloralkali cells.86 They are also used in reclamation of heavy metals from plant effluents and in regeneration of the streams in the plating and metals industry.85 The resins containing sulfonic acid groups have been used as powerful acid catalysts.87 Perfluorinated ionomers are widely used in worldwide development efforts in the held of fuel cells mainly for automotive applications as PEFC (polymer electrolyte fuel cells).88-93 The subject of fluorinated ionomers is discussed in much more detail in Reference 85. 

A convenient solid of perfluorinated-sulfonic acid can be made readily from DuPont s commercially available Nafion brand ion membrane resins. Powder granules of the 1200-EW polymer, Nafion 501, have been used most frequently in catalytic applications the price in the K+ form of the perfluorosulfonic salt, 501X, was 650/kg in 1981. Because only the potassium salt derivative is commercially available, the salt is converted to the free sulfonic acid by treatment with mineral acid. A standard procedure for the conversion is described below. This procedure also serves to regenerate the resin in various catalytic cycles. 

A slurry of 100 g of perfluorinated ion-exchange polymer in 130 ml concentrated HC1 (36%) and 400 ml distilled water is stirred at 50-60°C for 2 h. The aqueous acid is decanted away from the resin and fresh acid/ water solution added. The mixture is heated and stirred for another 2 h. After the third exchange, the resin is isolated by filtration and washed with distilled water until the washings are neutral. The resin is dried in a vacuum oven under N2 at — I I0°C for 6 h. Conversions 95% are obtained with this procedure. 

Polymer-bound reagents for silylation have been reported. Murata and Noyori treated Nation, a perfluorinated resin-sulfonic acid, with trimethylsilyl chloride to afford a polymer-bound trimethylsilyl ester that functions as a polymer-bound equivalent of trimethylsilyl trifluoromethanesulfonate, converting alcohols, eth-anethiol and diethylamine into the corresponding silylated compounds in high yields (Scheme 6.16) [70]. Acetic acid could also be silylated, albeit with moderate conversion. The corresponding polystyrene-bound reagent is commercially available. 

Polymer-supported tetrabromooxomolybdate(V) was claimed to be a heterogeneous catalyst for alcohol oxidations with TBHP . However, it seems likely that molybdenum is leached from the surface and the observed catalysis may be, at least partially, homogeneous in nature. The same applies to Cr(III) and Ce(IV) catalysts supported on a perfluorinated sulfonic acid resin (Nafion K) which catalyze the oxidation of alcohols with TBHP . Similarly, vanadium-pillared montmorillonite clay (V-PILC) ° and a zeolite-encapsulated vanadium picolinate complex were shown to catalyze... 

In general, the preparation of ionomers is a straightforward procedure. The particular acid group of interest can be introduced onto the hydrocarbon backbone either by direct copolymerization or post-synthesis reaction. The following five important groups of ionomers illustrate the various methods of preparation. These ionomer families are ethylene-based materials, ionic elastomers, modified polystyrenes, perfluorinated resins and halato-telechelic polymers. 

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