Sulfonated polymers

The aromatic sulfone polymers are a group of high performance plastics, many of which have relatively closely related stmctures and similar properties (see Polymers containing sulfur, polysulfones). Chemically, all are polyethersulfones, ie, they have both aryl ether (ArOAr) and aryl sulfone (ArS02Ar) linkages in the polymer backbone. The simplest polyethersulfone (5) consists of aromatic rings linked alternately by ether and sulfone groups. 

The first aromatic sulfone polymer produced commercially was introduced as Bakelite polysulfone but now is sold by Union Carbide under the trade name Udel. It is made by reaction of the disodium salt of bisphenol A (BPA) with 4,4 -dichIorodiphenyl sulfone in a mixed solvent of chlorobenzene and dimethyl sulfoxide (eq. 12). 

PoIysuIfonyIa.tlon, The polysulfonylation route to aromatic sulfone polymers was developed independendy by Minnesota Mining and Manufacturing (3M) and by Imperial Chemical Industries (ICI) at about the same time (81). In the polymerisation step, sulfone links are formed by reaction of an aromatic sulfonyl chloride with a second aromatic ring. The reaction is similar to the Friedel-Crafts acylation reaction. The key to development of sulfonylation as a polymerisation process was the discovery that, unlike the acylation reaction which requires equimolar amounts of aluminum chloride or other strong Lewis acids, sulfonylation can be accompHshed with only catalytic amounts of certain haUdes, eg, FeCl, SbCl, and InCl. The reaction is a typical electrophilic substitution by an arylsulfonium cation (eq. 13). 

An elegant synthesis method which is specific to sulfone polymers containing phenyl—phenyl linkages (such as PPSF) is the nickel-catalysed coupling of aryl dihahdes. The scheme for this synthesis involves a two-step process. First, an aromatic dihaUde intermediate is formed which carries the backbone features of the desired polymer. This aromatic dihahde intermediate is then self-coupled in the presence of sero-valent nickel, triphenylphosphine, and excess sine to form the biphenyl- or terphenyl-containing polymer. AppHcation of this two-step scheme to PPSF can be depicted as follows ... 

The sulfonic acid moiety has been iacorporated iato a variety of nonfluofinated polymeric materials (111). Chain-end sulfonated polymers are produced by the reaction of sultones with polymeric organolithiums (112). Polymeric sulfonic acids such as these are iacorporated ia positive-working photoresist compositions (113). 

Modification of the membranes affects the properties. Cross-linking improves mechanical properties and chemical resistivity. Fixed-charge membranes are formed by incorporating polyelectrolytes into polymer solution and cross-linking after the membrane is precipitated (6), or by substituting ionic species onto the polymer chain (eg, sulfonation). Polymer grafting alters surface properties (7). Enzymes are added to react with permeable species (8—11) and reduce fouling (12,13). 

This is an ion-exchanger like the sulfonated polymer. The siUca surface can also be functionalized with phosphine complexes when combined with rhodium, these give anchored complexes that behave like their soluble and polymer-supported analogues as catalysts for olefin hydrogenation and other reactions ... 

In 1988, the United States consumption of monochlorobenzene was 120 million kilograms 42% for the production of nitrochlorobenzenes, 28% for solvent uses, and the remaining 30% for other appHcations such as diphenyl ether, ortho- and i ra-phenylphenols, sulfone polymers, and diphenyldichlorosilane, an intermediate for specialty siHcones. 

AA/COPS aciylic acid/sodium 3-allyloxy-2-hydroxy-propane sulfonate (polymer)... 

AA/SA AA/SA/NI AA/SA/SSS sulfonate (polymer) aciylic acid/sulfonic acid aciylic acid/sulfonic acid/ nonionic (polymer) aciylic acid/sulfonic acid/sodium styrene sulfonate acrylic acid/sulfonic acid/substituted acrylamide (polymer)... 

Polydrill is a sulfonated polymer for filtration control in water-based drilling fluids [1775]. Tests demonstrated the product s thermal stability up to 200° C and its outstanding electrolyte tolerance. Polydrill can be used in NaCl-saturated drilling fluids as well as in muds containing 75,000 ppm of calcium or 100,000 ppm of magnesium. A combination of starch with Poly drill was used successfully in drilling several wells. The deepest hole was drilled with 11 to 22 kg/m of pregelatinized starch and 2.5 to 5.5 kg/m of Polydrill to a depth of 4800 m. Field experience with the calcium-tolerant starch/Polydrill system useful up to 145° C has been discussed in detail [1774]. 

A water-soluble polymer of monoallylamine can be used in conjunction with a sulfonated polymer, such as a water-soluble lignosulfonate, condensed naphthalene sulfonate, or sulfonated vinyl aromatic polymer, to minimize fluid loss from the slurry during well cementing operations [1510,1511]. The polymer... 

Melamine sulfonate polymer, vinyl sulfonate polymer. [1250]... 

A. Audibert and J. F. Argillier. Thermal stability of sulfonated polymers. In Proceedings Volume, pages 81-91. SPE Oilfield Chem Int Symp (San Antonio, TX, 2/14-2/17), 1995. 

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... 

One of the first fictional fluoropolymers was poly-1,2,2-trifluorostyrene. On one hand, it has much better oxidation and chemical resistance in comparison with common hydrocarbon polymers and, on the other hand, a wide range of functional groups can be attached to the aromatic ring. A sulfonated polymer was successfully used as a membrane for fuel cells by General Electric Co.3... 

Sulfonated polyesters, 23 536 Sulfonated polymers, 23 534-536 Sulfonated polystyrene membranes, 23 720 Sulfonated products... 

Sulfonation equipment, 23 515 Sulfonation operations, industrial changes affecting, 23 515-516 Sulfonation plant gas effluents, 23 552 Sulfonation plants, operations of, 23 552 Sulfonation polymer, derivation by, 13 546 Sulfonation processes... 

Blends of sulfonated polymers and polymers containing basic moieties have also been made. Represented schematically in Figure 3.35, ionic cross-linking between acidic and basic sites generally leads to improved mechanical and thermal stabilities. strong interactions within these blends results... 

Schuster, M., Kreuer, K. D., Anderson, H. T. and Maier, J. 2007. Sulfonated poly(phenylene sulfone) polymers as hydrolytically and thermooxidatively stable proton conductors. Macromolecules 40 598-607. 

Ogato, N. and Rikukawa, M. 1995. Sulfonated polymers for solid polymer electrolytes. US Patent 5,403,675. 

Jung, B., Kim, B. and Yang, J. M. 2004. Transport of methanol and protons through partially sulfonated polymer blend membranes for direct methanol fuel cell. Journal of Membrane Science 245 61-69. 

Sulfonated poly(4-substituted benzoyl-1,4-phenylene) homopolymers and copolymers using concentrated sulfuric acid or fuming sulfuric acid have been shown to form sulfonated polymers with variable degrees of sulfonation. To improve film formation of the sulfonated polyphenylenes, multiblock copolymers have been synthesized by reacting a more flexible poly(arylene ether sulfone) with sulfonated poly-phenylenes. ... 

Allcock s research led to the development of poly-phosphazene-based PEMs by his small molecule studies of the sulfonation of cyclic trimeric phosphazenes and the surface chemistry of polyphosphazene macromolecules. In a 1993 report, he described the sulfonation of aminophosphazenes with 1,3—propanesultone. While these specific materials are not necessarily ideal as PEMs, this study demonstrated a novel technique for creating sulfonated polyphosphazene materials that may provide more control over the sulfonated polymer product than wholesale sulfonation of a base polymer by a strong sulfonating agent. 

Solution-cast membranes (100—200 /urn in thickness) from sulfonated polymers with an ion exchange... 

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