Poly sulfonation reaction

Poly(arylether ketone), conducting, 7 524 Poly(aryl ether ketone)s, sulfonation reaction of, 23 717-718 Poly(di-n-alkylsilanes), thermochromic materials, 6 619... 

Al-Omran and Rose controlled the location and extent of sulfonation on poly (ary lene ether) backbones by copolymerizing 4,4 -dichlorodiphenyl sul-fone, durohydroquinone, and hydroquinone to form random copolymers, where only the hydroquinone residue would be expected to be susceptible to sulfonation by sulfuric acid. Although these authors observed sulfonation at positions other than at the desired hydroquinone locations, designing sulfonation sites into a polymer backbone remains an attractive strategy for producing copolymers with known structures. This allows the chemical structure and composition of the material to dictate the extent of sulfonation rather than trying to externally control sensitive and sometimes unpredictable macromolecu-lar sulfonation reactions. 

Kobayashi et al. reported sulfonation of poly(4-phenoxybenzoyl-1,4-phenylene) (PPBP) with sulfuric acid and compared the data with those of sulfonated PEEK. As reported, the authors employed sulfuric acid for the sulfonation reaction to avoid or at least minimize degradation of the polymer by chlorosulfonic acid or fuming sulfuric acid (Figure 27). 

Figure 27. Sulfonation reaction of poly(4-phenoxybenzoyl-1,4-phenylene). ...

The sulfonation reaction is controllable, but one report indicates that reaction of the backbone nitrogen occurs before sulfonation on the pendent ring with poly [(3-methylphenoxy) (phenoxy) phosphazene], as shown in Figure 38. ° ... 

Other poly(sulfones) can be obtained similarly to poly(sulfides) by polycondensation. Many of these sulfones also contain an ether group in the backbone. A typical reaction for the formation of a poly(ether sulfone) is that of 4,4 -dichlorodiphenylsulfone with 4,4 -sulfonyldiphenol or bisphenol S in the presence of K2CO3 (as a base) as shown below ... 

Morawetz, H., and Vogel, B. Catalysis of ionic reactions by polyelectrolytes, reaction of pentaamminechlorocobalt(iii) ion and pentaamminebromocobalt(iii) ion with mercuric ion in poly(sulfonic acid) solution. Journal of the American Chemical Society, 1969, 91, No. 3, p. 563-568. 

PS-fc-poly(4-f-butylstyrene)]n, (PS-fi-PfBuS) star-block copolymers were prepared by anionic polymerization and sequential addition of monomers with DVB as the linking agent for the formation of the star structure [156]. The functionality of the stars ranged between 10 and 20. Selective sulfonation of PS blocks was subsequently performed using the sulphur trioxide and triethyl phosphate complex in 1,2-dichloroethane, followed by neutralization with sodium methoxide. For this reason DVB was used for the linking reaction instead of chlorosilanes, where a better control could be achieved. DVB stars are more robust and the sulfonation reaction proceeds without cleavage of the arms from the star structure. 

Some oxidoreductases require expensive cofactors, such as NADH. This requires continuous regeneration of the cofactor in a separate enzymatic reaction using a sacrificial substrate. Nanofiltration membranes have been used to separate the two enzyme systems.256 A sulfonated poly-sulfone nanofiltration was used in the reduction of fructose to mannitol, using glucose to gluconolactone to regenerate the NADH. 

Matthews and Strange [42] reported a similar reaction of isoprene with sulfur dioxide in the presence of hydrogen chloride. Seyer and King [Id] reported that 1,3-cyclohexadiene reacted with sulfur dioxide to give a white amorphous compound, as earlier reported by Hofmann and Damm [43]. 2-Methyl- and 4-methyl-1,3-pentadiene were reported by Morris and Van Winkle [44] to react with sulfur dioxide to yield a cyclic sulfone and some hydrocarbon polymer. Starkweather [45] in 1945 reported that chloroprene (2-chloro-l,3-butadiene) reacted with sulfur dioxide in an emulsion system to give a copolymer. Poly-sulfone is the major product when radical initiators are used. Cyclic products predominate when radical inhibitors (hydroquinone) or temperatures in excess of the ceiling temperature are used. For example ... 

Poly(biphenyl ether sulfone)s can be prepared, with carbonates or with the alkali metal hydroxides as activators. In the carbonate method, the poly(sulfone)s are prepared by the reaction of equimolar amounts of dihydroxy aromatic compounds and dihalodiaryl sulfones. Dihydroxy aromatic compounds are BP, 4,4 -dihydroxydiphenyl sulfone, hydroquinone, bisphenol A. Dihalodiaryl sulfones, are 4,4 -dichlorodiphenyl sulfone or 4,4 -difluorodiphenyl sulfone. 0.5 to about 1.0 mole of an alkali metal carbonate per mole of hydroxyl group is added. The condensation is conducted as azeotropic condensation, at a temperature of 210-300°C up to 15 hours. 

Rader, H. J., Spickermann, and Mullen, K., MALDI-TOF Mass Spectrometry in Rolymer Analytics 1. Monitoring the Rolymer-Analogous Sulfonation Reaction of Poly(Styrene), Macromol. Chem. Phys., 196, 3967, 1995. 

Sulfonated aromatic polymers have been widely studied as alternatives to Nafion due to potentially attractive mechanical properties, thermal and chemical stability, and commercial availability of the base aromatic polymers. Aromatic polymers studied in fuel cell apphcations include sulfonated poly(p-phenylene)s, sulfonated polysulfones, sulfonated poly(ether ether ke-tone)s (SPEEKs), sulfonated polyimides (SPIs), sulfonated polyphosphazenes, and sulfonated polybenzimidazoles. Representative chemical structures of sulfonated aromatic polymers are shown in Scheme 3. Aromatic polymers are readily sulfonated using concentrated sulfuric acid, fuming sulfuric acid, chlorosulfonic acid, or sulfur trioxide. Post-sulfonation reactions suffer from a lack of control over the degree and location of functionalization, and the... 

Poly(arylene ether)s are one of the most studied aromatic polymers for the sulfonation reactions. Poly(arylene ether)s include poly(phenylene ether), poly(arylene ether ketone), poly(arylene ether ether ketone), and poly(arylene ether sul-fone). These polymers contain electron-rich phenylene rings linked by ether bonds, which are susceptible for the sulfonation reactions with typical sulfonating reagents such as sulfuric acid, chlorosulfonic acid, or sulfur trioxide. The first attempt was the sulfonation of poly(2,6-dimethyl-phenylene ether) (PPO) by General Electric in 1960s [4]. Since then, a number of... 

Miyatake et al. have combined two strategies in a single polymer architecture (multiblock copolymers containing sulfonic acid clusters in their hydrophilic blocks) [62]. They have successfully synthesized a series of multiblock poly (arylene ether sulfone ketone)s (SPESKs) containing fully sulfonated fluorenylidene biphenylene units (Fig. 7.23) [63, 64]. The well-controlled post-sulfonation reaction of the precursor polymers enabled preferential sulfonation on... 

Another dramatic example of the usefulness of DPE end-capping of polymeric organolithium compounds to promote efficient functionalization reactions is the sulfonation reaction using sultones [142]. A careful examination of the functionalization of poly(styryl)lithium with 1,3-propane sultone showed that the corresponding sulfonated polymer (see Eq. 32) was obtained in maximum yields of only 30% and 53% in benzene or tetrahydrofuran, respectively [142] ... 

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