Chlorosulfonic acid poly

The most common way to modify aromatic polymers for application as a PEM is to employ electrophilic aromatic sulfonation. Aromatic polymers are easily sulfonated using concentrated sulfuric acid, fuming sulfuric acid, chlorosulfonic acid, or sulfur trioxide (or complexs thereof). Postmodification reactions are usually restricted due to their lack of precise control over the degree and location of functionalization, the possibility of side reactions, or degradation of the polymer backbone. Regardless, this area of PEM synthesis has received much attention and may be the source of emerging products such as sulfonated Victrex poly (ether ether ketone). 

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). 

Solutions of poly(l,4-phenylene-2,6-benzobisthiazole), PBT, exhibit an isotropic to nematic phase transition in a variety of solvents including methane sulfonic acid, MSA, chlorosulfonic acid, CSA, and poly phosphoric acid, PPA (1-4). In the latter case the transition occurs over a range of water -P2O5 compositions. In these acids the polymer, with repeating unit... 

Examples are the sulfonating of polyethylene film with chloro-sulfonic acid (60) the sulfonating of sheets of phenolformaldehyde resin (77) the treatment of a film consisting of polystyrene and polyvinylchloride with concentrated sulfuric acid (4) the sulfonating of films consisting of aliphatic vinylpolymers with chlorosulfonic acid (125) the sulfonating of copolymers of a monovinyl- and a polyvinyl compound (30). Also are used copolymers of aromatic monovinyl-compounds and linear aliphatic polyene hydrocarbons (3) copolymers of an unsaturated aromatic compound and an unsaturated aliphatic compound (76), and of reaction products of poly olefines and partially polymerized styrene (173). 

Chlorinated, sulfonated, chlorosulfonated or epoxidized polymers, homopolymers and copolymers of functionalized monomers, e.g. poly(methacryl aldehyde), poly(2,3-epoxypropyl acrylate), poly(4-vinylphenol), poly(propylene-co-10-unde-cene-l-ol), poly(butadiene-co-methacryl aldehyde), poly(butadiene-co-acrylic acid), poly(ethylene-co-alkyl acrylate), poly(alkyl acrylate-co-2,3-epoxypropyl acrylate), poly(alkyl acrylate-co-maleic anhydride), poly(styrene-co-4-vinylbenzyl chloride)... 

A method for the preparation of organosilicon sulphoacids without the necessity for synthesis of a monomer with HSO3 groups was also described [23-25]. It consisted of oxidation of pre-synthesized PMPS by potassium permanganate or the treatment of poly(phenyl-benzyl-2- phenylethyl)siloxanes by chlorosulfonic acid with - CHCI3 as a solvent. 

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... 

The chemical structures of sulfonated poly(4-phenoxybenzoyl-l,4-phenyl-ene) (S-PPBP) (1), poly(p-xylylene) (S-PPX) (2), poly(phenylene sulfide) (S-PPS) (3), poly(phenylene oxide) (S-PPO) (4), poly(ether ether ketone) (S-PEEK) (5), poly(ether ether sulfone) (S-PEES) (6), arylsulfonated poly(ben-zimidazole) (S-PBl) (7) sulfonated polyphenylquinoxiiline (S-PPQ) (8) and sulfonated phenoxy polyperyleneimide (PSPPI) (9) are shown below. ACPs are sulfonated using common sulfonating agents [82-85]. In particular, PEEK can be sulfonated in concentrated sulfuric acid [50], chlorosulfonic acid [86], SO3 (either pure or as a mixture) [53,65,86,87], a mixture of methanesulfonic acid with concentrated sulfuric acid [88] and acetyl sulfate [89,90]. 

When polystyrene is sulfonated in chlorinated hydrocarbons with a complex of dioxane-SOs, the polymer precipitates from solution at low concentrations. Complexes of ketones with SO3 can also be used to sulfonate polystyrene in halogenated solvents. The ratio of sulfonation is more favorable for poly(vinyl toluene) than it is for polystyrene at the same conditions. Also, sulfur dioxide swells polystyrene. The polymer can be sulfonated in this medium with sulfur trioxide or with chlorosulfonic acid. Polystyrene, sulfonated in CS2 with aluminum chloride catalyst, is water insoluble in a free acid form. ... 

M.H. Jeong, K.S. Lee, Y.T. Hong, J.S. Lee, Selective and quantitative sulfonation of poly(arylene ether ketone)s containing pendant phenyl rings by chlorosulfonic acid, J. Memb. Sci. 314 (1-2) (2008) 212-220. 

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... 

In order to prepare advanced molecules of poly(arylene ether sulfones) for fuel cell apphcations without sacrificing their excellent physical properties, Noshay and Robeson developed a mild sulfonation procedure for the commercially available bisphenol-A-based poly(ether sulfone) [62,63]. The sulfonation agents that have been used for this polymer modification are chlorosulfonic acid and a sulfur trioxide-triethyl phosphate complex. Recently, Kerres and co-workers [102] reported an alternative sulfonation process of commercial polysulfone based on a series of steps, including metalation-sulfmation-oxidation reactions. 

In the chlorosulfonation 344 to 345 (Equation 109), the large steric size of the acetamido group effectively precludes o-sulfonation, so the p-sulfonyl chloride is essentially the sole product isolated. Studies of the chlorosulfonation of acetanilide 344 with excess chlorosulfonic acid (five equivalents) in the temperature range 0 to 100 °C indicated that the optimium temperature for the production of the monosulfonyl chloride 345 was 55-60 C. Some disulfonation occurred > 40 °C, poly sulfonation > 70 °C and even at 100 C (2 hours), die reaction gave no sulfone. ... 

Alkanes (C1-C5) can be polymerized by treatment with a combination of a strong Lewis acid and a strong Bronsted acid. For example, n-pentane, by reaction with a mixture of chlorosulfonic acid and antimony pentafluoride at 30 °C (18 hours), gave oligomeric branched poly-n-pentane." Some of die polymers derived from the lower alkanes were useful as petrol additives."... 

Poly-/>-phenylene (PPP), after doping with a mixture of antimony pentachloride and chlorosulfonic acid, had a greatly increased electrical conductivity due to the formation of a charge-transfer complex. The term doping refers to the addition of an impurity to a material to enhance its physical properties. 

Poly(phenylene oxide) is stablized by a reaction with chlorosulfonic acid and poly(aryl ether) resins are sulfonated by a mixture of chlorosulfonic acid and a silyl halide followed by base-catalysed cleavage of the silyl group. Antistatic polyoxyphenylenes were obtained by surface sulfonation with a saturated solution of chlorosulfonic acid in n-hexane for 25-30 minutes. ... 

Poly-3,5-dimethylphenyl ether is sulfonated by chlorosulfonic acid, the sulfonated polymer was cast from a 2-10% methanolic solution to give negatively charged membranes with an ion-exchange capacity of up to 5 mequiv. g which can be used in desalination. ... 

The sulfonation of polyethersulfone with sulfuric and chlorosulfonic acid has been investigated experiments demonstrated that the degree of sulfonation increased with time and temperature. The resultant sulfonated material functions as a polymer electrolyte with an ion-exchange equivalent of 800-5000 gmol . Formaldehyde can be cationically polymerized at low temperatures by strong acids, e.g. chlorosulfonic acid in n-hexane, while trioxan is polymerized to poly(oxymethylene) by heating at 65 °C in the presence of a catalytic amount of chlorosulfonic acid. ... 

Polyketones are sulfonated by reaction with chlorosulfonic acid (see Chapter 5, p 162) and sulfonated aromatic polyether-polyketones have been obtained by treatment with mixtures of sulfur trioxide and chlorosulfonic acid. The sulfonated polymers are compression mouldable at high temperatures. Poly(arylether ketone) fibres of good dyeability were produced by treating the fibres with chlorosulfonic acid, sulfuric acid or sulfur trioxide. ... 

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