Sulfonic acid, functionalization

Ion exchange resins based on poly(styrene-divinylbenzene) backbones display mixed mode retention mechanisms. The ion exchange functionality (sulfonic acid or carboxylic acid for cation exchangers and quartemary or primary, secondary, or tertiary amines for anion exchangers) contributes to the ionic mechanism and the backbone polymer to hydrophobic retention. This is exemplified... 

Freshly distilled SO3 added dropwise to a soln. of dimethyl sulfide in dichloroethane at 0-10°, warmed to room temp., 2,3-dimethyl-1,3-butadiene added, and stirred for 2 h at 65° — (E)-4-dimethylsulfonio-X3-dimethyl-2-butene-l-sulfonate. Y 71%. F.e.s. T.V. Popkova et al., Zh. Org. Khim. 24, 1160-5 (1988) functionalized sulfonic acid salts from sulfoniosulfonic acid betaines s. ibid. 25, 746-9 (1989). 

Despoponlos, A. Kopp, A. Simms, Q. Congruence of renal and hepatic excretory functions. Sulfonic acid dyes. Am. J. Physiol. 1971, 220, 1755-1758. 

The addition of a fugitive acid such as camphorsulfonic acid to styrene polymerizations contaminates the polymer with a substance that could lead to corrosion of equipment being used to process the polymer. To solve this problem, Dow researchers added vinyl functional sulfonic acids (eg, 2-sulfoethyl methacrylate) to the polymerization (175). The acid then becomes copolymerized into the polymer, thus immobilizing it. Also, they found that the addition of as low as 10 ppm... 

Previously, the enhancement of the device performance in ITO/polyaniline/MEH-PPV/Ca devices has also been observed (9). The metallic emeraldine salt form of PANI is prepared by doping and complexation with functionalized sulfonic acids (e.g. camphor sulphonic acid, CSA), yielding a conducting PANI-complex soluble in common organic solvents. Hence, based on the results obtained from our research, we conclude that the enhancement of the device performance in ITO/PANI/MEH-PPV/Ca devices is probably due to the fact that the CSA dopes the surface of MEH-PPV and subsequently eidiances the charge injection and lowers the device operating voltage. 

Cation exchange resins — gel type—strongly acidic—sulfonic acid functionality ... 

Cation exchange resin— -macroreticular type- — sulfonic acid functionality... 

Esters. Most acryhc acid is used in the form of its methyl, ethyl, and butyl esters. Specialty monomeric esters with a hydroxyl, amino, or other functional group are used to provide adhesion, latent cross-linking capabihty, or different solubihty characteristics. The principal routes to esters are direct esterification with alcohols in the presence of a strong acid catalyst such as sulfuric acid, a soluble sulfonic acid, or sulfonic acid resins addition to alkylene oxides to give hydroxyalkyl acryhc esters and addition to the double bond of olefins in the presence of strong acid catalyst (19,20) to give ethyl or secondary alkyl acrylates. 

Direct, acid catalyzed esterification of acryhc acid is the main route for the manufacture of higher alkyl esters. The most important higher alkyl acrylate is 2-ethyIhexyi acrylate prepared from the available 0x0 alcohol 2-ethyl-1-hexanol (see Alcohols, higher aliphatic). The most common catalysts are sulfuric or toluenesulfonic acid and sulfonic acid functional cation-exchange resins. Solvents are used as entraining agents for the removal of water of reaction. The product is washed with base to remove unreacted acryhc acid and catalyst and then purified by distillation. The esters are obtained in 80—90% yield and in exceUent purity. 

The main by-products of the Ullmaim condensation are l-aniinoanthraquinone-2-sulfonic acid and l-amino-4-hydroxyanthraquinone-2-sulfonic acid. The choice of copper catalyst affects the selectivity of these by-products. Generally, metal copper powder or copper(I) salt catalyst has a greater reactivity than copper(Il) salts. However, they are likely to yield the reduced product (l-aniinoanthraquinone-2-sulfonic acid). The reaction mechanism has not been estabUshed. It is very difficult to clarify which oxidation state of copper functions as catalyst, since this reaction involves fast redox equiUbria where anthraquinone derivatives and copper compounds are concerned. Some evidence indicates that the catalyst is probably a copper(I) compound (28,29). 

Softening Cation Polystyrene matrix Sulfonic acid functional groups Nad... 

The antiparasitic drug clorsulon (206), contains a rather unusual trichloroethylene group. This function is established early in the syntliesis by treatment of the perhalogenated compound 203 obtained from reduction of 202 with iron powder. Chlorosulfonation of 204 by means of chloro-sulfonic acid, followed by conver.sion of. sulfonyl chloride 205 to the amide, gives clorsulon (206) 153],... 

Reactive compatibilization of engineering thermoplastic PET with PP through functionalization has been reported by Xanthos et al. [57]. Acrylic acid modified PP was used for compatibilization. Additives such as magnesium acetate and p-toluene sulfonic acid were evaluated as the catalyst for the potential interchange or esterification reaction that could occur in the melt. The blend characterization through scanning electron microscopy, IR spectroscopy, differential scanning calorimetry, and... 

In addition to alkyl-substituted derivatives, soluble PPPs 6 are also known today containing alkoxy groups as well as ionic side groups (carboxy and sulfonic acid functions) [18]. Schliiter et al. recently described the generation of soluble PPPs decorated with densely packed stcrically demanding dendrons on the formation of cylindrically shaped dendrimers, so-called cylinder dendrimers ] 19]. 

The organic resin material is often a styrene divinylbenzene (DVB) copolymer in a network or matrix, to which are attached functional groups such as a sulfonic acid, carboxylic acid, and quaternary ammonium. The nature of these groups determines whether the resin is classified as a strong/weak acid (cation resin) or strong/weak base (anion resin) ion-exchanger. 

Some acrylic acid copolymers are promoted as having a very wide range of functions that permit them to act as calcium phosphate DCAs, barium sulfate antiprecipitants, particulate iron oxides dispersants, and colloidal iron stabilizers. One such popular copolymer is acrylic acid/sulfonic acid (or acrylic acid/ 2-acrylamido-methylpropane sulfonic acid, AA/SA, AA/AMPS). Examples of this chemistry include Acumer 2000 (4,500 MW) 2100 (11,000 MW) Belclene 400, Acrysol QR-1086, TRC -233, and Polycol 43. 

Acrylic acid terpolymers have appeared on the market in recent years. With their broad spectrum of functions, they offer the potential for excellent waterside conditions. In particular, the terpolymers have proved to be very effective particulate iron oxides dispersants and colloidal iron stabilizers. Examples include acrylic acid/sulfonic acid/sodium styrene sulfonate (AA/SA/SSS), such as Good-Rite K781, K797, K798. A further example is acrylic acid/ sulfonic acid/substituted acrylamide (AA/SA/NI), such as Acumer 3100. 

Normally, reactive derivatives of sulfonic acids serve to transfer electrophilic sulfonyl groups259. The most frequently applied compounds of this type are sulfonyl halides, though they show an ambiguous reaction behavior (cf. Section III.B). This ambiguity is additionally enhanced by the structure of sulfonyl halides and by the reaction conditions in the course of electrophilic sulfonyl transfers. On the one hand, sulfonyl halides can displace halides by an addition-elimination mechanism on the other hand, as a consequence of the possibility of the formation of a carbanion a to the sulfonyl halide function, sulfenes can arise after halide elimination and show electrophilic as well as dipolarophilic properties. 

Sulfonic esters are most frequently prepared by treatment of the corresponding halides with alcohols in the presence of a base. The method is much used for the conversion of alcohols to tosylates, brosylates, and similar sulfonic esters. Both R and R may be alkyl or aryl. The base is often pyridine, which functions as a nucleophilic catalyst, as in the similar alcoholysis of carboxylic acyl halides (10-21). Primary alcohols react the most rapidly, and it is often possible to sulfonate selectively a primary OH group in a molecule that also contains secondary or tertiary OH groups. The reaction with sulfonamides has been much less frequently used and is limited to N,N-disubstituted sulfonamides that is, R" may not be hydrogen. However, within these limits it is a useful reaction. The nucleophile in this case is actually R 0 . However, R" may be hydrogen (as well as alkyl) if the nucleophile is a phenol, so that the product is RS020Ar. Acidic catalysts are used in this case. Sulfonic acids have been converted directly to sulfonates by treatment with triethyl or trimethyl orthoformate HC(OR)3, without catalyst or solvent and with a trialkyl phosphite P(OR)3. ... 

Weiss et al. [75] have synthesized Na and Zn salt of sulfonated styrene(ethylene-co-butylene)-styrene triblock ionomer. The starting material is a hydrogenated triblock copolymer of styrene and butadiene with a rubber mid-block and PS end-blocks. After hydrogenation, the mid-block is converted to a random copolymer of ethylene and butylene. Ethyl sulfonate is used to sulfonate the block copolymer in 1,2-dichloroethane solution at 50°C using the procedure developed by Makowski et al. [76]. The sulfonic acid form of the functionalized polymer is recovered by steam stripping. The neutralization reaction is carried out in toluene-methanol solution using the appropriate metal hydroxide or acetate. 

Sulfonic Acid Functionalization of Ordered Mesoporous Materials and Periodic Organosilicas... 

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