Sulfonic acids, ion-exchange

The ratio of reactants had to be controlled very closely to suppress these impurities. Recovery of the acrylamide product from the acid process was the most expensive and difficult part of the process. Large scale production depended on two different methods. If soHd crystalline monomer was desired, the acrylamide sulfate was neutralized with ammonia to yield ammonium sulfate. The acrylamide crystallized on cooling, leaving ammonium sulfate, which had to be disposed of in some way. The second method of purification involved ion exclusion (68), which utilized a sulfonic acid ion-exchange resin and produced a dilute solution of acrylamide in water. A dilute sulfuric acid waste stream was again produced, and, in either case, the waste stream represented a... 

Even ia 1960 a catalytic route was considered the answer to the pollution problem and the by-product sulfate, but nearly ten years elapsed before a process was developed that could be used commercially. Some of the eadier attempts iacluded hydrolysis of acrylonitrile on a sulfonic acid ion-exchange resia (69). Manganese dioxide showed some catalytic activity (70), and copper ions present ia two different valence states were described as catalyticaHy active (71), but copper metal by itself was not active. A variety of catalysts, such as Umshibara or I Jllmann copper and nickel, were used for the hydrolysis of aromatic nitriles, but aUphatic nitriles did not react usiag these catalysts (72). Beginning ia 1971 a series of patents were issued to The Dow Chemical Company (73) describiag the use of copper metal catalysis. Full-scale production was achieved the same year. A solution of acrylonitrile ia water was passed over a fixed bed of copper catalyst at 85°C, which produced a solution of acrylamide ia water with very high conversions and selectivities to acrylamide. 

ButylatedPhenols and Cresols. Butylated phenols and cresols, used primarily as oxidation inhibitors and chain terrninators, are manufactured by direct alkylation of the phenol using a wide variety of conditions and acid catalysts, including sulfuric acid, -toluenesulfonic acid, and sulfonic acid ion-exchange resins (110,111). By use of a small amount of catalyst and short residence times, the first-formed, ortho-alkylated products can be made to predominate. Eor the preparation of the 2,6-substituted products, aluminum phenoxides generated in situ from the phenol being alkylated are used as catalyst. Reaction conditions are controlled to minimise formation of the thermodynamically favored 4-substituted products (see Alkylphenols). The most commonly used is -/ fZ-butylphenol [98-54-4] for manufacture of phenoHc resins. The tert-huty group leaves only two rather than three active sites for condensation with formaldehyde and thus modifies the characteristics of the resin. 

Catalysts used are usually acids such as sulfuric acid, -toluenesulfonic acid, sulfonic acid ion-exchange resins, and others. The water from the reaction of the citric acid and the alcohol is continuously removed as the azeotrope until no more water is formed. At this point, the reaction is usually complete and the solvent and any excess alcohol is distilled off under mild vacuum. The catalyst is neutralized using carbonate or sodium hydroxide, leaving a cmde product. If a pure product is desired, the ester can be distilled under high vacuum. 

Other Polymerization Methods. Although none has achieved commercial success, there are a number of experimental alternatives to clay-catalyzed or thermal oligomeriza tion of dimer acids. These iaclude the use of peroxides (69), hydrogen fluoride (70), a sulfonic acid ion-exchange resia (71), and corona discharge (72) (see Initiators). 

Commercially, sulfonic acid ion-exchange resins are used in fixed-bed reactors to make these tertiary alkyl ethers (14). Since the reaction is very selective to tertiary olefins and also reversible, a two-step procedure is also used to recover commercially pure tertiary olefins from mixed olefin process streams. The corresponding tertiary alkyl ether is produced in the olefin mixture and then easily separated from the unreacted olefins by simple fractionation. The reaction is then reversed in a second step to make a commercially pure tertiary olefin, usually isobutylene or isoamylene. 

The same authors later on presented their results of the epoxidation of various cyclic and acyclic olefins employing a heterogeneous catalyst with an oxovanadium(IV) ion incorporated on a sulfonic acid ion-exchange resin and TBHP as oxidant . Selectivities... 

Np through Lr are all prepared artificially by bombardment with neutrons and/or light element ions (He-4, B-10, B-11, C-12,0-16,0-18, Ca-48, Fe-56). Some routes are presented in Table 18.1. The elements have been separated from the targets and other product species by redox reactions, ion exchange, and solvent extraction. In a typical separation, a sulfonic acid ion exchange resin is placed in a column, the tripositive ions of Am through Lr are poured into the column where they are taken up, then the column is eluted with a solution of ammonium a-hydroxybutyrate. As elution proceeds, the An+ ions come off in this order Lr-Md-Fm-Es-Cf-Bk-Cm-Am. They are detected by the distinctive energies of their radioactive emissions. 

Other Polymerization Methods. Experimental allemalives include the use of peroxides, hydrogen fluoride, a sulfonic acid ion-exchange resin, and corona discharge. 

HNF2 reacts with saturated and unsaturated mono- and diacetals at ambient temperature to 100°C (250) and also smoothly in the presence of a sulfonic acid ion-exchange resin (Amberlyst-15) (140, 276) to give a-difluoroamino ethers (140). These compounds react with a second molecule of HNF2 in the presence of sulfuric acid to give bis(difluoro-amino) derivatives (140). 

Propyl sulfonic acid Ion exchange/normal-phase/reversed-phase... 

The objective was to detennine how the yield of the ether depends on the reaction temperature and the amount of acid catalyst (Nation ). The catalyst is a strongly acidic perfluorinated sulfonic acid ion-exchange resin. The levels of the variables are given in Table 12.1, and the experimental design and yields obtained are given in Table 12.2. The yields obtained after 10 h are given. 

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