Impurities, resins

In 1924, Herrmann and Haenel added alkali to a clear alcohohc solution of polyvinyl acetate to saponify this polymeric ester from the experience with the saponification of monomeric vinyl acetate, they expected that some impure resinous precipitate would be produced. In contrast to their expectation, however, ivory-colored PVA was obtained [3]. It was remarkable—water-soluble PVA was obtained from hydrophobic polyvinyl acetate. 

After preparation, colloidal suspensions usually need to undergo purification procedures before detailed studies can be carried out. A common technique for charged particles (typically in aqueous suspension) is dialysis, to deal witli ionic impurities and small solutes. More extensive deionization can be achieved using ion exchange resins. 

The exchange resins 6nd application in (i) the purification of water (cation-exchange resin to remove salts, followed by anion-exchange resin to remove free mineral acids and carbonic acid), (ii) removal of inorganic impurities from organic substances, (iii) in the partial separation of amino acids, and (iv) as catalysts in organic reactions (e.g., esterification. Section 111,102, and cyanoethylation. Section VI,22). 

Properly end-capped acetal resins, substantially free of ionic impurities, are relatively thermally stable. However, the methylene groups in the polymer backbone are sites for peroxidation or hydroperoxidation reactions which ultimately lead to scission and depolymerisation. Thus antioxidants (qv), especially hindered phenols, are included in most commercially available acetal resins for optimal thermal oxidative stabiUty. 

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... 

In contrast to trace impurity removal, the use of adsorption for bulk separation in the liquid phase on a commercial scale is a relatively recent development. The first commercial operation occurred in 1964 with the advent of the UOP Molex process for recovery of high purity / -paraffins (6—8). Since that time, bulk adsorptive separation of liquids has been used to solve a broad range of problems, including individual isomer separations and class separations. The commercial availability of synthetic molecular sieves and ion-exchange resins and the development of novel process concepts have been the two significant factors in the success of these processes. This article is devoted mainly to the theory and operation of these Hquid-phase bulk adsorptive separation processes. 

Pharmaceutical. Ion-exchange resins are useful in both the production of pharmaceuticals (qv) and the oral adrninistration of medicine (32). Antibiotics (qv), such as streptomycin [57-92-17, neomycin [1404-04-2] (33), and cephalosporin C [61-24-5] (34), which are produced by fermentation, are recovered, concentrated, and purified by adsorption on ion-exchange resins, or polymeric adsorbents. Impurities are removed from other types of pharmaceutical products in a similar manner. Resins serve as catalysts in the manufacture of intermediate chemicals. 

Tetrahydronaphthalene [119-64-2] (Tetralin) is a water-white Hquid that is insoluble in water, slightly soluble in methyl alcohol, and completely soluble in other monohydric alcohols, ethyl ether, and most other organic solvents. It is a powerhil solvent for oils, resins, waxes, mbber, asphalt, and aromatic hydrocarbons, eg, naphthalene and anthracene. Its high flash point and low vapor pressure make it usehil in the manufacture of paints, lacquers, and varnishes for cleaning printing ink from rollers and type in the manufacture of shoe creams and floor waxes as a solvent in the textile industry and for the removal of naphthalene deposits in gas-distribution systems (25). The commercial product typically has a tetrahydronaphthalene content of >97 wt%, with some decahydronaphthalene and naphthalene as the principal impurities. 

The three types of rosin perform differently because of different distributions of resin acids, as well as different types and quantities of impurities. These differences are reflected in end-use performance. 

Black Liquor Soap Acidulation. Only two-thirds of a typical black Hquor soap consists of the sodium salts of fatty acids and resin acids (rosin). These acids are layered in a Hquid crystal fashion. In between these layers is black Hquor at the concentration of the soap skimmer, with various impurities, such as sodium carbonate, sodium sulfide, sodium sulfate, sodium hydroxide, sodium Hgnate, and calcium salts. This makes up the remaining one-third of the soap. Cmde tall oil is generated by acidifying the black Hquor soap with 30% sulfuric acid to a pH of 3. This is usually done in a vessel at 95°C with 20—30 minutes of vigorous agitation. Caution should be taken to scmb the hydrogen sulfide from the exhaust gas. 

Many attempts have been made to reduce the ammoniacal and sulfurous odor of the standard thioglycolate formulations. As the cosmetics market is very sensitive to the presence of impurities, odor, and color, various treatments of purification have been claimed to improve the olfactory properties of thioglycolic acid and its salts, such as distillation (33), stabilization against the formation of H2S using active ingredients (34), extraction with solvents (35), active carbon (36), and chelate resin treatments (37). 

Isolation. Isolation procedures rely primarily on solubiHty, adsorption, and ionic characteristics of the P-lactam antibiotic to separate it from the large number of other components present in the fermentation mixture. The penicillins ate monobasic catboxyHc acids which lend themselves to solvent extraction techniques (154). Pencillin V, because of its improved acid stabiHty over other penicillins, can be precipitated dkecdy from broth filtrates by addition of dilute sulfuric acid (154,156). The separation process for cephalosporin C is more complex because the amphoteric nature of cephalosporin C precludes dkect extraction into organic solvents. This antibiotic is isolated through the use of a combination of ion-exchange and precipitation procedures (157). The use of neutral, macroporous resins such as XAD-2 or XAD-4, allows for a more rapid elimination of impurities in the initial steps of the isolation (158). The isolation procedure for cephamycin C also involves a series of ion exchange treatments (103). 

Brine Preparation. Rock salt and solar salt (see Chemicals frombrine) can be used for preparing sodium chloride solution for electrolysis. These salts contain Ca, Mg, and other impurities that must be removed prior to electrolysis. Otherwise these impurities are deposited on electrodes and increase the energy requirements. The raw brine can be treated by addition of sodium carbonate and hydroxide to reduce calcium and magnesium levels to below 10 ppm. If further reduction in hardness is required, an ion-exchange resin can be used. A typical brine specification for the Huron chlorate ceU design is given in Table 6. 

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