Formaldehyde modification

Many recent studies have focused on the mechanisms of formaldehyde modification, cross-linking, and reversal.19,37 8 In general, these studies found that formaldehyde is very specific, particularly when reaction times are relatively short. The amino-termini, lysine, tryptophan, and cysteine are the targets of modification in this case. Longer reaction times reveal more extensive modifications, including arginine, histidine, tyrosine, and phenylalanine. 

Even low levels of formaldehyde modification result in significant reductions in the EMC of wood (Minato and Norimoto, 1985 Minato, 1993). For example, Yasuda elal. (1995) found that a WPG level of only 3.5 % resulted in a 50 % reduction of the EMC compared to unmodified wood. This is attributable to the formation of rigid cross-links within the cell wall matrix preventing swelling of the cell wall in the presence of atmospheric moisture. 

Enzymatic detoxification or modification AGAC antibiotics /(-Lactams Chloramphenicol Erythromycin Tetracyclines Mercury compounds Formaldehyde Modification by acetyltransferases, adenylylases or phosphotransferases Inactivation (/(-lactamases) Inactivation (acetyltransferases) Esterases produce anhydroerythromycin Enzymatic inactivation Inactivation (hydrolases, lyases) Dehydrogenase... 

Disproportionation/dehydrogenation of rosin is also a process that decreases the ability of colophony to oxidize, since the amount of resin acids with conjugated double bonds is diminished in favour of dehydroabietic acid. Polymerization dimerization of colophony decreases its tendency to crystallize. Major products formed are dimers of resin acids, but the degree of polymerisation varies with the conditions (time, temperature) under which the modification is performed. Formaldehyde modification of colophony includes several different reactions performed under various conditions where formaldehyde reacts with resin acids. Colophony can also be modified by reacting metal salts, e.g. sodium, potassium, or barium, calcium, cobalt and zinc, with resin acids to form salts resinates) (McSweeney et al. 1987 Soltes and Zinkel 1989). 

Formaldehyde modification Paper size, printing inks... 

Another modification of this process was reported in 1988 (84). In this process, a precondensate of THPC and urea, plus excess urea, are neutralized to a pH of about 5.7, and the buffer salt is added. The fabric is then given a standard pad-dry-cure process followed by oxidation and laundering. The principal advantage of this modification is a reduction in both formaldehyde vapors and phosphine-like odors released during processing (84). 

Oxidation of methanol to formaldehyde with vanadium pentoxide catalyst was first patented in 1921 (90), followed in 1933 by a patent for an iron oxide—molybdenum oxide catalyst (91), which is stiU the choice in the 1990s. Catalysts are improved by modification with small amounts of other metal oxides (92), support on inert carriers (93), and methods of preparation (94,95) and activation (96). In 1952, the first commercial plant using an iron—molybdenum oxide catalyst was put into operation (97). It is estimated that 70% of the new formaldehyde installed capacity is the metal oxide process (98). 

The aromatic ring of a phenoxy anion is the site of electrophilic addition, eg, in methylolation with formaldehyde (qv). The phenoxy anion is highly reactive to many oxidants such as oxygen, hydrogen peroxide, ozone, and peroxyacetic acid. Many of the chemical modification reactions of lignin utilizing its aromatic and phenoHc nature have been reviewed elsewhere (53). 

Prior to 1965, it was not unusual for unwashed finished fabrics to release 3—5000 ppm of formaldehyde when tested by an AATCC test method. Formaldehyde release was reduced to the level of 2000 or less by appHcation of DMDHEU or dimethyl olcarhama tes. This level was reduced to approximately 1000 in the mid-1970s. Modification of the DMDHEU system and use of additives demonstrated that release values below 100 ppm were achievable. As of this writing (1997), good commercial finishing ranges between 100 and 200 ppm of formaldehyde release. 

Other modifications of the polyamines include limited addition of alkylene oxide to yield the corresponding hydroxyalkyl derivatives (225) and cyanoethylation of DETA or TETA, usuaHy by reaction with acrylonitrile [107-13-1/, to give derivatives providing longer pot Hfe and better wetting of glass (226). Also included are ketimines, made by the reaction of EDA with acetone for example. These derivatives can also be hydrogenated, as in the case of the equimolar adducts of DETA and methyl isobutyl ketone [108-10-1] or methyl isoamyl ketone [110-12-3] (221 or used as is to provide moisture cure performance. Mannich bases prepared from a phenol, formaldehyde and a polyamine are also used, such as the hardener prepared from cresol, DETA, and formaldehyde (228). Other modifications of polyamines for use as epoxy hardeners include reaction with aldehydes (229), epoxidized fatty nitriles (230), aromatic monoisocyanates (231), or propylene sulfide [1072-43-1] (232). 

Otner Collectors Tarry particulates and other difficult-to-handle hquids have been collected on a dry, expendable phenol formaldehyde-bonded glass-fiber mat (Goldfield, J. Air Pollut. Control A.SSOC., 20, 466 (1970)] in roll form which is advanced intermittently into a filter frame. Superficial gas velocities are 2.5 to 3.5 m/s (8.2 to 11.5 ft/s), and pressure drop is typically 41 to 46 cm (16 to 18 in) of water. CoUection efficiencies of 99 percent have been obtained on submicrometer particles. Brady [Chem. Eng. Prog., 73(8), 45 (1977)] has discussed a cleanable modification of this approach in which the gas is passed through a reticulated foam filter that is slowly rotated and solvent-cleaned. 

Modification of urea-formaldehyde resins with other reagents gives rise to a number of useful materials. For example, co-condensation of urea-formaldehyde and a monohydric alcohol in the presence of small quantities of an acidic catalyst will involve simultaneous etherification and resinification. n-Propanol, n-butanol and isobutanol are commonly used for this purpose. As an example n-butanol will react with the methylol urea as shown in Figure 24.4. 

Zavitsas et al. account for the effects of water in their calculations. Water promotes depolymerization of the paraformaldehyde as well as the hemiformals. Their modifications correct for the apparent reduction in methylolation rate as the extent of reaction proceeds, in that the hemiformals remove formaldehyde reactivity from the reaction mixture. Their rate constants look large because they are written for phenate concentrations rather than phenol and because of the formaldehyde equilibrium adjustments. They note that unsalted phenol is a by-... 

More recently, a modification of the system described by Kreibich has been used extensively in industry with good success. Part A of the adhesive is again a standard phenol-resorcinol-formaldehyde (PRF) cold-setting adhesive, with powder hardener added at its standard pH. Part B can be either the same PRF adhesive with no hardener and the pH adjusted to 12, or a 50 to 55% tannin extract solution at a pH of 12-13, provided that the tannin is of the condensed or flavonoid type, such as mimosa, quebracho, or pine bark extract, with no hardener [118,135-137], The results obtained with these two systems are good and the resin not only has all the advantages desired but also the use of vegetable tannins and the halving of the resorcinol content makes the system considerably cheaper [118,135-137]. 

Polymers are very large organic molecules that are either made synthetically or are of natural origin, and find use as plastics, rubber, fibers, and coatings. Polymers were first produced commercially in 1860 by modification of cellulose from wood or cotton, followed by a fully synthetic product made from phenol and formaldehyde in 1910. 

The effect of various chemical modifications on the mechanical properties of reconstituted collagen and the diffusion rates of the steroid medroxyprogesterone was investigated (38). Formaldehyde-treated films, which are heavily crosslinked, have high moduli and low rates of drug release. Films treated with chrome quickly become hydrated in solution and have low moduli and very rapid drug release characteristics. 

The second example that is used to illustrate the design methodologies is a modification to the EDTA problem as follows. The structure of the flowsheet is exactly the same as the one presented in Section IV. The only change to the problem is the statement that sulfuric acid and formaldehyde should not be allowed to come into contact with each other. 

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