Preservatives phenols

Anti-HBe/POD Conjugate Monoclonal anti-HBe, conjugated with peroxidase (POD), preservative phenol (max. 1 g/L)... 

D-Limone, 2% pet (paints, coatings) Pentachlorophenol (PCP), 1% aq (wood preservatives) Phenol-formaldehyde resin, 1% pet. Resol (resins, glues, plywood)... 

Beeswax, 30% pet (adhesives and waxes) p-tert-Butylphenol, 2% pet (glues, preservatives) Cobalt chloride, 1% pet (dryers in stains and varnishes) Mixed dialkyl thioureas, 1% pet Pentachlorophenol, 1% pet (wood preservatives) Phenol-formaldehyde resin, 10% pet (adhesives) o-Phenylphenol, 1% pet (preservative in adhesives) Polyurethane resins and catalysts Propylene glycol, 4% aq (varnishes)... 

Approximately 50—55% of the product from a coal-tar refinery is pitch and another 30% is creosote. The remaining 15—20% is the chemical oil, about half of which is naphthalene. Creosote is used as a feedstock for production of carbon black and as a wood preservative. Because of modifications to modem coking processes, tar acids such as phenol and cresyUc acids are contained in coal tar in lower quantity than in the past. To achieve economies of scale, these tar acids are removed from cmde coal tar with a caustic wash and sent to a central processing plant where materials from a number of refiners are combined for recovery. 

Phenolics. Phenol (qv) and the chlotinated phenoHcs formerly comprised the largest class of iadustrial antimicrobials (see Chlorophenols). Table 5 shows the remaining phenoHcs of importance. Use of pentachlorophenol has been severely restricted only one manufacturer suppHes product for the wood preservation market. 

Actual water treatment challenges are multicomponent. For example, contamination of groundwater by creosote [8021-39-4], a wood (qv) preservative, is a recurring problem in the vicinity of wood-preserving faciUties. Creosote is a complex mixture of 85 wt % polycycHc aromatic hydrocarbons (PAHs) 10 wt % phenohc compounds, including methylated phenols and the remaining 5 wt % N—, S—, and O— heterocycHcs (38). Aqueous solutions of creosote are therefore, in many ways, typical of the multicomponent samples found in polluted aquifers. 

In the case of low temperature tar, the aqueous Hquor that accompanies the cmde tar contains between 1 and 1.5% by weight of soluble tar acids, eg, phenol, cresols, and dihydroxybenzenes. Both for the sake of economics and effluent purification, it is necessary to recover these, usually by the Lurgi Phenosolvan process based on the selective extraction of the tar acids with butyl or isobutyl acetate. The recovered phenols are separated by fractional distillation into monohydroxybenzenes, mainly phenol and cresols, and dihydroxybenzenes, mainly (9-dihydroxybenzene (catechol), methyl (9-dihydtoxybenzene, (methyl catechol), and y -dihydroxybenzene (resorcinol). The monohydric phenol fraction is added to the cmde tar acids extracted from the tar for further refining, whereas the dihydric phenol fraction is incorporated in wood-preservation creosote or sold to adhesive manufacturers. Naphthalene Oils. Naphthalene is the principal component of coke-oven tats and the only component that can be concentrated to a reasonably high content on primary distillation. Naphthalene oils from coke-oven tars distilled in a modem pipe stiU generally contain 60—65% of naphthalene. They are further upgraded by a number of methods. 

Benzoic Acid. Ben2oic acid is manufactured from toluene by oxidation in the liquid phase using air and a cobalt catalyst. Typical conditions are 308—790 kPa (30—100 psi) and 130—160°C. The cmde product is purified by distillation, crystallization, or both. Yields are generally >90 mol%, and product purity is generally >99%. Kalama Chemical Company, the largest producer, converts about half of its production to phenol, but most producers consider the most economic process for phenol to be peroxidation of cumene. Other uses of benzoic acid are for the manufacture of benzoyl chloride, of plasticizers such as butyl benzoate, and of sodium benzoate for use in preservatives. In Italy, Snia Viscosa uses benzoic acid as raw material for the production of caprolactam, and subsequendy nylon-6, by the sequence shown below. 

Composition and Methods of Manufacture. The vaccine consists of a mixture of purified capsular polysaccharides from 23 pneumococcal types that are responsible for over 90% of the serious pneumococcal disease in the world (47,48). Each of the polysaccharide types is produced separately and treated to remove impurities. The latter is commonly achieved by alcohol fractionation, centrifugation, treatment with cationic detergents, proteolytic en2ymes, nucleases or activated charcoal, diafiltration, and lyophili2ation (49,50). The vaccine contains 25 micrograms of each of the types of polysaccharide and a preservative such as phenol or thimerosal. 

In the United States all other processes have been completely phased out and virtually all benzoic acid is manufactured by the continuous hquid-phase air oxidation of toluene. In the late 1950s and the early 1960s both Dow Chemical and Snia Viscosa constmcted faciUties for Hquid-phase toluene oxidation because of large requirements for benzoic acid in the production of phenol and caprolactam. Benzoic acid, its salts, and esters are very useful and find appHcation in medicinals, food and industrial preservatives, cosmetics, resins, plasticizers, dyestuffs, and fibers. 

Ethanol and 2-propanol have also found use ia disinfecting clinical thermometers, and as preservatives to prevent microbial deterioration of cosmetics and mediciaals. They are sometimes combiaed with other disiafectants, namely formaldehyde (69), phenoHcs (70), chlorhexidine (71), hypochlorite (72), and phenols (70). 

Important chemicals derived from phenol are salicylic acid acetylsali-cyclic acid (aspirin) 2,4-dichlorophenoxy acetic acid (2,4-D), and 2,4,5-triphenoxy acetic acid (2,4,5-T), which are selective herbicides and pentachlorophenol, a wood preservative ... 

Other halophenols are miticides, bactericides, and leather preservatives. Halophenols account for about 5% of phenol uses. 

Though much benzoic acid gets used as a mordant in calico printing, it also serves to season tobacco, preserve food, make dentifrices, and kill fungus. Furthermore it is a precursor for caprolactam, phenol, and tereph-thalic acid. 

In addition lo its use in making resins and adhesives, phenol is also the starting material for the synthesis of chlorinated phenols and the food preservatives BHT (butylated hvdroxytoiuene) and BHA (butylated bydroxyanisole). Penta-chlorophenol, a widely used wood preservative, is prepared by reaction of phenol with excess CI2- The herbicide 2,4-D (2,4-dichlorophenoxyacetjc acid) is prepared from 2,4-dichlorophenol, and the hospital antiseptic agent hexa-chlorophene is prepared from 2,4,5-trichlorophenol. 

Phenol was the first commercial antiseptic its introduction into hospitals in the 1870s led to a dramatic decrease in deaths from postoperative infections. Its use for this purpose has long since been abandoned because phenol burns exposed tissue, but many modern antiseptics are phenol derivatives. Toluene has largely replaced benzene as a solvent because it is much less toxic. Oxidation of toluene in the body gives benzoic acid, which is readily eliminated and has none of the toxic properties of the oxidation products of benzene. Indeed, benzoic acid or its sodium salt (Na+, C6H5COO ions) is widely used as a preservative in foods and beverages, including fruit juices and soft drinks. 

Tubular reactors are used for some polycondensations. Para-blocked phenols can be reacted with formalin to form linear oligomers. When the same reactor is used with ordinary phenol, plugging will occur if the tube diameter is above a critical size, even though the reaction stoichiometry is outside the region that causes gelation in a batch reactor. Polymer chains at the wall continue to receive formaldehyde by diffusion from the center of the tube and can crosslink. Local stoichiometry is not preserved when the reactants have different diffusion coefficients. See Section 2.8. 

Many derivatives of phenol are now made by a synthetic process. Homologous series of substituted derivatives have been prepared and tested for antimicrobial activity. A combination of alkyl substitution and halogenation has produced useful derivatives including clorinated phenols which are constituents of a number of proprietary disinfectants. Two ofthe most widely used derivatives are/ -chloro-m-cresol (4-chloro-3-methylphenol, chlorocresol, Fig. 10.7C) which is mostly employed as a preservative at a concentration of 0.1%, and / -chloro-m-xylenol (4-chloro-3,5-dimethylphenol, chloroxylenol. Fig. 10.7C) which is used for skin disinfection, although less than formerly. Chloroxylenol is sparingly soluble in water and must be solubihzed, for example in a suitable soap solution in conjunction with terpineol or pine oil. Its antimicrobial capacity is weak and is reduced by the presence of organic matter. 

As is apparent from the above information, there is no ideal disinfectant, antiseptic or preservative. All chemical agents have their limitations either in terms of their antimicrobial activity, resistance to organic matter, stability, incompatibility, irritancy, toxicity or corrosivity. To overcome the limitations of an individual agent, formulations consisting of combinations of agents are available. For example, ethanol has been combined with chlorhexidine and iodine to produce more active preparations. The combination of chlorhexidine and cetrimide is also considered to improve activity. QACs and phenols have been combined with glutaraldehyde so that the same effect can be achieved with lower, less irritant concentrations of glutaraldehyde. Some... 

Phenol concentration. When phenol is used to preserve a vaccine its concentration must not exceed 0.25% wA or, in the case of some vaccines, 0.5% w/v. Phenol is estimated by the colour reaction with amino-phenazone and hexacyanoferrate. 

Preservative availability may be appreciably reduced by interaction with packaging materials. Examples include the permeation of phenolic preservatives into the rubber wads and teats of multi-dose injection or eye-drop containers and by their interaction with flexible nylon tubes for creams. Quaternary ammonium preservative levels in formulations have been significantly reduced by adsorption onto the surfaces of plastic and glass containers. Volatile preservatives such as chloroform are so readily lost by the routine opening and closing of containers that their usefulness is somewhat restricted to preservation of medicines in sealed, impervious containers during storage, with quite short use lives once opened. 

BisHov s J, MASUOKA Y and KAPSALis J G (1977) Antioxidant effect of spices, herbs and protein Hydrolyzates in freeze-dried model systems Synergistic action with synthetic phenolic antioxidants, J Foot/ Processing Preservation, 1, 153-66. 

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