Thermal phenols

These water streams contain mainly dissolved salts ammonium chloride and sulfide, sodium chloride, traces of cyanide, phenols for water coming from catalytic and thermal cracking operations. 

The controlled thermal decomposition of dry aromatic diazonium fluoborates to yield an aromatic fluoride, boron trifluoride and nitrogen is known as the Schiemann reaction. Most diazonium fluoborates have definite decomposition temperatures and the rates of decomposition, with few exceptions, are easily controlled. Another procedure for preparing the diazonium fluoborate is to diazotise in the presence of the fluoborate ion. Fluoboric acid may be the only acid present, thus acting as acid and source of fluoborate ion. The insoluble fluoborate separates as it is formed side reactions, such as phenol formation and coupling, are held at a minimum temperature control is not usually critical and the temperature may rise to about 20° without ill effect efficient stirring is, however, necessary since a continuously thickening precipitate is formed as the reaction proceeds. The modified procedure is illustrated by the preparation of -fluoroanisole ... 

Claisen rearrangement (Section 24 13) Thermal conversion of an allyl phenyl ether to an o allyl phenol The rearrange ment proceeds via a cyclohexadienone intermediate... 

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. 

Because of the high melt viscosity of polyolefins, normal spinning melt temperatures are 240—310°C, which is 80—150°C above the crystalline melting point. Because of the high melt temperatures used for polyolefin fiber spinning, thermal stabilizers such as substituted hindered phenols are added. In the presence of pigments, the melt temperature must be carefully controlled to prevent color degradation and to obtain uniform color dispersion. 

Polyphenols. Another increa singly important example of the chemical stabilization process is the production of phenoHc foams (59—62) by cross-linking polyphenols (resoles and novolacs) (see Phenolic resins). The principal features of phenoHc foams are low flammabiUty, solvent resistance, and excellent dimensional stabiUty over a wide temperature range (59), so that they are good thermal iasulating materials. 

Catalysis is usually accompHshed through the use of tertiary amines such as triethylenediamine. Other catalysts such as 2,4,6-/m(/V,/V-dimethylaminomethyl)phenol are used in the presence of high levels of cmde MDI to promote trimerization of the isocyanate and thus form isocyanurate ring stmctures. These groups are more thermally stable than the urethane stmcture and hence are desirable for improved flammabiUty resistance (236). Some urethane content is desirable for improved physical properties such as abrasion resistance. 

Phenol—formaldehyde resins are used as mol ding compounds (see Phenolic resins). Their thermal and electrical properties allow use in electrical, automotive, and kitchen parts. Other uses for phenol—formaldehyde resins include phenoHc foam insulation, foundry mold binders, decorative and industrial laminates, and binders for insulating materials. 

Fig. 3. Aging effect on thermal conductivity of cellular plastics A, extmded polystyrene B, unfaced polyurethane C, unfaced phenolic and D, polyurethane...

Phosphatase Test. The phosphatase [9001-78-9] test is a chemical method for measuring the efficiency of pasteurization. AH raw milk contains phosphatase and the thermal resistance of this enzyme is greater than that of pathogens over the range of time and temperature of heat treatments recognized for proper pasteurization. Phosphatase tests are based on the principle that alkaline phosphatase is able, under proper conditions of temperature and pH, to Hberate phenol [108-95-2] from a disodium phenyl phosphate substrate. The amount of Hberated phenol, which is proportional to the amount of enzyme present, is determined by the reaction of Hberated phenol with 2,6-dichloroquinone chloroimide and colorimetric measurement of the indophenol blue formed. Under-pasteurization as well as contamination of a properly pasteurized product with raw milk can be detected by this test. 

Mesitylene. One of the principal derivatives of mesitylene is the stericaHy hindered phenol of the stmcture shown in Eigure 4. Its trade name is Ethanox 330 and it is produced by Albemarle Corporation (formerly Ethyl Corporation) (31). Ethanox 330 is an important noncoloring antioxidant and thermal stabiHzer for plastics, adhesives, mbber, and waxes (qv) (32,33) (see Antioxidants). The oral toxicity of Antioxidant 330 is extremely low (oral LD q in rats >15 g/kg) since its large size, C H gO, effectively eliminates absorption from the gastrointestinal tract. 

Methylphenol is converted to 6-/ f2 -butyl-2-methylphenol [2219-82-1] by alkylation with isobutylene under aluminum catalysis. A number of phenoHc anti-oxidants used to stabilize mbber and plastics against thermal oxidative degradation are based on this compound. The condensation of 6-/ f2 -butyl-2-methylphenol with formaldehyde yields 4,4 -methylenebis(2-methyl-6-/ f2 butylphenol) [96-65-17, reaction with sulfur dichloride yields 4,4 -thiobis(2-methyl-6-/ f2 butylphenol) [96-66-2] and reaction with methyl acrylate under base catalysis yields the corresponding hydrocinnamate. Transesterification of the hydrocinnamate with triethylene glycol yields triethylene glycol-bis[3-(3-/ f2 -butyl-5-methyl-4-hydroxyphenyl)propionate] [36443-68-2] (39). 2-Methylphenol is also a component of cresyHc acids, blends of phenol, cresols, and xylenols. CresyHc acids are used as solvents in a number of coating appHcations (see Table 3). 

Production of a-methylstyrene (AMS) from cumene by dehydrogenation was practiced commercially by Dow until 1977. It is now produced as a by-product in the production of phenol and acetone from cumene. Cumene is manufactured by alkylation of benzene with propylene. In the phenol—acetone process, cumene is oxidized in the Hquid phase thermally to cumene hydroperoxide. The hydroperoxide is spHt into phenol and acetone by a cleavage reaction catalyzed by sulfur dioxide. Up to 2% of the cumene is converted to a-methylstyrene. Phenol and acetone are large-volume chemicals and the supply of the by-product a-methylstyrene is weU in excess of its demand. Producers are forced to hydrogenate it back to cumene for recycle to the phenol—acetone plant. Estimated plant capacities of the U.S. producers of a-methylstyrene are Hsted in Table 13 (80). 

The corrosion behavior of tantalum is weU-documented (46). Technically, the excellent corrosion resistance of the metal reflects the chemical properties of the thermal oxide always present on the surface of the metal. This very adherent oxide layer makes tantalum one of the most corrosion-resistant metals to many chemicals at temperatures below 150°C. Tantalum is not attacked by most mineral acids, including aqua regia, perchloric acid, nitric acid, and concentrated sulfuric acid below 175°C. Tantalum is inert to most organic compounds organic acids, alcohols, ketones, esters, and phenols do not attack tantalum. 

Hyperbranched polyurethanes are constmcted using phenol-blocked trifunctional monomers in combination with 4-methylbenzyl alcohol for end capping (11). Polyurethane interpenetrating polymer networks (IPNs) are mixtures of two cross-linked polymer networks, prepared by latex blending, sequential polymerization, or simultaneous polymerization. IPNs have improved mechanical properties, as weU as thermal stabiHties, compared to the single cross-linked polymers. In pseudo-IPNs, only one of the involved polymers is cross-linked. Numerous polymers are involved in the formation of polyurethane-derived IPNs (12). 

Alternatively, thermal cracking of acetals or metal-catalyzed transvinylation can be employed. Vinyl acetate or MVE can be employed for transvinylation and several references illustrate the preparation especially of higher vinyl ethers by such laboratory techniques. Special catalysts and conditions are required for the synthesis of the phenol vinyl ethers to avoid resinous condensation products (6,7). Direct reaction of ethylene with alcohols has also been investigated (8). 

Methylene chloride is one of the more stable of the chlorinated hydrocarbon solvents. Its initial thermal degradation temperature is 120°C in dry air (1). This temperature decreases as the moisture content increases. The reaction produces mainly HCl with trace amounts of phosgene. Decomposition under these conditions can be inhibited by the addition of small quantities (0.0001—1.0%) of phenoHc compounds, eg, phenol, hydroquinone, -cresol, resorcinol, thymol, and 1-naphthol (2). Stabilization may also be effected by the addition of small amounts of amines (3) or a mixture of nitromethane and 1,4-dioxane. The latter diminishes attack on aluminum and inhibits kon-catalyzed reactions of methylene chloride (4). The addition of small amounts of epoxides can also inhibit aluminum reactions catalyzed by iron (5). On prolonged contact with water, methylene chloride hydrolyzes very slowly, forming HCl as the primary product. On prolonged heating with water in a sealed vessel at 140—170°C, methylene chloride yields formaldehyde and hydrochloric acid as shown by the following equation (6). 

Eor shifting coal-derived gas, conventional iron—chromium catalysts can be used. Because coal gas has a significantly higher concentration of carbon monoxide than is found in gas streams in conventional refineries, the catalyst must be able to withstand high thermal loads. However, potential catalyst poisons such as phenol and other hydrocarbons are not a concern in entrained-bed gasifiers. 

Phenols of stmcture (4) are also claimed to show markedly improved dye stabiUty both in the presence of ferrous ion and, with a second carbonamido group in the 5-position, to simple thermal fade (62). Numerous substituent variations are described in the Hterature to adjust dye hue. A perfluoroacylamido in the 2-position shifts the hues bathochromicaHy while maintaining thermal stabHity of the dyes (63). Phenols of stmcture (5) are said to show outstanding light stabHity, which makes them especiaHy suitable for display materials like color paper (64). 

Ethyleneamines are used in certain petroleum refining operations as well. Eor example, an EDA solution of sodium 2-aminoethoxide is used to extract thiols from straight-mn petroleum distillates (314) a combination of substituted phenol and AEP are used as an antioxidant to control fouling during processing of a hydrocarbon (315) AEP is used to separate alkenes from thermally cracked petroleum products (316) and TEPA is used to separate carbon disulfide from a pyrolysis fraction from ethylene production (317). EDA and DETA are used in the preparation and reprocessing of certain... 

The thermal stabiUty of epoxy phenol—novolak resins is useful in adhesives, stmctural and electrical laminates, coatings, castings, and encapsulations for elevated temperature service (Table 3). Filament-wound pipe and storage tanks, liners for pumps and other chemical process equipment, and corrosion-resistant coatings are typical appHcations using the chemically resistant properties of epoxy novolak resins. 

Polynuclear Phenol—Glycidyl Ether-Derived Resins. This is one of the first commercially available polyfunctional products. Its polyfunctionahty permits upgrading of thermal stabiUty, chemical resistance, and electrical and mechanical properties of bisphenol A—epoxy systems. It is used in mol ding compounds and adhesives. 

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