Phenol Convention

Sample BET Plots of Reversible Adsorption of Phenol Plateau of the Reversible Adsorption Isotherm of Phenol Conventional BET (N2) Method... 

Diazotization Routes. Conventional Sandmeyer reaction conditions are not suitable to make fluoroaromatics. Phenols primarily result from high solvation of fluoride ion in aqueous media. 

Synthetic phenol capacity in the United States was reported to be ca 1.6 x 10 t/yr in 1989 (206), almost completely based on the cumene process (see Cumene Phenol). Some synthetic phenol [108-95-2] is made from toluene by a process developed by The Dow Chemical Company (2,299—301). Toluene [108-88-3] is oxidized to benzoic acid in a conventional LPO process. Liquid-phase oxidative decarboxylation with a copper-containing catalyst gives phenol in high yield (2,299—304). The phenoHc hydroxyl group is located ortho to the position previously occupied by the carboxyl group of benzoic acid (2,299,301,305). This provides a means to produce meta-substituted phenols otherwise difficult to make (2,306). VPOs for the oxidative decarboxylation of benzoic acid have also been reported (2,307—309). Although the mechanism appears to be similar to the LPO scheme (309), the VPO reaction is reported not to work for toluic acids (310). 

Phenol can be oxidi2ed and hence removed, ie, to levels <20 / g/L, from wastewater (248). Moreover, addition of potassium permanganate to the return activated sludge results in reduction of odors issued from the aeration tanks of conventional activated sludge wastewater treatment plants without any change occurring to the microbiology of the system (249). 

Novolak Resins. In a conventional novolak process, molten phenol is placed into the reactor, foHowed by a precise amount of acid catalyst. The formaldehyde solution is added at a temperature near 90°C and a formaldehyde-to-phenol molar ratio of 0.75 1 to 0.85 1. For safety reasons, slow continuous or stepwise addition of formaldehyde is preferred over adding the entire charge at once. Reaction enthalpy has been reported to be above 80 kj /mol (19 kcal/mol) (29,30). The heat of reaction is removed by refluxing the water combined with the formaldehyde or by using a small amount of a volatile solvent such as toluene. Toluene and xylene are used for azeotropic distillation. FoHowing decantation, the toluene or xylene is returned to the reactor. 

Allied-Signal Process. Cyclohexanone [108-94-1] is produced in 98% yield at 95% conversion by liquid-phase catal57tic hydrogenation of phenol. Hydroxylamine sulfate is produced in aqueous solution by the conventional Raschig process, wherein NO from the catalytic air oxidation of ammonia is absorbed in ammonium carbonate solution as ammonium nitrite (eq. 1). The latter is reduced with sulfur dioxide to hydroxylamine disulfonate (eq. 2), which is hydrolyzed to acidic hydroxylamine sulfate solution (eq. 3). 

Dutch State Mines (Stamicarbon). Vapor-phase, catalytic hydrogenation of phenol to cyclohexanone over palladium on alumina, Hcensed by Stamicarbon, the engineering subsidiary of DSM, gives a 95% yield at high conversion plus an additional 3% by dehydrogenation of coproduct cyclohexanol over a copper catalyst. Cyclohexane oxidation, an alternative route to cyclohexanone, is used in the United States and in Asia by DSM. A cyclohexane vapor-cloud explosion occurred in 1975 at a co-owned DSM plant in Flixborough, UK (12) the plant was rebuilt but later closed. In addition to the conventional Raschig process for hydroxylamine, DSM has developed a hydroxylamine phosphate—oxime (HPO) process for cyclohexanone oxime no by-product ammonium sulfate is produced. Catalytic ammonia oxidation is followed by absorption of NO in a buffered aqueous phosphoric acid... 

Glassy, or vitreous, carbon is a black, shiny, dense, brittle material with a vitreous or glasslike appearance (10,11). It is produced by the controUed pyrolysis of thermosetting resins phenol—formaldehyde and polyurethanes are among the most common precursors. Unlike conventional artificial graphites, glassy carbon has no filler material. The Hquid resin itself becomes the binder. 

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. 

Bisphenol F Resin. Bisphenol F [2467-02-9] epoxy resin is of the same general stmcture as the epoxy phenol novolaks. Bisphenol F is 2,2Emethylene bisphenol. Whereas the epoxy phenol novolaks vary from viscous Hquids to soHd materials, the bisphenol F resin has a low viscosity (ca 4 Pa-s (40 P)) and 165 epoxy equivalent weight. Its n value (degree of polymerization) is about 0.15 and crystallization, often a problem with low viscosity conventional bisphenol A resins, is reduced with the bisphenol F resin. 

With the advent of these compounds in the 1960s, the hitherto more conventional insulating materials, such as phenol formaldehyde (popularly known as Bakelite) and wood (veneered impregnated) have been almost replaced by them. These compounds offer better electromechanical properties than conventional materials. Below we describe the basic mix and properties of these two basic compounds, for a brief reference. 

Mention has already been made of epoxide stabilisers. They are of two classes and are rarely used alone. The first class are the epoxidised oils, which are commonly employed in conjunction with the cadmium-barium systems. The second class are the conventional bis-phenol A epoxide resins (see Chapter 22). Although rarely employed alone, used in conjunction with a trace of zinc octoate (2 parts resin, 0.1 part octoate) compounds may be produced with very good heat stability. 

To enhance the resistance to heat softening his-phenol A is substituted by a stiffer molecule. Conventional bis-phenol A polycarbonates have lower heat distortion temperatures (deflection temperatures under load) than some of the somewhat newer aromatic thermoplastics described in the next chapter, such as the polysulphones. In 1979 a polycarbonate in which the bis-phenol A was replaced by tetramethylbis-phenol A was test marketed. This material had a Vicat softening point of 196 C, excellent resistance to hydrolysis, excellent resistance to tracking and a low density of about l.lg/cm-. Such improvements were obtained at the expense of impact strength and resistance to stress cracking. 

Polycarbonates with superior notched impact strength, made by reacting bisphenol A, bis-phenol S and phosgene, were introduced in 1980 (Merlon T). These copolymers have a better impact strength at low temperatures than conventional polycarbonate, with little or no sacrifice in transparency. These co-carbonate polymers are also less notch sensitive and, unlike for the standard bis-phenol A polymer, the notched impact strength is almost independent of specimen thickness. Impact resistance increases with increase in the bis-phenol S component in the polymer feed. Whilst tensile and flexural properties are similar to those of the bis-phenol A polycarbonate, the polyco-carbonates have a slightly lower deflection temperature under load of about 126°C at 1.81 MPa loading. 

Whilst conventional polycarbonate based on bis-phenol A is essentially linear, branched polymers have recently been introduced. These materials have flow properties and a melt stability that makes them particularly suitable for large (20 litre) water and milk containers. Branched polymers have also been used in the manufacture of twin-walled sheet for the building industry. 

The commercial appearance of phenolic resins fibres in 1969 is, at first consideration, one of the more unlikelier developments in polymer technology. By their very nature the phenolic resins are amorphous whilst the capability of crystallisation is commonly taken as a prerequisite of an organic polymer. Crystallisability is not, however, essential with all fibres. Glass fibre, carbon fibre and even polyacrylonitrile fibres do not show conventional crystallinity. Strength is obtained via other mechanisms. In the case of phenolic resins it is obtained by cross-linking. 

A condensible blowdown tank, designed on a similar basis to that described above for phenol, may be provided in other services where a conventional condensible blowdown drum would not be acceptable (e.g., due to effluent water pollution considerations). Examples of such cases are methyl ethyl ketone (MEK) and dimethyl formamide (DMF). A suitable absorbing material is specified (e.g., a lube oil stock for MEK water for DMF), and the design must include consideration of maximum permissible operating temperatures to prevent excessive vapor evolution or the boiling of water. 

Irg 1076, AO-3 (CB), are used in combination with metal dithiolates, e.g., NiDEC, AO-30 (PD), due to the sensitized photoxidation of dithiolates by the oxidation products of phenols, particularly stilbenequinones (SQ, see reaction 9C) (Table 3). Hindered piperidines exhibit a complex behavior when present in combination with other antioxidants and stabilizers they have to be oxidized initially to the corresponding nitroxyl radical before becoming effective. Consequently, both CB-D and PD antioxidants, which remove alkyl peroxyl radicals and hydroperoxides, respectively, antagonise the UV stabilizing action of this class of compounds (e.g.. Table 3, NiDEC 4- Tin 770). However, since the hindered piperidines themselves are neither melt- nor heat-stabilizers for polymers, they have to be used with conventional antioxidants and stabilizers. 

One of the interesting properties of PBPCP [187] was its fast heat dissipation characteristics and so it was tested by the well-known oxy-acetylene panel test (ASTM 285-70) for ablative materials. Figure 13 shows the survival of a flower for 100 s. kept on the 6.35-mm asbestos fiber-reinforced hexamine-cured panel. The ablation rate value of this material was 3.2 x 10 in/s in comparison with 3.6 x 10 in/s for asbestos-phenolic. As the char content of PBPCP was only 27% compared with 60% for conventional phenolics, mechanisms involving transpiration processes rather than heat blocking by char formation might be playing a greater role in this case [188]. 

A low acid polyvinyl butyral-based pretreatment primer ( etch or wash primer are alternative names) is usually advantageous as the first treatment of a metal-sprayed surface before painting. Up to an equal volume of spirit soluble phenolic resin is used as a diluent to the polyvinyl butyral of conventional pretreatment primers. This has an incidental, but particularly valuable effect, in reducing the free acid available to penetrate into the pores of the coating. The modified pretreatment primer is highly water resistant and this helps to avoid damage due to condensation. 

Paints used for protecting the bottoms of ships encounter conditions not met by structural steelwork. The corrosion of steel immersed in sea-water with an ample supply of dissolved oxygen proceeds by an electrochemical mechanism whereby excess hydroxyl ions are formed at the cathodic areas. Consequently, paints for use on steel immersed in sea-water (pH 8-0-8-2) must resist alkaline conditions, i.e. media such as linseed oil which are readily saponified must not be used. In addition, the paint films should have a high electrical resistance to impede the flow of corrosion currents between the metal and the water. Paints used on structural steelwork ashore do not meet these requirements. It should be particularly noted that the well-known structural steel priming paint, i.e. red lead in linseed oil, is not suitable for use on ships bottoms. Conventional protective paints are based on phenolic media, pitches and bitumens, but in recent years high performance paints based on the newer types of non-saponifiable resins such as epoxies. 

Conventional non-bituminous system Tung oil/phenolic medium Airless spray. 2-3 150-200... 

Gas-filled plastics are polymer materials — disperse systems of the solid-gas type. They are usually divided into foam plastics (which contain mostly closed pores and cells) and porous plastics (which contain mostly open communicating pores). Depending on elasticity, gas-filled plastics are conventionally classified into rigid, semi-rigid, and elastic, categories. In principle, they can be synthesized on the basis of any polymer the most widely used materials are polystyrene, polyvinyl chloride, polyurethanes, polyethylene, polyepoxides, phenol- and carbamideformaldehyde resins, and, of course, certain organosilicon polymers. 

Jaffe (1953)52 showed that while many rate or equilibrium data conform well to the Hammett equation (as indicated by the correlation coefficient), many such data are outside the scope of the equation in its original form and mode of application. Deviations are commonly shown by para-substituents with considerable + Rot — R effect53. Hammett himself found that p-NOz (+ R) showed deviations in the correlation of reactions of anilines or phenols. The deviations were systematic in that a a value of ca. 1.27 seemed to apply, compared with 0.78 based on the ionization of p-nitrobenzoic acid. Other examples were soon discovered and it became conventional to treat them similarly in terms of a duality of substituent constants . 

Mn(II) > Mg(II).270 It should be underlined that titanium and zirconium alkoxides are efficient catalysts for both stages of reaction. Lanthanide compounds such as 2,2/-bipyridyl, acetylacetonate, and o-formyl phenolate complexes of Eu(III), La(III), Sm(III), Er(III), and Tb(III) appear to be even more efficient than titanium alkoxides, Ca or Mn acetates, Sb203, and their mixtures.273 Moreover, PET produced with lanthanides has been reported to exhibit better thermal and hydrolytic stability as compared to PET synthesized with the conventional Ca acetate -Sb203 catalytic system.273... 

The Ullman reaction has long been known as a method for the synthesis of aromatic ethers by the reaction of a phenol with an aromatic halide in the presence of a copper compound as a catalyst. It is a variation on the nucleophilic substitution reaction since a phenolic salt reacts with the halide. Nonactivated aromatic halides can be used in the synthesis of poly(arylene edier)s, dius providing a way of obtaining structures not available by the conventional nucleophilic route. The ease of halogen displacement was found to be the reverse of that observed for activated nucleophilic substitution reaction, that is, I > Br > Cl F. The polymerizations are conducted in benzophenone with a cuprous chloride-pyridine complex as a catalyst. Bromine compounds are the favored reactants.53,124 127 Poly(arylene ether)s have been prepared by Ullman coupling of bisphenols and... 

For the synthesis of coumarins, the Pechmann reaction [145] is one of the most popular synthetic routes. As the reaction is conventionally carried out at high temperature, two microwave-assisted versions have been recently described. Besson and co-workers described the cyclocondensation of different m-amino phenols 226 with /1-ketoesters 227 on graphite/montmorillonite KIO support (Scheme 83). The use of graphite was crucial in the development of the reaction conditions. In fact, microwave irradiation of the reagents using different conditions gave poor results in terms of yields and purity. The optimized conditions, using a monomode microwave system, employed... 

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