Phenolic condensate

Phenol condenses with phthahc anhydride in the presence of concentrated sulphuric acid or anhydrous zinc chloride to yield the colourless phenolphthalein as the main product. When dilute caustic alkah is added to an alcoholic solution of phenolphthalein, an intense red colouration is produced. The alkali opens the lactone ring in phenolphthalein and forms a salt at one phenolic group. The reaction may be represented in steps, with the formation of a h3q)othetical unstable Intermediate that changes to a coloured ion. The colour is probably due to resonance which places the negative charge on either of the two equivalent oxygen atoms. With excess of concentrated caustic alkali, the first red colour disappears this is due to the production of the carbinol and attendant salt formation, rendering resonance impossible. The various reactions may be represented as follows ... 

The para and ortho positions of phenols condense at the carbonyl group of acetone to make bisphenols, eg, bisphenol A, 4,4 -(l-methylethyhdene)bisphenol [80-05-07]). If the H atom is activated, CICH— compounds add to the carbonyl group in the presence of strong base chloroform gives chloretone (l,l,l-trichloro-2-methyl-2-propanol [57-15-8]). 

Catalysts. In industrial practice the composition of catalysts are usuaUy very complex. Tellurium is used in catalysts as a promoter or stmctural component (84). The catalysts are used to promote such diverse reactions as oxidation, ammoxidation, hydrogenation, dehydrogenation, halogenation, dehalogenation, and phenol condensation (85—87). Tellurium is added as a passivation promoter to nickel, iron, and vanadium catalysts. A cerium teUurium molybdate catalyst has successfliUy been used in a commercial operation for the ammoxidation of propylene to acrylonitrile (88). 

In general their work indicates that at temperatures below 160°C cross-linking occurs by phenol methylol-phenol methylol and phenol methylol-phenol condensations, viz Figure 23.13. 

Another example of an unsteady state condensible blowdown system is the design for a phenol condensible blowdown tank. A blowdown tank is used in phenol treating plants to handle streams containing phenol and heavy hydrocarbons (lubricating oil stocks). The blowdown tank is illustrated in Figure 4. The design basis is as rollows ... 

Organophilic polyphenolic materials for oil-based drilling fluids have been described [407], The additives are prepared from a polyphenolic material and one or more phosphatides. The phosphatides are phosphoglycerides obtained from vegetable oils, preferably commercial lecithin. Humic acids, ligno-sulfonic acid, lignins, phenolic condensates, tannins the oxidized, sulfonated, or sulfomethylated derivatives of these polyphenolic materials may serve as polyphenolic materials. 

Polyphenolic materials prepared from a polyphenolic material (humic acids, lignosulfonic acid, lignins, phenolic condensates, tannins) and phosphatides (lecithin) - [407]... 

Cation-exchange resins are used as catalysts in the produdion of MTBE (methyl tertiary-butyl ether, 2-methoxy-2-methylpropane) and various other oxygenates and, lately, also in the dimerization of isobutene [30]. Other commercial applications of the cation-exchange resins indude dehydration of alcohols, alkylation of phenols, condensation readions, alkene hydration, purification of phenol, ester hydrolysis and other reactions [31]. The major producers of ion-exchange resins are Sybron Chemicals Incorporated [32] (Lewatit resins), Dow Chemical Company [33] (DOWEX resins), Purolite [28] (Purolite resins), and Rohm and Haas Company [27] (Amberlyst resins). 

If lignin is heated with phenol, the phenol condenses with lignin in the a-position of the side chain. Phenol generally couples in its para- position (15). Under optimum conditions, from 2.5 to 3 moles of phenol or phenolic derivative per phenylpropane unit are added to the protolignin (18). 

Lee, L-H. "Mechanism of Thermal Degradation of Phenolic Condensation Polymers" in Proceedings of Battelle Sym., on Thermal Stability of Polymers" Dec. 5,6, 1963. 

Acid Catalyzed. Although ketonic carbonyl groups are less reactive than aldehydic carbonyls in the presence of basic catalysts, this is not the case with acid catalysts. Thus acetone undergoes aldol addition in the presence of sulfuric acid to give mesityl oxide, which then condenses with a third molecule of acetone to give a mixture ofphorone (2,6-dimethyl-2,6-heptadien-4-one) and mesitylene (1,3,5-trimethylbenzene). Ketones also condense with activated aromatic products in the presence of sulfuric acid to give coupled aromatic products. For example, acetone and phenol condense to bisphenol A (4,4 -isopropylidenediphenol), which is used in the manufacture of epoxy resins (qv) and polycarbonates (qv). 

GLYCOLS. POLYETHYLENE, MONO((1,1,3,3-TETRAMETHYLBUTYL)PHENYL) ETHER OCTYL PHENOL condensed with 20 MOLES ETHYLENE OXIDE OCTYL PHENOL condensed with 8-10 MOLES ETHYLENE OXIDE OCTYL PHENOL condensed with 16 MOLES ETHYLENE OXIDE OCTYL PHENOL condensed with 3 MOLES ETHYLENE OXIDE... 

Hyder, P.W., Fredrickson, E.L., Estell, R.E., Tellez, M., Gibbens, R.P. Distribution and concentration of total phenolics, condensed tannins, and nordihydroguaiaretic acid (NDGA) in creosotebush (Larrea tridentata). Biochem Systemat Ecol 2002 30 905-912. 

Under comparable reaction conditions the much more reactive formaldehyde and phenol do not only give the para- but also the ortho-substituted phenol derivative. This reaction ultimately leads to the three-dimensional network of formaldehyde/phenol condensation resins such as Bakelite and to related, well-defined receptor molecules known as cahxarenes. 

Tellurium tetrachloride and phenols condense at elevated temperatures to form triaryl telluronium chlorides1,2. The reaction with benzene in refluxing benzene required the presence of aluminum trichloride3. 

A method was also developed for the synthesis of phenols. Condensation of different cyclic and acyclic tertiary enaminones and 3-oxoglutarate affords substituted phenols, including condensed systems2110 (equation 150). 

Other aldehydes used for the synthesis of phenolic polycondensates include butyraldehyde, furfural or chloral. Efficient AO, e.g. polycondensate 129, were prepared with sulfur containing aldehydes [161]. Linear polycondensates of phenols and aldehydes were tested as AO in mineral oils, PE, PP, poly (ethylene-co-propylene), PS, PA and/or diene based rubbers [159, 162]. Cyclic phenolic condensates, calixarenes (130) posses interesting properties. Calixarenes were synthesized from 4-acyl-, 4-methyl-, 4-tm-butyl- or 4-phenylphenol in alkaline catalysed processes. Cycles containing 4 to 7 phenolic units were formed and tested as AO in PE or PP [163,164], Nickel(II) salt of 130 (R = lerf-butyl, n = 1)... 

Analogously, carbonyl azide, N3CON3, gives iV-azidocarbonylaze-pine" when thermolysed in benzene. Substituted benzenes give mixtures of azepines ", which can be quite complex and intractable, because of prototropic and valence isomerizations, as observed in the reaction with phenol Condensed aromatics, such as naphthalene, anthracene and phenanthrene, give the apparent C—H insertion products instead of isolable azepines, at least in part due to isomerization of intermediary azepines The formation of the azepines... 

Phenol condensations. A cation-exchange resin is an excellent catalyst for the alkylation of phenol with isobutene." A mixture of phenol and the resin was stirred at 80° and isobutene was passed in over a period of 3 hrs. The temperature was... 

Supramine XA [BASF], TM for a leather chemical, solubilized sulfur phenol condensate, 75% active. 

The liberated phenol condenses with 4-aminoantipyrine and, in the presence of oxidizing conditions (alkaline ferricyanide), gives rise to an organic product in which the phenol residue contains the chromophoric quinonoid group. 

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