Water phenol alkylation

Alkyl hydroperoxides can be Hquids or soHds. Those having low molecular weight are soluble in water and are explosive in the pure state. As the molecular weight increases, ie, as the active oxygen content is reduced, water solubiUty and the violence of decomposition decrease. Alkyl hydroperoxides are stronger acids than the corresponding alcohols and have acidities similar to those of phenols, Alkyl hydroperoxides can be purified through their alkali metal salts (28). 

P. E. Chaplanov, A. D. Chemikov, O. G. Mironov, G. N. Semanov, A. G. Svinukhov, A. G. Yaremenko, F. V. Linchevskij, N. A. Melnik, 1. A. Murashev, and I. S. Akhmetzhanov. Removing oils and petroleum products from water surfaces—using mixture of oxyethylated alkyl-phenol, alkyl-phosphate and fatty acid diethanolamine. Patent SU 1325816-A, 1992. 

The replacement of the diethylhexyl phthalate(DEHP)-plasticised PVC film in Akva Waterbeds water mattresses with PVC plasticised with Bayer Chemicals Mesamoll phenol alkyl sulphonate is discussed. The performance advantages resulting from this switch are considered with particular attention to the greater saponification resistance of these plasticisers and their much reduced tendency to migrate. Data are given on the stability of Mesamoll and phthalate plasticisers in terms of saponification and hydrolysis and on the change in EB with time of Mesamoll- and DEHP-plasticised PVC films. 

The breakdown of P4Oi0 with various reagents (alcohols, water, phenols, ethers, alkyl phosphates, etc.) is a very general one and is illustrative also of the general reaction schemes for the breakdown of P4S1Q and for the reaction of P4 with alkali... 

Alcohols are appreciably harder than phenols to alkylate with dialkyl sulfates. Here an essential point for success is complete exclusion of water.691 Alkylation of alcohols is relatively smooth only if they contain activated hydroxyl groups, as in allyl alcohol, benzyl alcohol,692 acetylenic alcohols,693 cyanohydrins, trifluoroethanol,694 mandelic acid,695 2-chloro-ethanol,696 or 2-alkoxyethanols.697... 

The effect of solvent on the site of alkylation has been clearly demonstrated for phenolate ions. In solvents such as dimethyl sulfoxide, dimethylformamide, ethers, and alcohols, O-alkylation is dominant. In water, phenol, and trifluoroethanol, however, extensive amounts of C-alkylation occur. These latter solvents would be expected to form particularly strong hydrogen bonds with the oxygen atom of the phenolate anion. This strong solvation decreases the reactivity at oxygen and favors carbon alkylation. 

Boron Trifluoride Etherate Catalyst — - — - E - — in phenol and water during alkylation. Alloy C = 0.2 mpy (vapor). <0.1 mpy (bqmd)... 

Features Requires no coupler rinses clean at any water temp. alkyl phenol ethoxylate free leaves surfaces streak free Properties Cl. yel. liq. dens. 8.42 Ib/gal f.p. 32 F pH (1% aq.) 7 Environmental EPA compliant readily blodeg. 

Uses Wetting agent, spreading agenL surfactant for all-puqx>se cleaners, polished stone cleaners, neutral floor cleaners, glass cleaners Features Performs at high pH levels (>11.5) where cationic surfactants are not effective rinses clean at any water temp. alkyl phenol ethoxylate free reduces or eliminates the need for VOC compat. with cationic, anionic, and nonlonic surfactant... 

Uses Surfactant, wetting agent, spreading agent, penetration agent, and antiredeposition aid for frictionless vehicle detergents, aircraft cleaners, tire and wheel cleaners, hard surface cleaners and degreasers Features Hard water tolerant alkyl phenol ethoxylate free requires no coupler ... 

Oxidation of LLDPE starts at temperatures above 150°C. This reaction produces hydroxyl and carboxyl groups in polymer molecules as well as low molecular weight compounds such as water, aldehydes, ketones, and alcohols. Oxidation reactions can occur during LLDPE pelletization and processing to protect molten resins from oxygen attack during these operations, antioxidants (radical inhibitors) must be used. These antioxidants (qv) are added to LLDPE resins in concentrations of 0.1—0.5 wt %, and maybe naphthyl amines or phenylenediamines, substituted phenols, quinones, and alkyl phosphites (4), although inhibitors based on hindered phenols are preferred. 

The in situ process is simpler because it requires less material handling (35) however, this process has been used only for resole resins. When phenol is used, the reaction system is initially one-phase alkylated phenols and bisphenol A present special problems. As the reaction with formaldehyde progresses at 80—100°C, the resin becomes water-insoluble and phase separation takes place. Catalysts such as hexa produce an early phase separation, whereas NaOH-based resins retain water solubiUty to a higher molecular weight. If the reaction medium contains a protective coUoid at phase separation, a resin-in-water dispersion forms. Alternatively, the protective coUoid can be added later in the reaction sequence, in which case the reaction mass may temporarily be a water-in-resin dispersion. The protective coUoid serves to assist particle formation and stabUizes the final particles against coalescence. Some examples of protective coUoids are poly(vinyl alcohol), gum arabic, and hydroxyethjlceUulose. 

The solubihty of alkylphenols in water falls off precipitously as the number of carbons attached to the ring increases. They are generally soluble in common organic solvents acetone, alcohols, hydrocarbons, toluene. Solubihty in alcohols or heptane follows the generalization that "like dissolves like." The more polar the alkylphenol, the greater its solubihty in alcohols, but not in ahphatic hydrocarbons likewise with cresols and xylenols. The solubihty of an alkylphenol in a hydrocarbon solvent increases as the number of carbon atoms in the alkyl chain increases. High purity para substituted phenols, through Cg, can be obtained by crystallization from heptane. 

The aromatic ring of alkylphenols imparts an acidic character to the hydroxyl group the piC of unhindered alkylphenols is 10—11 (2). Alkylphenols unsubstituted in the ortho position dissolve in aqueous caustic. As the carbon number of the alkyl chain increases, the solubihty of the alkah phenolate salt in water decreases, but aqueous caustic extractions of alkylphenols from an organic solution can be accomphshed at elevated temperatures. Bulky ortho substituents reduce the solubihty of the alkah phenolate in water. The term cryptophenol has been used to describe this phenomenon. A 35% solution of potassium hydroxide in methanol (Qaisen s alkah) dissolves such hindered phenols (3). 

The triaLkoxy(aryloxy)boranes are typically monomeric, soluble in most organic solvents, and dissolve in water with hydrolysis to form boric acid and the corresponding alcohol and phenol. Although the rate of hydrolysis is usually very fast, it is dependent on the bulk of the alkyl or aryl substituent groups bonded to the boron atom. Secondary and tertiary alkyl esters are generally more stable than the primary alkyl esters. The boron atom in these compounds is in a trigonal coplanar state with bond hybridization. A vacantp orbital exists along the threefold axis perpendicular to the BO plane. 

Procedures for shipping boric acid esters depend on the particular compound. Aryl borates produce phenols when in contact with water and are therefore subject to shipping regulations governing such materials and must carry a Corrosive Chemical label. Lower alkyl borates are flammable, flash points of methyl, ethyl, and butyl borates are 0, 32, and 94°C, respectively, and must be stored in approved areas. Other compounds are not hazardous, and may be shipped or stored in any convenient manner. Because borate esters are susceptible to hydrolysis, the more sensitive compounds should be stored and transferred in an inert atmosphere, such as nitrogen. 

Di- and Triisobutylcncs. Diisobutylene [18923-87-0] and tnisobutylenes are prepared by heating the sulfuric acid extract of isobutylene from a separation process to about 90°C. A 90% yield containing 80% dimers and 20% trimers results. Use centers on the dimer, CgH, a mixture of 2,4,4-trimethylpentene-1 and -2. Most of the dimer-trimer mixture is added to the gasoline pool as an octane improver. The balance is used for alkylation of phenols to yield octylphenol, which in turn is ethoxylated or condensed with formaldehyde. The water-soluble ethoxylated phenols are used as surface-active agents in textiles, paints, caulks, and sealants (see Alkylphenols). 

O- Alkylation is comparable to A/-alkylation, but since the sodium salts are water-soluble it is most convenient to treat the phenol or naphthol in aqueous caustic solution with dimethyl sulfate or diethyl sulfate. These are comparatively expensive reagents, and therefore, alkoxy groups are introduced at a prior stage by a nucleophilic displacement reaction whenever possible. 

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