Alkylphenol condensates

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). 

ButylatedPhenols and Cresols. Butylated phenols and cresols, used primarily as oxidation inhibitors and chain terrninators, are manufactured by direct alkylation of the phenol using a wide variety of conditions and acid catalysts, including sulfuric acid, -toluenesulfonic acid, and sulfonic acid ion-exchange resins (110,111). By use of a small amount of catalyst and short residence times, the first-formed, ortho-alkylated products can be made to predominate. Eor the preparation of the 2,6-substituted products, aluminum phenoxides generated in situ from the phenol being alkylated are used as catalyst. Reaction conditions are controlled to minimise formation of the thermodynamically favored 4-substituted products (see Alkylphenols). The most commonly used is -/ fZ-butylphenol [98-54-4] for manufacture of phenoHc resins. The tert-huty group leaves only two rather than three active sites for condensation with formaldehyde and thus modifies the characteristics of the resin. 

A branched, high-molecular-weight condensation product of cardanol, an alkylphenol, and an aldehyde can be further ethoxylated and may be sul-fonated by the addition of sodium bisulfite in the presence of a free radical... 

Alkylphenol ethoxylates Fatty alcohol ethoxylates Castor oil ethoxylates Ethylene oxide-propylene oxide co-polymers Polyarylphenol ethoxylates Alkylphenol ethoxylate-formaldehyde condensates Non-ionic emulsifiers... 

Alkylphenol ethoxylate -formaldehyde condensates Sulphosuccinates Wetting agents... 

A sulfur moiety introduces a hydroperoxide deactivating effect into the stabilizer molecule. Moreover, the condensation of low molecular weight compounds with halides of sulfur represents an easy synthetic approach to the increase of the molecular weight and consequently to the improvement of the physical persistency of stabilizers. Efficient AO were prepared by this way from alkylphenols, aromatic amines or phenothiazine [21,174]. Most of them contain two active units connected with a sulfide/disulfide bridge and should be listed rather among high molecular weight stabilizers. Antioxidant 136 (n > m), prepared from pyrocatechol and... 

The alkylphenol ethylene oxide condensates have been the most widely produced nonionic detergent. These condensates are solubilized by the ethylene oxide units forming hydrates with water. Compared with all other materials that dissolve in water, these products show an apparent anomaly their solutions are completely clear in the cold, but when heated they become turbid and, if the temperature is raised sufficiently, separation into two phases can take place. This is explained by the fact that at an elevated temperature the hydrates are destroyed. 

Alkylphenols are weak acids, but substitution on the alkylphenol with methylene or sulphur increases the acidity. The methylene-substituted phenates originate from a condensation product between the alkylphenol and formaldehyde. Phen-ate sulphides can be obtained by at least three sulphurization reagents (1) sulphur monochloride, (2) sulphur dichloride and (3) elemental sulphur. The percentage of sulphur contained in a phenate sulphide detergent directly dictates the chemistry of the detergent because of the variable ratio of sulphur atoms to alkylphenol substrate and the variety of ways the sulphur atoms can be attached to the alkylphenol. Phenol detergents are more difficult materials to describe based on analytical data. Nevertheless, the same chemical concepts applied to sulphonates also apply to phenates. Table 7.2 summarizes the compositional ranges typically observed in phenate lubricant additives. 

The possibility of the occurrence of unusual condensation reactions with alkylphenols might be anticipated from the increased activation of the ring. Amongst the first, dimerisation of the alkenylphenol shown may be mentioned. 4-iso-Propenylphenol intrifluoracetic acid at ambient temperature furnished after 5mins.,1-(4-hydroxyphenyl)-1,3,3-trimethylindan-6-olin acceptable yiekJ(ref.64). 

Whilst arguably, the formaldehyde condensation reactions in the preceding section are, under acidic conditions, electrophilic in type, a considerably wider range of compounds result from the commercially available C4, Cg, and Cg alkylphenols with a variety of reactants in other electrophilic substitution reactions. Thus 2,6-di-tert-butylphenol condensed with formaldehyde in hydrochloric acid gives 3,5-di-tert-butyl-4-hydroxybenzyl chloride which can be utilised in an Arbuzov reaction with trialkylphosphites to afford the dialkyl phosphonate depicted (ref. 80). The diethyl ester (Irganox 1222, Ciba-Geigy Ltd.) in this series is a significant stabiliser for polyester fibres in the prevention of photo and oxidative deterioration. 

At high-temperature conditions, the product distributions of typical decar-boxylative and aldol condensations vary with temperature, time on stream, and catalyst age. Several ketone isomers can be produced. With acetic acid, e.g., C5-C7 (e.g., methylhexanone, pentan-2-one, 3,3 -dimethylbutan-2-one) ketones and alkylphenols arise from acetone aldolization. An important cyclic product in low temperature acetone aldolization is isophorone (2-cyclohexen-l-one, 3,5,5 -trimethyl), formed by the aldol condensation of acetone with mesityl oxide, followed by 1,6-Michael addition. In reactions with acetic acid, we have observed 2-cyclohexen-l-one, 3,5-dimethyl, which is probably a cracking product of isophorone, and small amounts of isophorone itself. Cracking to produce... 

A newer development in alkylphenol—formaldehyde resias has been the application of this condensation reaction to produce calixarenes, cydic oligomers of methylene-bridged alkylphenols (20). The smallest cycHc oligomer that has been isolated to date contains four alkylphenol groups. 

The original Zinke synthesis employed NaOH as the base to induce the condensation of / -alkylphenols and formaldehyde, and base induction remains the method of choice noi only for the three major calixarenes 2, 4, and 6 (R = tert Bu) but also for the two minor calixarenes 3 and 5 (R = tert B x). With NaOH (in small amounts) as the base and refluxing diphenyl ether as the solvent, a 50% yield of pure p-rcrr-butyicalix[4]arene 2 is produced."" With KOH (in larger amounts) as the base and refluxing xylene as the solvent, ca. 85% yields of p-tert-butylcalix[6]arene 4 are produced.With NaOH (in small amounts) as the base and refluxing xylene as the solvent, ca. 65% yields o/p- err-butylcalix[8]arene d are produced.The p- crr-butylcalix[5]arene and p-... 

Another common approach to water-based coating formulations is post-emulsification of a polymer in water. Several condensation polymers, e.g. alkyds, i.e. fatty-acid-modified polyesters, polyurethanes and epoxy resins, have been made into dispersions by the use of a suitable emulsifier and application of high shear. For instance, long oil alkyd resins of the type used in white-spirit-based formulations have been successfully emulsified by using nonionic surfactants such as fatty alcohol ethoxylates, alkylphenol ethoxylates or fatty acid monoethanolamide ethoxylates. Neutralization of alkyd carboxylic groups helps in producing small emulsion droplets and with the proper choice of surfactant, droplet diameters of less than 1 pm can be obtained. Such dispersions are sufficiently stable for most applications. 

The formation of calixarenes was first reported by Zinke [59]. In general, the condensation of 4- alkylphenols with methanal leads to the formation of such materials in the presenee of bivalent metal salts and alkaline ions, respectively (equation 11). 

NON-IONIC SURFACTANTS Polyoxyethylenated alkylphenols, alkylphenol ethoxylates Polyoxyethylenated straight- chain alcohols, alcohol ethoxylates Polyoxyethylenated polyoxypropylene glycols Polyoxyethylenated mercaptans Long-chain carboxylic acid esters Alkanolamine condensates, alkanolamides Tertiary acetylenic glycols Polyoxyethylenated silicones N-alkylpyrrolidones Alkylpolyglycosides... 

This high reactivity is especially essential for the production of phenol/formal-dehyde condensation products (Bakelite resins) phenol/formaldehyde resins were the first synthetic plastics, with production patented by Leo H. Baekeland in 1907. In addition to phenol, cresols, xylenols and long-chain alkylphenols are used to obtain special quality characteristics. Phenolic resins are used widely for numerous applications. Phenolic resin production in Western Europe in 1985 was around 500,0001, in the USA 1,150,0001 and in Japan 325,0001. 

The synthesis of such stabilizers can be accomplished by several methods. The most widespread method is the condensation of 2,6-di-h3 lroxymethylene-4-alkylphenols (mesitylene diols) with alkylated phenols [204-210] ... 

The synthesis of such compounds is accomplished by condensing di-or tri-alkylphenols possessing one unsubstituted ortho-position with sulfur monochloride, S2CI2, in an inert solvent at normal or increased temperatures [95, 140, 222] ... 

TLC has been useful in the analysis of polyethylene oxide compounds. Compounds containing a small, medium or large number of ethylene oxide units are formed, depending on the amount introduced in the reaction. Burgeb [10] has determined the ethylene oxide content and molecular weight distribution of polyethylene oxide condensates with fatty acids, fatty alcohols and alkylphenols, using silica gel and the upper layer of a well shaken mixture of methyl ethyl ketone-water (50 + 50) (Fig. 189). Polymeric products ( condensates ) from reaction of ethylene oxide with fatty amines can be chromatographed in the upper phase of the mixture methyl ethyl ketone-2.5 % ammonium hydroxide... 

TRYCOL Ethoxylated Alkylphenols are nonionic polyoxyethylene surfactants prepared commercially by the condensation or addition of ethylene oxide to alkylphenol at the site of its active hydrogen. 

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