Patent GB-470181-A (GB)
Title: Manufacture and application of polyglycol ethers
IPC: C09K23/00
Filed: 1935-12-31
Abstract: An aromatic hydroxy compound substituted in the nucleus by at least one hydrocarbon or acyl radicle of at least four carbon atoms, or a hydroaromatic hydroxy compound substituted in the nucleus by at least one hydrocarbon radicle (other than an aliphatic radicle) of at least four carbon atoms, is treated with one or more mols. of an a , b -alkylene oxide or a corresponding halogenhydrin, the term "a , b -alkylene oxide" meaning alkylene oxides in which the oxide oxygen atom is linked to adjacent carbon atoms of an alkylene residue but not necessarily to the ultimate and penultimate carbon atoms. Alternatively, an aromatic or hydroaromatic hydroxy compound substituted as above, or a hydroaromatic hydroxy compound substituted in the nucleus with at least one aliphatic hydrocarbon radicle of at least four carbon atoms, is treated in the form of its alkali compound with an a , b -halogen hydrin, the resulting hydroxyalkyl ether is converted into a halogenalkyl ether, e.g. by treatment with thionyl chloride, and the halogenalkyl ether is treated with a poly-a , b -glycol in the presence of caustic alkali.  The aromatic hydroxy compounds used as starting materials are obtainable (a) by reaction of aromatic hydroxy compounds with olefines containing at least four carbon atoms, e.g. with isobutylene, diisobutylene, n-dodecylene, cyclohexene or comphene, or with olefine mixtures obtainable by dehydrating mixtures of primary alcohols containing 4--8 carbon atoms, produced from carbon monoxide and hydrogen, or with olefine mixtures obtainable by polymerization of lower olefines such as ethylene, propylene, isobutylene, or the olefines obtainable from the alcohols specified above, or (b) by condensing aromatic hydroxy compounds with halogenated compounds containing at least four carbon atoms, such as pinene hydrochloride, isobutyl chloride, halogenated natural or synthetic hydrocarbon oils, or halogenated fractions of brown-coal tar, the condensation being effected in the presence of any of the usual catalysts, e.g. aluminium chloride, zinc chloride, ferric chloride, activated aluminium, or zinc dust, or (c) by condensing aromatic hydroxy compounds in known manner with alcohols containing at least four carbon atoms, e.g. tertiary butyl alcohol, cyclohexanol, methylcyclohexanols, or primary alcohols of 4--8 carbon atoms produced from carbon monoxide and hydrogen; alkyl-substituted aromatic starting materials are also obtainable from the acyl-substituted aromatic hydroxy compounds by reduction of the carbonyl group, and the acyl-substituted aromatic compounds are themselves obtainable by esterifying aromatic hydroxy compounds with appropriate carboxylic acids and treating the esters with aluminium chloride, whereby molecular rearrangement to the corresponding ketones is effected; the hydroaromatic compounds used as starting materials are obtainable by catalytic reduction of the corresponding aromatic compounds.  Specified starting materials are n-butylphenols, isobutyl - o - cresols, diisobutyl-phenols, isoamylcresols, isohexylxylenols, isooctylphenols, isooctyl-o-chlorophenols, isooctyl-b -naphthols, isononylresorcinols, n- and isododecylphenols, isododecylcyclohexanols, n-octadecylphenols, n - undecyl - p - oxyphenyl ketone, n-heptdecyl-p-oxyphenyl ketone, o- and p - benzylphenol, cyclohexyl - o - cresols, p-oxydiphenyl, p-oxyphenylcamphanes, and the condensation products of phenol or cresols with diterpenes.  Specified alkylene oxides are ethylene oxide, 1 : 2-propylene oxide, 1 : 2- or 2 : 3-butylene oxide, butadiene dioxide, cyclohexene oxide, glycide and epichlorhydrin. The reaction of the alkylene oxides with the aromatic or hydroaromatic hydroxy compounds may be effected at 50--250 DEG  C. in the presence of a catalyst consisting of a caustic alkali, an alkali alcoholate, a tertiary organic base, or an acid substance such as potassium bisulphate.  The products may be after-treated with organic reagents capable of reacting with hydroxy groups, and particularly with polybasic organic acids or with halogenated carboxylic or sulphonic acids.  The ethers or their conversion products, obtained as described above, are useful, particularly in the textile industry, as wetting, washing, dispersing, foaming and softening agents, and also in the dyeing industry as through-dyeing or levelling agents.  The products may be used alone or with appropriate additions, particularly (a) aliphatic, hydroaromatic or aromatic sulphonic acids (particularly in the form of their water-soluble salts) such as sulphonation products of heavy benzene, solar oil, solvent naphtha or naphthalene, or condensation products of such sulphonation products containing methylene groups, alkyl groups or benzyl groups, or the sulphonation products of Edeleanu extract, naphthenes, or naphthenic acids, or the sulphonation products obtained in refining petroleum or benzine with sulphuric acid, or sulphonation products of the turkey red oil type, including sulphonates of fatty alcohols and the condensation products of fatty acids of high molecular weight with aliphatic or aromatic hydroxy- or aminosulphonic acids, (b) salts of fatty, resinic or naphthenic acids or of benzoic or phthalic acid, (c) reaction products of fatty acid chlorides with sarcosine, albumen hydrolysis products, aromatic aminocarboxylic acids, or tartaric or salicylic acid, (d) inorganic salts such as alkali meta- or pyrophosphates, sodium carbonate, waterglass, or sodium sulphate or chloride, and (e) bleaching agents.  The following examples are given: (1) (a) an excess of ethylene oxide (6 mols. or more) is caused to act on p-isooctylphenol (from phenol and diisobutylene), or on a mixture of alkylphenols obtained from phenol and an isobutylene polymerization product containing di- and tri-isobutylene and other olefines, or on an isooctyl-o-cresol; (b) cotton goods are washed in a bath containing isooctyl-o-cresol polyglycol ether, sodium pyrophosphate, and sodium metaphosphate; (c) three washing baths for cotton containing, respectively, isooctylphenol polyglycol ether, a reaction product of oleyl chloride and an albumen hydrolysate, and both these substances together, are compared; (d) comparison is made also of three washing baths containing (a ) isooctylphenol polyglycol ether and soda, (b ) partly degraded glue and soda, and (g ) the components of both the other baths; (e) a washing agent for textiles contains isooctylphenol polyglycol ether, soda, and a product obtained by treating sodium cellulose with ethylene oxide and sodium chlorethanesulphonate; the washing effect is compared with that of a bath containing soap and soda; (f) solid washing compositions containing liquid isooctylphenol polyglycol ether are obtained by mixing the latter with soda and a product obtained from sodium cellulose, ethylene oxide and sodium chlorethanesulphonate; glue or degraded glue may be used in place of the cellulose derivative, and the soda may be replaced or supplemented by sodium perborate, sodium bicarbonate or a mixture of sodium peroxide and a bicarbonate (g) comparison is made of four washing baths containing (a ) soap, soda, sodium perborate, sodium pyrophosphate, and sodium silicate, (b ) isooctylphenol polyglycol ether, sodium butylnaphthalenesulphonate, soda, sodium pyrophosphate, sodium silicate, sodium perborate, magnesium sulphate, and sodium sulphate, (g ) as under (b ), but containing a reaction product of oleyl chloride with sodium oxyethanesulphonate or with sodium methyltaurine in place of sodium butylnaphthalene-sulphonate, (d ) as under (b ), but containing the sodium salt of oleyl alcohol sulphuric ester in place of sodium butylnaphthalenesulphonate; (h) a washing composition contains isooctylphenol polyglycol ether, cattle pancreas and soda; other enzymes may replace the pancreatic enzymes; (i) washing compositions for textiles soiled with oil contain isooctylphenol polyglycol ether, a solvent such as turpentine, butanol or amyl alcohol, and water. (2) (a) Isododecylphenol is treated with an excess of ethylene oxide; the isododecylphenol may be obtained by condensing phenol with a propylene polymerization product consisting mainly of hydrocarbons of twelve carbon atoms, or by treating phenol with isododecyl chloride (prepared by chlorinating a light oil fraction containing dodecanes) in the presence of aluminium chloride; (b) ethylene oxide is caused to act on an alkylated cresol mixture obtained by treating crude cresol, in the presence of zinc chloride or aluminium chloride, with a monochlorinated middle oil fraction boiling at 160--220 DEG  C.; (c) laundry goods are soaked in a bath containing soda and an isododecylphenol polyglycol ether; they are then rinsed, and boiled in a bath containing soda, sodium perborate, and isododecylphenol polyglycol ether.  (3) Isohexylphenol is treated with ethylene oxide; a bath containing the product and soda is used for washing wool greased with olive oil.  (4) Heptadecenyl-p-oxyphenyl ketone or undecyl-p-oxyphenyl ketone is treated with ethylene oxide; a bath containing soda and the product from undecyl-p-oxyphenyl ketone is used for washing wool.  (5) Isobutylphenol is treated with ethylene oxide; a mixture of the product with xylenol is added as a wetting agent to a mercerizing lye.  (6) Decylphenol (from crude decyl chloride and phenol) is treated with ethylene oxide.  (7) Isononylphenol is treated with ethylene oxide; a dispersion of the product may be used for greasing wool; the isononylphenol is obtained by condensing phenol with a propylene polymerization product consisting of isononylenes.  (8) Tetradecylphenol is treated with ethylene oxide, and the product is optionally treated with a halogenated carboxylic acid; the tetradecylphenol is obtained by treating phenol with tetradecene in the presence of boron fluoride. (9) Phenol is treated, in the presence of boron fluoride,