Patent GB-457391-A (GB)
Title: Complex phenolic soaps
IPC: C11D13/02
Filed: 1935-05-24
Abstract: Saponaceous products are obtained by neutralizing soap-forming acids containing more than seven carbon atoms with bases obtained by condensing a phenol with a non-aromatic secondary amine and formaldehyde.  In preparing the bases, up to 1 mol. each of phenol and formaldehyde is used per mol. of amine unless the latter contains more than one secondary amino group, in which event up to 1 mol. each of phenol and formaldehyde may be used for each secondary amino group in the amine.  The phenols used must be unsubstituted in at least one o- or p-position to the (or a) hydroxy group, and must not contain aldehyde groups or acid groups such as carboxylic or sulphonic groups; substituents such as hydroxy, alkoxy, aryloxy, aryl alkyl, nitro, amino, hydroxyalkyl (including methylol) and acyl groups, and chlorine, bromine and iodine, may be present.  Specified phenols are phenol, o-, m- and p-cresol, 1 : 3 : 5-xylenol, thymol, carvacrol, chlorophenols, guaiacol, resorcinol and its monoethyl ether, a - or b -naphthol, o-, m- or p-phenylphenol, cyclohexylphenols, p-sec.-butylphenol, 1 : 3-dihydroxy-4-n-hexylbenzene, 1 : 3-dihydroxy-4-n-caproylbenzene, a , a , g , g -tetramethylbutylphenols, p-, p<1>-dihydroxydiphenyl dimethyl methane, 1 - 3-dihydroxy-4-isopropylbenzene, di-isopropylresorcinol, p-ter.-butylphenol, p-ter.-amylphenol, p-sec.-hexylphenol, diamylphenols, 2-hydroxyquinoline and 1 : 5-dihydroxynaphthalene. Specified secondary amines are dimethylamine, diethylamine, ethylmethylamine, dipropylamine, diethanolamine, morpholine, piperidine, piperazine, triethylenetetramine, dibutylamine, and diamylamine; amines containing aldehyde or acid groups, such as carboxylic or sulphonic groups, must not be used.  The preparation of the bases may be effected in water or an inert solvent at a temperature below 45 DEG  C.  Specified soap-forming acids are (a) aliphatic acids such as lauric, palmitic, undecylenic, stearic, oleic, ricinoleic, erucic, cerotic, linoleic, elaeostearic and elaidic acids, either in pure form or as obtained by the hydrolysis of their glycerides, and the halogenated, hydroxylated, arylated or sulphonated derivatives of these acids, such as chloro- or dichloro-stearic acids, mono-, di- or tri-hydroxystearic acids, sulphonated ricinoleic or castor-oil acids, a -sulphostearic acid, and phenylstearic acids; (b) resin acids such as abietic or montanic acids, naphthenic acids obtained from petroleum, and acids obtained by oxidizing paraffin oils or waxes; (c) sulphonated hydrocarbons, phenols or aromatic ethers having more than seven carbon atoms, such as hexadecylsulphonic acid, octylbenzenesulphonic acid, isopropylnaphthalene sulphonic acids, butylphenolsulphonic acids, and octyloxyphenylsulphonic acids; (d) sulphuric or phosphoric esters of aliphatic, aromatic or alicyclic alcohols containing more than seven carbon atoms, such as octylsulphuric acid, laurylsulphuric acid, cetylsulphuric acid, octadecylsulphuric acid, oleylsulphuric acid, lauryl phosphoric cetylphosphoric acid, cresoxyethylsulphuric acid, and a -terpineolsulphuric acid.  The reaction between the base and the soap-forming acid may be effected in the presence or absence of an organic solvent.  The salts are soluble in water and/or hydrocarbon oils and may be used as germicidal soaps, alone or with ordinary soaps, as emulsifying agents for oils, fats or waxes, as pigment-suspending agents in printing inks, as detergents and wetting agents in laundering, scouring, dyeing, tanning and mordanting, and as constituents of insecticidal compositions, boring or metal-cutting oils, cattle dips, metal-pickling baths (as inhibitors), and pharmaceutical preparations.  Examples are given of the preparation of bases from (1) phenol, formaldehyde, and dimethylamine, (2) o-cresol, formaldehyde and dimethylamine, (3) 1 : 3 : 5-xylenol, formaldehyde and dimethylamine, (4) phenol, formaldehyde, and diethanolamine and (5) p-p<1>-dihydroxydiphenyldimethylmethane, formaldehyde and dimethylamine; resorcinol, guaiacol, thymol, a chlorophenol or a chlorocresol may be used in place of the specified phenols.  In examples of the preparation of salts, (6) the product of any of examples 1--3 is treated with oleic, palmitic, or ricinoleic acids, or the acids of coconut oil or linseed oil, or a resin acid; (7) the product of any of examples 1--3 is treated with laurylsulphuric acid, cetylsulphuric acid, or octadecylsulphuric acid; (8) the product of example 4 is treated with oleic acid, laurylsulphuric acid, cetylsulphuric acid, or octadecylsulphuric acid; (9) the product of example 5 is treated with oleic acid; (10) a base prepared from phenol (2 mols.), formaldehyde (2 mols.), and triethylenetetramine (1 mol.) is treated with oleic acid; (11) a base prepared from b -naphthol, formaldehyde, and dimethylamine is treated with laurylsulphuric acid.  Specification 444,351 is referred to.ALSO:Saponaceous products are obtained by neutralizing soap-forming acids containing more than seven carbon atoms with bases obtained by condensing a phenol with a non-aromatic secondary amine and formaldehyde.  In preparing the bases, up to 1 mol. each of phenol and formaldehyde is used per mol. of amine unless the latter contains more than one secondary amino group, in which event up to 1 mol. each of phenol and formaldehyde may be used for each secondary amino group in the amine.  The phenols used must be unsubstituted in at least one o- or p-position to the (or a) hydroxy group, and must not contain aldehyde groups or acid groups such as carboxylic or sulphonic groups; substituents such as hydroxy, alkoxy, aryloxy, aryl, alkyl, nitro, amino, hydroxyalkyl (including methylol) and acyl groups, and chlorine, bromine and iodine, may be present.  Specified phenols are phenol, o-, m- and p-cresol, 1 : 3 : 5-xylenol, thymol, carvacrol, chlorophenols, guaiacol, resorcinol and its monoethyl ether, a - or b -naphthol, o-, m- or p-phenylphenol, cyclohexylphenols, p-sec.-butylphenol, 1 : 3-dihydroxy-4-n-hexylbenzene, 1 : 3-dihydroxy-4-n-caproylbenzene, a , a , g , g ,-tetramethylbutylphenols, p, p<1>-dihydroxydiphenyldimethylmethane, 1 : 3-dihydroxy-4-isopropylbenzene, di-isopropylresorcinol, p-ter.-butylphenol, p-ter.-amylphenol, p-sec.-hexylphenol, diamylphenols, 2-hydroxyquinoline, and 1 : 5-dihydroxynaphthalene. Specified secondary amines are dimethylamine, diethylamine, ethylmethylamine, dipropylamine, diethanolamine, morpholine, piperidine, piperazine, triethylenetetramine, dibutylamine, and diamylamine; amines containing aldehyde or acid groups, such as carboxylic or sulphonic groups, must not be used.  Specified soap-forming acids are (a) aliphatic acids such as lauric, palmitic, undecylenic, stearic, oleic, ricinoleic, erucic, cerotic, linoleic, elaeostearic, and elaidic acids, either in pure form or as obtained by the hydrolysis of their glycerides, and the halogenated, hydroxylated, arylated or sulphonated derivatives of these acids, such as chloro- or dichloro-stearic acids, mono-, di- or tri-hydroxystearic acids, sulphonated ricinoleic or castor-oil acids, a -sulphostearic acid, and phenylstearic acids; (b) resin acids such as abietic or montanic acids, naphthenic acids obtained from petroleum, and acids obtained by oxidizing paraffin oils or waxes; (c) sulphonated hydrocarbons, phenols or aromatic ethers having more than seven carbon atoms, such as hexadecylsulphonic acid, octylbenzenesulphonic acid, isopropylnaphthalenesulphonic acids, butylphenolsulphonic acids, and octyloxyphenylsulphonic acids; (d) sulphuric or phosphoric esters of aliphatic, aromatic or alicyclic alcohols containing more than seven carbon atoms, such as octylsulphuric acid, laurylsulphuric acid, cetylsulphuric acid, octadecylsulphuric acid, oleylsulphuric acid, laurylphosphoric cetylphosphoric acid, cresoxyethylsulphuric acid, and a -terpineolsulphuric acid.  The salts are soluble in water and (or) hydrocarbon oils and may be used as germicidal soaps, alone or with ordinary soaps, as emulsifying agents for oils, fats or waxes, as pigmentsuspending agents in printing inks, and as detergents in laundering, scouring, dyeing, tanning and mordanting.  Examples are given of the preparation of bases from (1) phenol, formaldehyde, and dimethylamine, (2) o-cresol, formaldehyde and dimethylamine, (3) 1 : 3 : 5-xylenol, formaldehyde and dimethylamine, (4) phenol, formaldehyde, and diethanolamine and (5) p,p<1>-dihydroxydiphenyldimethylmethane, formaldehyde and dimethylamine; resorcinol, guaiacol, thymol, a chlorophenol or a chlorocresol may be used in place of the specified phenols.  In examples of the preparation of salts, (6) the product of any of examples 1-3 is treated with oleic, palmitic, or ricinoleic acids, or the acids of cocoanut oil or linseed oil, or a resin acid; (7) the product of any of examples 1-3 is treated with laurylsulphuric acid, cetylsulphuric acid, or octadecylsulphuric acid; (8) the product of example 4 is treated with oleic acid, laurylsulphuric acid, cetylsulphuric acid, or octadecylsulphuric acid; (9) the product of example 5 is treated with oleic acid; (10) a base prepared from phenol (2 mols.), formaldehyde (2 mols.), and triethylenetetramine (1 mol.) is treated with oleic aicd; (11) a base prepared from b -naphthol, formaldehyde, and dimethylamine is treated with laurylsulphuric acid.  Specification 444,351 is referred to.ALSO:Products useful as inhibitors in metal-pickling baths are obtained by neutralizing soap-forming acids containing more than seven carbon atoms with bases obtained by condensing a phenol with a non-aromatic secondary amine and formaldehyde.  In preparing the bases, up to 1 mol. each of phenol and formaldehyde is used per mol. of amine unless the latter contains more than one secondary amino group, in which event up to 1 mol. each of phenol and formaldehyde may be used for each secondary amino group in the