Patent GB-444351-A (GB)
Title: Manufacture of condensation products from phenols, formaldehyde and amines
IPC: C08G14/06
Filed: 1934-12-17
Abstract: Basic products are obtained by the interaction of formaldehyde, a non - aromatic secondary amine containing less than seven carbon atoms, and a phenol substituted in the nucleus with a hydrocarbon radicle of more than three carbon atoms and having at least one free o-position to the hydroxyl group.  The phenol may be mono- or poly-cyclic, and may contain, in addition to the hydrocarbon radicle, other nuclear substituents such as additional hydroxyl groups, halogen atoms, or alkyl, alkoxy, nitro, amino or methylol groups; aldehyde groups or free acid groups, such as sulphonic or carboxylic groups, must not be present.  The hydrocarbon radicle may be an aromatic or hydroaromatic radicle, or a straight or branched aliphatic radicle of more than three carbon atoms.  Specified phenols are butylphenols, butylbromophenols, butylchlorophenols, butyliodophenols, the corresponding amyl-, hexyl-, heptyl-, octyl-, dodecyl-, hexadecyl-, and octadecyl-phenols, cyclohexyl-phenols, bornylphenols, tetrahydronaphthylphenols, phenylphenols, and benzylphenols, and the corresponding cresol, resorcinol, hydroquinone or naphthol derivatives.  Crude substituted phenols may be used such as are obtainable by treating a phenol, in the presence of sulphuric acid, with an olefine of more than three carbon atoms, and neutralizing the mixture; olefines specified for use in this way are butylenes, amylenes, hexenes, octenes, triand tetra-isobutylene, diamylene and higher olefines obtained by cracking petroleum.  Specified secondary amines are dimethylamine, diethylamine, methylethylamine, diisopropylamine, diethanolamine, di - n - propylamine, piperidine and piperazine; the use of secondary amines containing primary amino or free acid groups is excluded. The reagents may be brought to reaction simultaneously, preferably in an inert solvent such as alcohol, ether, benzene or dioxane, and in the presence or absence of a trace of an alkali, such as soda or caustic soda.  Alternatively, the phenol may be added to the reaction product of the amine and formaldehyde.  At least one mol. of formaldehyde and of amine is taken per mol. of phenol. The reaction may be effected at atmospheric or raised temperature. The salts of the products with water-soluble acids, e.g. acetic, phosphoric, lactic, gluconic, oxalic, sulphuric, hydrochloric or hydrofluoric acid, are useful (a) as wetting, cleansing and emulsifying agents in dyeing, laundering and bleaching, (b) as bactericides in acidic media, and (c) as fat-splitting catalysts. The quaternary ammonium salts obtained by treating the products with organic halides such as benzyl chloride, with organic sulphates such as dimethyl sulphate, or with ethyl chloroformate have similar properties.  The salts of the products with water-insoluble acids, e.g. higher fatty, naphthenic or resin acids, are soluble in oils and hydrocarbons and are useful as emulsifying agents, wax substitutes, plasticizers, ingredients of rubber compositions, and intermediates for dyes.  In the examples, products are obtained from (1) formaldehyde, dimethylamine or diethylamine, and p-tert.-butylphenol, p-tert.-amylphenol, p-benzylphenol, or p-cyclohexylphenol; (2) formaldehyde, dimethylamine, and o-phenylphenol or p-phenylphenol; (3) formaldehyde, piperidine, and a , a , g , g -tetramethylbutylphenol; (4) formaldehyde, dimethylamine, diethylamine, or diethanolamine, and a , a , g , g -tetramethylbutylphenol; (5) formaldehyde, dimethylamine, and (a) a dodecylphenol mixture obtained by condensing phenol with tri-isobutylene in the presence of sulphuric acid, or (b) a hexadecylphenol mixture obtained by condensing phenol with tetraisobutylene in the presence of sulphuric acid, or (c) laurylphenol, obtained by condensing phenol with lauryl alcohol in the presence of zinc chloride, or (d) cetylphenol, made by condensing phenol with cetyl alcohol in the presence of zinc chloride; (6) formaldehyde, dimethylamine, and a , a , g , g -tetramethylbutyl-p-cresol, obtained by condensing p-cresol with diisobutylene in the presence of sulphuric acid; (7) formaldehyde, dimethylamine, and (a) a , a , g , g -tetramethylbutylresorcinol, obtained by condensing resorcinol with diisobutylene in the presence of sulphuric acid, or (b) n-hexylresorcinol.ALSO:Basic products are obtained by the interaction of formaldehyde, a non-aromatic secondary amine containing less than seven carbon atoms, and a phenol substituted in the nucleus with a hydrocarbon radicle of more than three carbon atoms and having at least one free o-position to the hydroxyl group.  The phenol may be mono- or polycyclic, and may contain, in addition to the hydrocarbon radicle, other nuclear substituents such as additional hydroxyl groups, halogen atoms, or alkyl, alkoxy, nitro, amino or methylol groups; aldehyde groups or free acid groups, such as sulphonic or carboxylic groups, must not be present.  The hydrocarbon radicle may be an aromatic or hydroaromatic radicle, or a straight or branched aliphatic radicle of more than three carbon atoms.  Specified phenols are butylphenols, butylbromo-phenols, butylchlorophenols, butyliodophenols, the corresponding amyl-, hexyl-, heptyl-, octyl-, dodecyl-, hexadecyl-, and octadecyl-phenols, cyclohexylphenols, bornylphenols, tetrahydronaphthylphenols, phenylphenols, and benzylphenols, and the corresponding cresol, resorcinol, hydroquinone or naphthol derivatives.  Specified secondary amines are dimethylamine, diethylamine, methylethylamine, diisopropylamine, diethanolamine, di-n-propylamine, piperidine and piperazine; the use of secondary amines containing primary amino or free acid groups is excluded.  The salts of the products with water-soluble acids, e.g., acetic, phosphoric, lactic, gluconic, oxalic, sulphuric, hydrochloric or hydrofluoric acid, are useful as emulsifying agents in dyeing, laundering and bleaching, and as fat-splitting catalysts.  The quaternary ammonium salts obtained by treating the products with organic halides such as benzyl chloride, with organic sulphates such as dimethyl sulphate, or with ethyl chloroformate have similar properties.  The salts of the products with water-insoluble acids, e.g., higher fatty, naphthenic or resin acids, are soluble in oils and hydrocarbons and are useful as emulsifying agents.  In the examples, products are obtained from (1) formaldehyde, dimethylamine or diethylamine, and p-tert.-butylphenol, p-tert.-amylphenol, p-benzylphenol, or p-cyclohexylphenol; (2) formaldehyde, dimethylamine, and o-phenylphenol or p-phenylphenol; (3) formaldehyde, piperidine, and a g , a , g , g , -tetramethylbutylphenol; (4) formaldehyde, dimethylamine, diethylamine, or diethanolamine, and a , a , g , g , -tetramethylbutylphenol; (5) formaldehyde, dimethylamine, and (a) a dodecylphenol mixture, (b) a hexadecylphenol mixture or (c) laurylphenol, or (d) cetyphenol, (6) formaldehyde, dimethylamine, and a , a , g , g , -tetramethylbutyl-p-cresol; (7) formaldehyde, dimethylamine, and (a) a , a , g , g , -tetramethylbutylresorcinol or (b) n-hexylresorcinol.ALSO:Basic products are obtained by the interaction of formaldehyde, a nonaromatic secondary amine containing less than seven carbon atoms, and a phenol substituted in the nucleus with a hydrocarbon radicle of more than three carbon atoms and having at least one free o-position to the hydroxyl group.  The phenol may be mono- or poly-cyclic, and may contain, in addition to the hydrocarbon radicle, other nuclear substituents such as additional hydroxyl groups, halogen atoms, or alkyl, alkoxy, nitro, amino or methylol groups; aldehyde groups or free acid groups, such as carboxylic or sulphonic groups, must not be present.  The hydrocarbon radicle may be an aromatic or hydroaromatic radicle, or a straight or branched aliphatic radicle of more than three carbon atoms. Specified phenols are butylphenols, butylbromo-phenols, butylchlorophenols, butyliodophenols, the corresponding amyl-, hexyl-, heptyl-, octyl-, dodecyl-, hexadecyl-, and octadecyl-phenols, cyclohexylphenols, bornylphenols, tetrahydronaphthylphenols, phenylphenols, and benzylphenols, and the corresponding cresol, resorcinol, hydroquinone or naphthol derivatives.  Specified secondary amines are dimethylamine, diethylamine, methylethylamine, diisopropylamine, diethanolamine, di-n-propylamine, piperidine and piperazine; the use of secondary amines containing primary amino or free acid groups is excluded.  The salts of the products with water-insoluble acids, e.g. higher fatty, naphthenic or resin acids, are soluble in oils and hydrocarbons and are useful as plasticizers and ingredients of rubber compositions.  In the examples, products are obtained from (1) formaldehyde, dimethylamine or diethylamine, and p-tert.-butylphenol, p-tert-amylphenol, p-benzylphenol, or p-cyclohexylphenol; (2) formaldehyde, dimethylamine, and o-phenylphenol or p-phenylphenol; (3) formaldehyde, piperidine, and a , a , g , g , -tetramethyl-butylphenol; (4) formaldehyde, dimethylamine, diethylamine, or diethanolamine, and a , a , g , g , -tetramethylbutylphenol; (5) formaldehyde, dimethylamine, and (a) a dodecylphenol mixture or (b) a hexadecylphenol mixture or (c) laurylphenol, or (d) cetyphenol; (6) formaldehyde, dimethylamine, and a , a , g , g , -tetramethylbutyl-p-cresol; (7) formaldehyde, dimethylamine, and (a) a , a , g , g  -tetramethylbutylresorcinol or (b) n-hexylresorcinol.