Patent GB-468399-A (GB)
Title: Improvements in water-soluble phenolic derivatives
IPC: C08G14/06
Filed: 1936-02-05
Abstract: Phenolic products primarily adapted for use as soaps, wetting, emulsifying, tanning and germicidal agents are obtained by heating an alcohol containing a primary alcoholic group and a hydrohalide or sulphuric acid salt of a phenolic amine obtained by condensing a phenol, formaldehyde and a secondary amine of the formula XNHX1, in which X and X1 are alkyl groups which may link up to form a polymethylene ring.  Not more than one molecule each of the phenol and formaldehyde is used for each molecule of secondary amine and the term phenol covers mono and polycyclic phenols and Novolak resins which are soluble in dilute caustic soda.  The manufacture of the said salts is described in Specifications 444,351 and 457,391.  In examples: (1) a condensate obtained from phenol, dimethylamine and formaldehyde is converted into its sulphuric acid salt in the presence of toluene and reacted with lauryl, cetyl and oleyl alcohols, a  - ethylhexanol, 1 : 10 - decamethyleneglycol, octadecanediol, and a  : a  : g  : g -tetramethylbutylphenoxyethanol; (2) a condensate obtained from o-cresol, dimethylamine and formaldehyde is converted into its sulphuric acid salt and reacted with lauryl and cetyl alcohols; (3) a condensate obtained from a  : a : g  : g -tetramethylbutylphenol, dimethylaniline and formaldehyde is converted into its hydrochloride or sulphate and reacted with ethyl and lauryl alcohols, glycerol, and diethyleneglycol; (4) laurylalcohol is reacted with the sulphates of the phenolic amines obtained by condensing formaldehyde and dimethylamine with 1 : 3 : 5-xylenol, p-chlorphenol, o-phenylphenol, or b -naphthol or by condensing formaldehyde and piperidine with a  : a  : g  : g -tetramethylbutylphenol or by condensing formaldehyde and diethylamine with bis-(p-hydroxydiphenyl)-dimethylmethane.  The products may be used in washing, bleaching, bucking, tanning, mordanting and dyeing processes, in hydrolyzing fats, emulsifying oils and fats in water, breaking petroleum emulsions and dispersing pigments and dyestuffs.  They may also be added to pine oil and soapy germicides.  The products may be coupled with diazotized aromatic amines to give azo dyestuffs, and the product obtained by reacting laurylalcohol with the condensate from p-chlorphenol, formaldehyde and dimethylamine is stated to be a soft resin.  Trimethyleneglycol, triethyleneglycol, glycolmonoethyl or butyl ether, pentaerithrite, mannitol, phenoxyethanol, tetrahydrofurfurylalcohol, the alcohols obtained by reducing coconut oil, palm oil, tallow and castor oil, alcohols obtained from spermaceti, beeswax and wool grease and alcohols containing sulphur, oxygen, and the group CO-- in the molecule are mentioned as suitable alcohols, while the following phenolic compounds are specified: propylto octyl-phenols, decylphenol, laurylphenol, cetylphenol and the corresponding cresols and resorcinols, benzylphenol, cyclohexylphenol, thymol, guaiacol, pyrocatechol, hydroquinone and their halogen, alkoxy and acyl derivatives.ALSO:Phenolic products useful for splitting fats and for emulsifying oils and fats in water are obtained by heating an alcohol containing a primary alcoholic group and a hydrohalide or sulphuric acid salt of a phenolic amine obtained by condensing a phenol, formaldehyde and a secondary amine of the formula XNHX, in which X and X1 are alkyl groups which may link up to form a polymethylene ring.  The term phenol covers mono- and poly-cyclic phenols and Novolak resins which are soluble in dilute caustic soda.  In examples: (1) a condensate obtained from phenol, dimethylamine and formaldehyde is converted into its sulphuric acid salt and reacted with lauryl, cetyl and oleyl alcohols, a -ethylhexanol, 1 : 10-decamethyleneglycol, 1 : 12-octadecanediol, and a .a  : g  : g  - tetramethylbutylphenoxyethanol; (2) a condensate obtained from o-cresol, dimethylamine and formaldehyde is converted into its sulphuric acid salt and reacted with lauryl and cetyl alcohols; (3) a condensate obtained from a  : a  : g  : g -tetramethyl butylphenol, dimethylaniline and formaldehyde is converted into its hydrochloride or sulphate and reacted with ethyl and lauryl alcohols, glycerol and diethyleneglycol; (4) lauryl alcohol is reacted with the sulphates of the phenolic amines obtained by condensing formaldehyde and dimethylamine with 1 : 3 : 5-xylenol, p-chlorphenol, o-phenyl-phenol or b -naphthol, or by condensing formaldehyde and piperidine with a : a  : g  - g -tetramethylbutylphenol, or by condensing formaldehyde and diethylamine with bis-(p-hydroxydiphenyl)-dimethylmethane. Trimethyleneglycol, triethyleneglycol, glycolmonoethyl or butyl ether, pentaerythrite, mannitol, phenoxyethanol, tetrahydrofurfurylalcohol, the alcohols obtained by reducing coconut oil, palm oil, tallow and castor oil, alcohols obtained from spermaceti, beeswax and wool grease and alcohols containing sulphur, oxygen and the group CO-in the molecule are mentioned as suitable alcohols, while the following phenolic compounds are specified: propylto octyl-phenols, decylphenol, laurylphenol, cetylphenol and the corresponding cresols and resorcinols, benzylphenol, cyclohexylphenol, thymol, guaiacol, pyrocatechol, hydroquinone and their halogen, alkoxy and acyl derivatives.ALSO:Phenolic products obtained by heating an alcohol containing a primary alcoholic group and a hydrohalide or sulphuric acid salt of a phenolic amine derived from a phenol, formaldehyde and a secondary amine of the formula XNHX1, in which X and X1 are alkyl groups which may link up to form a polymethylene ring, are added to pine oil or soap to increase their germicidal power.  Alcohols specified are lauryl, oleyl and cetyl alcohol, 1 : 10-decamethyleneglycol, 1 : 12-octadecanediol, a  : a  : g  : g -tetramethylbutylphenoxyethanol, glycerol, diethyleneglycol, p trimethyleneglycol, pentaerithrite, mannitol, phenoxyethanol, and tetrahydrofurfurylalcohol.  The phenolic amines may be derived from phenol, cresol, xylenol, a  : a  : g  : g -tetramethylbutylphenol, p-chlorphenol, b -naphthol, bis-(p-hydroxydiphenyl) - dimethylmethane, propylphenol, laurylphenol, resorcinol, cyclohexylphenol, thymol, guaiacol, pyrocatechol, hydroquinone and their halogen, alkoxy and acylderivatives.  Dimethylamine, dimethylaniline and piperidine are mentioned as suitable secondary amines.