Patent GB-447898-A (GB)
Title: Improvements in or relating to the manufacture of detergent, wetting, emulsifying, penetrating and like agents
Filed: 1934-09-15
Abstract: Products having wetting, penetrating, foaming, detergent, and emulsifying properties are obtained by the sulphonation of phenols having an alkyl hydrocarbon radicle containing 12 or more carbon atoms and possibly a methyl group attached to the nucleus.  The alkyl phenols may be made by treating phenol, a cresol or mixtures thereof with alkylating agents, e.g. primary, secondary or tertiary alcohols, olefines--preferably having a double bond between the ultimate and penultimate carbon atoms--or halogenated aliphatic hydrocarbons. Zinc, aluminium, antimonic and ferric chlorides and sulphuric acid may be used as condensing agents. The preparation of alkyl-phenols and cresols is described using cetyl alcohol (pure and crude), lauryl alcohol, octadecyl alcohol, 1 : 2-heptadecene and cetene as alkylating agents.  In examples: (1) alkyl phenols made by condensing phenol with higher olefines obtained by the removal of hydrochloric acid from chlorinated petroleums are sulphonated with sulphuric acid monohydrate, chlorsulphoric acid or a mixture of oleum with acetic anhydride; the sulphonated product may be extracted with alcohol and neutralized with soda ash, pyridine or ethylamine: the resulting salts are foaming and tanning agents as well as detergents; (2) purified hexadecylphenol and higher alkylphenols prepared from mixtures containing hexadecyl alcohol, such as may be prepared by condensing coconut fatty acids with phenol and reducing the resulting ketonephenols, are sulphonated with oleum and acetic anhydride or other sulphonating agent; a mixture of cetyl alcohol and dimethylpentadecylcarbinol is condensed with phenol and sulphonated; p-normal cetylphenol, which may be prepared by reducing the product of condensation of phenol and palmitic acid or by reducing the product of condensation of benzene and palmityl chloride, sulphonating and fusing with caustic alkali is also sulphonated; (3) octadecylphenol is sulphonated with oleum and acetic anhydride; (4) a pentadecylphenol prepared from a pentadecyl alcohol obtained by condensing amyl alcohol with itself is sulphonated; (5) tricosanol phenol prepared from tricosanol-7 is sulphonated; (6) a tertiary higher alcohol is prepared from the condensation product of the isobutyl esters of coconut fatty acids with amylmagnesium bromide by saponification and is condensed with phenol and sulphonated. Diluents such as carbontetrachloride, dichlorethane, tetrachlorethane, and dichlorbenzene may be used in the sulphonation process, and the product may be neutralized with alkali hydroxides, carbonates and bicarbonates, magnesium oxide, triethanolamine, propanolamines, ethylenediamine, triethylenetetramine, butanolamines, diaminepropanol and aromatic mono and polyamines.  Polyvalent bases may serve to combine residues of different alkylphenolsulphonic acids.  The following examples relate to applications of the products; (7) compositions for washing, cleansing, laundering and scouring fibrous materials such as wool, silk, cotton, rayon, paperpulp and silk are made by mixing the sulphonated alkyl phenols with common salt, ammonium chloride, acid and normal sodium sulphate, sodium carbonate, lauryl alcohol, sodium dipropylnaphthalene-sulphonate, soap, e.g. Marseilles or Castile, sodium palmitate or palmitic acid; (8) an aqueous emulsion of carnauba wax prepared by means of the products is used for cleansing and polishing furniture, automobiles or leather; (9) an aqueous emulsion of white oil is used as a solvent composition or for textile or pest destroying purposes; (10) a mixture of the products with p-tert: amylphenol or tetradecyl phenol is used for wetting cotton or as a germicide; (11) for bleaching cotton or wood-pulp and stripping sulphur or other dyestuffs, additions of sodium hypochlorite or hydrosulphite are made to solutions of the sulphonated alkylphenols; (12) an emulsion of latex prepared with the products is used for impregnating cotton; (13) the products are added to bowking, sizing (magnesium sulphate) and fulling (palm soap) baths; (14) the products are used in dyeing cellulose esters and with a dyestuff such as 1 : 4-diaminoanthraquinone; (15) wool skeins or felt are dyed in a bath containing a sulphonated alkyl phenol, fast wool cyanone R, sodium bichromate and acetic acid; (16) the products are used for mordanting in dyeing cotton with Victoria green WB; (17) fabrics dyed with vat dyes or Naphthol AS colours are after-treated by boiling with a solution of one of the products; (18) cotton is dyed in a vat containing Vat pink FF, (6 : 6<1>-dichlor-4 : 4<1>-dimethylthioindigo), caustic soda, sodium hydrosulphite and the sulphonated alkyl phenol; (19) a padding liquor is prepared from gum arabic, gum tragacanth, the dyestuff No. 1118 of the Colour Index and the products; any anthraquinone, indigoid or thioindigoid dyestuff may be use; (20) a bath for dyeing a mixed cotton and silk skein contains Diazine black H extra, common salt and a sulphonated alkylphenol; the silk is not stained; (21) a dispersion of neat's foot oil is used for softening leather; the latter is also protected from mildew; (22) the products, in the presence of acetic acid are used for tanning sheepskin; (23) the products are added to mercerizing lyes and carbonizing liquids; (24) a solution is made up containing Naphthol AS, turkey red oil, caustic soda, salt, formaldehyde and a sulphonated alkylphenol and used for padding cloth prior to development; (25) barium chloride is added to a solution comprising wool orange A, aluminium hydrate and a sulphonated alkyl phenol to prepare a lake.  The products may be used for dispersing lampblack, sulphur, blanc-fixe, and minerals and may be used in the preparation of inks, pigments, plastics, stable diazonium and nitroso preparations, cosmetics, hair and mouth washes, dentifrices, fungicides, germicides, boring oils, lubricants for fibres and machinery, gas washing liquids, sunburn preventatives and soap-dye and dry cleaning preparations.  The sulphonated alkyl phenols may be incorporated with soaps, alcohols, hydrocarbons, esters, amines, fats, oils, waxes, unguents, alkylphenols, ketones, mineral oils, resins, alkyl sulphates, organic and inorganic acids, and bases and sterile starch, glue, wood and gelatine.  Their use in electrolysis, fat splitting, separating minerals by flotation, fire extinguishing, protecting oxidizable baths, felting, dyeing with aniline black, sulphur, chrome and acid, basic and chrome dyestuffs, washing nitrocellulose and precipitating viscose in a bath, is mentioned as well as the treatment of hair, straw, hides, skins and feathers. Since they contain a phenol group, the products may be used as coupling components for azo dyes.  Reference has been directed by the Comptroller to Specification 365,170.ALSO:Products having detergent, fat-splitting, and emulsifying properties are obtained by the sulphonation of phenols having an alkyl hydrocarbon radicle containing 12 or more carbon atoms and possibly a methyl group attached to the nucleus.  For the preparation of alkylphenols and cresols which may be used as starting materials, cetyl alcohol (pure and crude), lauryl alcohol, octadecyl alcohol, 1 : 2 heptadecene and cetene are mentioned as alkylating agents.  In examples: (1) alkyl phenols made by condensing phenol with higher olefines obtained by the removal of hydrochloric acid from chlorinated petroleums are sulphonated with sulphuric acid monohydrate, chlorsulphonic acid or a mixture of oleum with acetic anhydride; the sulphonated product may be extracted with alcohol and neutralized with soda ash pyridine or ethylamine: the resulting salts are stated to be detergents: (2) purified hexadecylphenol and higher alkylphenols prepared from mixtures containing hexadecyl alcohol, such as may be prepared by condensing coconut fatty acids with phenol and reducing the resulting ketonephenols, are sulphonated with oleum and acetic anhydride or other sulphonating agent; a mixture of cetyl alcohol and dimethylpentadecylcarbinol is condensed with phenol and sulphonated; p-normal cetylphenol is also sulphonated: (3) octadecylphenol is sulphonated with oleum and acetic anhydride: (4) a pentadecylphenol prepared from a pentadecyl alcohol obtained by condensing amyl alcohol with itself is sulphonated: (5) tricosanol phenol prepared from tricosanol-7 is sulphonated: (6) a tertiary higher alcohol is prepared from the condensation product of the isobutyl esters of coconut fatty acids with amylmagnesium bromide by saponification and is condensed with phenol and sulphonated.  The product may be neutralized with alkali hydroxides, carbonates and bicarbonates, magnesium oxide, triethanolamine propanolamines, ethylenediamine, triethylenetetramine, butanolamines, diamine propanol and aromatic mono- and polyamines.  Polyvalent bases may serve to combine residues of different alkylphenolsulphonic acids.  The following examples relate to applications of the products: (7) compositions for washing, cleansing, laundering and scouring fibrous materials such as wool, silk, cotton, rayon, paperpulp and silk are made by mixing the sulphonated alkyl phenols with common salt, ammonium chloride, acid and normal sodium sulphate, sodium carbonate, lauryl alcohol, sodium dipropylnaphthalenesulphonate, soap, e.g. Marseilles or Castile, sodium palmitate or palmitic acid: (8) an aqueous emulsion of carnauba wax prepared by means of the products is used for cleansing and polishing furniture, automobiles or leather: (9) an aqueous emulsion of white oil is used as a solvent composition: (10) an emulsion of latex prepared with the products is used for impregnating cotton: (1)1 a dispersion of neat's foot oil is used for softening leather; The products may be used for dispersing lampblack, sulphur, blanc-fixe, and minerals and may be used in the preparation of inks, pigments, toilet soaps, cosmetics, hair a