Patent GB-360539-A (GB)
Title: Improvements in the manufacture and production of wetting, cleansing, dispersing andlike agents
Filed: 1930-08-29
Abstract: Sulphonic acids or their salts are prepared by heating with sulphites the mineral acid esters of aliphatic alcohols containing at least eight carbon atoms in the molecule.  The mineral acid esters used as initial materials may be derived from sulphuric, hydrohalide, or phosphoric acids and octyl and higher alcohols, or alcohol mixtures obtainable (a) by reducing vegetable or animal oils or fats, e.g. olive, soya, coco nut or castor oil, hydrogenated train oils, or their acids, or (b) from waxes, or (c) by oxidizing hydrocarbons of high molecular weight with gaseous oxidants; other suitable alcohols are hydroxylated ethers such as glycerol monotetradecyl ether. According to the examples, (1) dodecanol is esterified with chlorsulphonic acid at 15-25 DEG  C. in the presence of ether, and the sodium salt of the resulting ester is heated to 200 DEG  C. in an autoclave with aqueous sodium sulphite; the reaction product is diluted and salted out; (2) the sodium salt of octodecyl alcohol sulphuric ester is heated to 250 DEG  C. with aqueous sodium sulphite; (3) the sodium salt of octodecyl alcohol sulphuric ester is heated to 200 DEG  C. with sodium sulphite in dilute ethyl alcohol; (4) an alcohol mixture obtained by the catalytic reduction of coco nut oil is treated with chlorsulphonic acid at 15-25 DEG  C., and after warming to 35 DEG  C., to remove hydrochloric acid, the resulting sulphuric esters are heated to 200 DEG  C. with aqueous sodium bisulphite and caustic soda; the product is concentrated and treated with alcohol, to precipitate inorganic salts; the residual sulphonates may be fractionated; (5) octodecyl bromide is heated at 130-160 DEG  C. with aqueous sodium, ammonium, or calcium sulphite; (6) octodecanediol is esterified with chlorsulphonic acid in ethereal suspension, and the product is neutralized with caustic soda and tertiary sodium phosphate, and evaporated; the product is heated at 180 DEG  C. with aqueous sodium bisulphite and caustic soda, and the resulting sulphonate is refluxed with dilute hydrochloric acid; (7) the sodium salt of the sulphuric ester of oleic alcohol is heated at 180 DEG  C. with aqueous sodium bisulphite and caustic soda, and the product is refluxed with dilute hydrochloric acid; (8) the ammonium salt of octodecyl alcohol sulphuric ester is heated with aqueous ammonium sulphite and carbonate; (9) tetradecyl dioxypropyl ether is treated with chlorsulphonic acid at 20-25 DEG  C. in ethereal suspension, and the ester is neutralized, freed from ether, diluted, and heated at 160-180 DEG  C. with potassium sulphite; the product is acidified with sulphuric acid, boiled, and evaporated. The preparation of sulphonic acids from mineral acid esters of decyl, cetyl, ceryl, myricyl, pentadecyl, and heptadecyl alcohols is referred to, and reference is made also to the manufacture of products still containing free hydroxyl groups.  The crude reaction products containing sulphites and sulphates, or the sulphonates, or sulphonic acids isolated therefrom, have cleansing and dispersing properties and may be applied as dispersing agents in the manufacture of dyestuff pastes, and in the preparation of aqueous emulsions of oils, fats, hydrocarbons, and water-insoluble alcohols or ketones, such emulsions being useful as greasing, oiling or de-greasing agents in the textile and leather industries, and as boring and lubricating oils.  For the purposes mentioned, the sulphonic acids or their salts may be used in association with other emulsifying &c. agents, such as soaps, turkey red oils, or aromatic sulphonic acids, or with protective colloids such as glue or vegetable mucilages or gums, or with salts such as sodium carbonate or bicarbonate, waterglass, common salt, or sodium sulphate or bisulphate, or with organic solvents such as ethyleneglycol monocresyl ether, cyclohexanol, cyclohexanone, or trichlorethylene or with bleaching agents such as perborates, percarbonates; and sodium p-toluenesulphochloramide. Specifications 342,761 and 343,071, [both in Group IV], are referred to.ALSO:Sulphonic acids or their salts are prepared by heating with neutral or acid sulphites the mineral acid esters of aliphatic non-carboxylated alcohols containing at least eight carbon atoms in the molecule.  The reaction is preferably effected in solution or suspension, and may be effected under pressure and/or in the presence of a superficially active catalyst, e.g. active carbon or silica gel, or of buffers, e.g. boric acid, tertiary sodium phosphate, or ammonium carbonate.  The mineral acid esters used as initial materials may be derived from sulphuric, hydrohalide, or phosphoric acids and octyl and higher alcohols, or alcohol mixtures obtainable (a) by reducing vegetable or animal oils or fats, e.g. olive, soya, cocoa nut or castor oil, hydrogenated train oils, or their acids, or (b) from waxes, or (c) by oxidizing hydrocarbons of high molecular weight with gaseous oxidants; other suitable alcohols are hydroxylated ethers such as glycerol monotetradecyl ether.  The esters may be prepared by interaction of the alcohol and the acid or its chlorides, or by addition of the acid to the olefines corresponding to the alcohols.  According to the examples, (1) dodecanol is esterified with chlorsulphonic acid at 15-25 DEG  C. in the presence of ether, and the sodium salt of the resulting ester is heated to 200 DEG  C. in an autoclave with aqueous sodium sulphite; the reaction product is diluted and salted out; (2) the sodium salt of octodecyl alcohol sulphuric ester is heated to 250 DEG  C. with aqueous sodium sulphite; (3) the sodium salt of octodecyl alcohol sulphuric ester is heated to 200 DEG  C. with sodium sulphite in dilute ethyl alcohol; (4) an alcohol mixture obtained by the catalytic reduction of coco nut oil is treated with chlorosulphonic acid at 15-25 DEG  C., and after warming to 35 DEG  C., to remove hydrochloric acid, the resulting sulphuric esters are heated to 200 DEG  C. with aqueous sodium bisulphite and caustic soda; the product is concentrated and treated with alcohol, to precipitate inorganic salts; the residual sulphonates may be fractionated; (5) octodecyl bromide is heated at 130-160 DEG  C. with aqueous sodium, ammonium, or calcium sulphite; (6) octodecanediol (obtained by the catalytic reduction of castor oil) is esterified with chlorsulphonic acid in ethereal suspension, and the product is neutralized with caustic soda and tertiary sodium phosphate, and evaporated; the product is heated at 180 DEG  C. with aqueous sodium bisulphite and caustic soda, and the resulting sulphonate is refluxed with dilute hydrochloric acid; (7) the sodium salt of the sulphuric ester of oleic alcohol (obtainable from the alcohol and oleic acid) is heated at 180 DEG  C. with aqueous sodium bisulphite and caustic soda, and the product is refluxed with dilute hydrochloric acid; (8) the ammonium salt of octodecyl alcohol sulphuric ester is heated with aqueous ammonium sulphite and carbonate; (9) tetradecyl dioxypropyl ether (obtainable from sodium tetradecyl alcoholate and glycerol a -mono-chlorhydrin) is treated with chlorsulphonic acid at 20-25 DEG  C. in ethereal suspension, and the ester is neutralized, freed from ether, diluted, and heated at 160-180 DEG  C. with potassium sulphite; the product is acidified with sulphuric acid, boiled, and evaporated. The preparation of sulphonic acids from mineral acid esters of decyl, cetyl, ceryl, myricyl, pentadecyl, and heptadecyl alcohols is referred to, and reference is made also to the manufacture of products still containing free hydroxyl groups.  The crude reaction products containing sulphites and sulphates, or the sulphonates or sulphonic acids isolated therefrom, have wetting, cleansing, and dispersing properties and may be applied (a) as assistants in dyeing, carbonizing, and mercerizing baths.  (b) as dispersing agents in the manufacture of dyestuff pastes, (c) in softening artificial silk or fabrics, (d) as additions to artificial silk spinning baths, (e) in soaking hides, and (f) in the preparation of aqueous emulsions of oils, fats, hydrocarbons, and water-insoluble alcohols or ketones, such emulsions being useful as greasing, oiling, or degreasing agents in the textile and leather industries, and as boring and lubricating oils.  For the purposes mentioned, the sulphonic acids or their salts may be used in association with other wetting &c. agents, such as soaps, Turkey red oils, or aromatic sulphonic acids, or with protective colloids such as glue or vegetable mucilages or gums, or with salts such as sodium carbonate or bicarbonate, waterglass, common salt, or sodium sulphate or bisulphate, or with organic solvents such as ethylene glycol monocresyl ether, cyclohexanol, cyclohexanone, or trichlorethylene, or with bleaching agents such as perborates, percarbonates, and sodium p-toluenesulphochloramide. Specifications 342,761 and 343,071 are referred to.