Patent GB-364669-A (GB)
Title: Improvements in the manufacture and production of wetting, cleansing and emulsifyingagents
Filed: 1930-10-06
Abstract: Assistants for the textile, leather, paper and other industries having dispersing and emulsifying properties are obtained by sulphonating olefines, which are free from carboxy groups, or mixtures of the same, which are produced by splitting off water and/or carbon dioxide from the products of the destructive oxidation of difficulty volatile liquid or solid non-aromatic hydrocarbons containing at least eight carbon atoms, with energetic sulphonating agents, namely, oleum, chlorsulphonic acid or liquid sulphur trioxide or with concentrated sulphuric acid at temperatures above 100 DEG  C. or in the presence of dehydrating agents, whereby true sulphonic acids are formed.  The olefines may be prepared according to the process of Specification 347,620, [Group IV], from hydrocarbons such as liquid or solid paraffin, naphthenes, petroleums, benzines, middle oils, brown coal tar oils, montan or other waxes and hydrogenated coals, tars or petroleums, by subjecting the oxidized hydrocarbons, which comprise compounds containing hydroxy, carboxylic or ester groups, e.g. hydroxycarboxylic acids, estolides, lactides or lactones, to distillation.  Before sulphonation, the olefines may be fractionated, or mixed with organic compounds containing more than eight carbon atoms, e.g. alcohols, carboxylic acids, hydroxycarboxylic acids or esters.  Solvents or diluents, e.g. chloroform, trichlorethylene, nitrobenzene, diethylether, and porous surface active catalysts, such as active carbon or diatomaceous earth may be used during the sulphonation. Phosphoric anhydride, acetyl chloride and other dehydrating agents may be present during the sulphonation even when energetic sulphonating agents are employed. The products may be used alone or in association with salts, soaps, saponine, Turkey red oil, aromatic sulphonic acids, glue, gelatine, gum arabic, mucilages or solvents, for the preparation of solutions, dispersions or emulsions of dyestuffs, oils, fats, waxes, paraffins, and solvents, for the preparation of polishing, drilling and lubricating compositions and as assistants in mercerizing, carbonizing, dressing and softening baths.  According to examples: (1) chlorsulphonic acid is used to sulphonate olefines prepared by the distillation of the oxidized products insoluble in petroleum ether of a hard paraffin wax.  The resulting sulphonic acids cannot be saponified by boiling aqueous mineral acids, and may be used as such or after neutralization with ammonia, alkali hydroxide, monodi- or triethanolamine, cyclohexylethanolamine or pyridine: (2) Russian gas oil is oxidized with air, using manganese naphthenate as a catalyst, and the oxidized product distilled.  Saponifiable constituents are removed by means of alkalies and the olefines after extraction with liquid sulphur dioxide sulphonated with a mixture of sulphuric acid and acetic anhydride: (3) soft paraffin wax is oxidized with air and the acid constituents removed with caustic soda solution.  The product is then separated into a liquid fraction consisting of hydroxy compounds, and a solid fraction by centrifuging, and the former treated with an agent for removing water, e.g. zinc chloride or sulphuric acid to produce a mixture of olefines.  These are finally sulphonated with oleum.  Specifications 324,031, [Class 2 (iii), Dyes &c.], 358,583, and 360,002 also are referred to.ALSO:Assistants for the textile, leather, paper, and other industries are obtained by sulphonating olefines, which are free from carboxy groups, or mixtures of the same, which are produced by splitting off water and/or carbon dioxide from the products of the destructive oxidation of difficultly volatile liquid or solid non-aromatic hydrocarbons containing at least eight carbon atoms, with energetic sulphonating agents, namely, oleum, chlorsulphonic acid or liquid sulphur trioxide or with concentrated sulphuric acid at temperatures above 100 DEG  C. or in the presence of dehydrating agents, whereby true sulphonic acids are formed.  The olefines may be prepared according to the process of Specification 347,620 from hydrocarbons such as liquid or solid paraffin, naphthenes, petroleums, benzines, middle oils, brown coal tar oils, montan or other waxes, and hydrogenated coals, tars or petroleums, by subjecting the oxidized hydrocarbons, which comprise compounds containing hydroxy, carboxylic or ester groups, e.g. hydroxycarboxylic acids, estolides, lactides, or lactones, to distillation.  Before sulphonation, the olefines may be fractionated, or mixed with organic compounds containing more than eight carbon atoms, e.g. alcohols, carboxylic acids, hydroxycarboxylic acids or esters.  Solvents or diluents, e.g. chloroform, trichlorethylene, nitrobenzene, diethylether, and porous, surface active catalysts, such as active carbon or diatomaceous earth may be used during the sulphonation. Phosphoric anhydride, acetyl chloride and other dehydrating agents may be present during the sulphonation even when energetic sulphonating agents are employed.  The products, which are stated to be wetting, cleansing, dispersing, and emulsifying agents may be used alone or in association with salts, soaps, saponine, Turkey red oil, aromatic sulphonic acids, glue, gelatine, gum arabic, mucilages, or solvents, for the preparation of solutions, dispersions, or emulsions of dyestuffs, oils, fats, waxes, paraffins, and solvents, for the preparation of polishing, drilling, and lubricating compositions and as assistants in mercerizing, carbonizing, dressing, and softening baths. According to examples: (1) chlorsulphonic acid is used to sulphonate olefines prepared by the distillation of the oxidized products insoluble in petroleum ether of a hard paraffin wax.  The resulting sulphonic acids cannot be saponified by boiling aqueous mineral acids, and may be used as such or after neutralization with ammonia, alkali hydroxide, mono-, di-, or tri-ethanolamine, cyclohexylethanolamine or pyridine; (2) Russian gas oil is oxidized with air, using manganese naphthenate as a catalyst, and the oxidized product distilled.  Saponifiable constituents are removed by means of alkalies and the olefines after extraction with liquid sulphur dioxide sulphonated with a mixture of sulphuric acid and acetic anhydride; (3) soft paraffin wax is oxidized with air and the acid constituents removed with caustic soda solution.  The product is then separated into a liquid fraction consisting of hydroxy compounds, and a solid fraction by centrifuging, and the former treated with an agent for removing water, e.g. zinc chloride or sulphuric acid, to produce a mixture of olefines.  These are finally sulphonated with oleum. Specifications 324,031, [Class 2 (iii), Dyes &c.], 358,583, and 360,002 also are referred to.