Patent GB-424951-A (GB)
Title: Manufacture of wetting agents and like substances
Filed: 1933-05-29
Abstract: Olefines containing at least eight carbon atoms in the molecule, and a double linkage at the end of the chain are treated with a halogen sulphuric acid in the presence of a halogenating catalyst and the products hydrolyzed.  The sulphonating agents are preferably chlorsulphonic and bromsulphonic acids and are employed in the proportions of 1--2 moles of acid for each double bond per mole of olefines.  The reaction is effected in a suitable liquid medium, preferably boiling below 100 DEG  C., e.g. carbon tetrachloride, ethylene-dichloride, trichlorethylene, tetrachlorethane, chloroform, liquid sulphur dioxide, diethyl ether, acetic anhydride, propionic acid and anhydride, and at a temperature within the range--10 to 35 DEG  C.  Suitable catalysts include antimony trioxide, antimony pentoxide, antimony trichloride, antimony pentachloride, antimony sulphate, cuprous chloride, cupric oxide, cuprous oxide, cupric sulphate, cupric acetate, manganese dioxide, pyrolusite, manganous sulphate, manganese oxide, ferric chloride, ferrous sulphate, ferric sulphate, ferric oxide, ferrous oxide, magnetite, vanadium pentoxide, sodium vanadate, vanadyl sulphate, aluminium chloride, aluminium sulphate, cuprous iodide, sodium iodide, potassium iodide and free iodine, and are used in proportions corresponding to about 0,1--5 per cent by weight of the reactants.  The sulphonation is continued until the product remains soluble in water on boiling with a hydrolyzing agent.  The hydrolysis of the product may be effected by diluting with water and boiling, or by boiling with mineral acids or alkalis, and is carried out at a temperature of about 100 DEG  C.  Any solvent or suspension medium should be removed prior to the hydrolysis.  The products are stated to be wetting, cleansing and dispersing agents and to be stable in all acidic, alkaline, or neutral aqueous media. They may be used for the laundering, dyeing, bleaching, carbonizing, mercerizing and finishing of textiles and as emulsifying agents for water immiscible solvents.  They may be employed together with alcohols, ketones or other wetting agents, e.g. trisodium phosphate, turkey red oils, soaps, sulphonic acids, acid amides, sodium saponin or sodium taurocholate, and are used in the dye, paper, textile and leather industries.  They may also be used in combination with neutral, acid or basic salts which increase their wetting and dispersing power, e.g. sodium sulphate, sodium chloride, sodium acetate, mono-, di- and tri-sodium phosphates, sodium carbonate, sodium bicarbonate and similar compounds, magnesium sulphate, magnesium chloride, magnesium acetate, zinc chloride and zinc acetate.  The products may also be combined with bleaching and disinfectant agents such as persulphates, percarbonates and perborates; filling materials such as talc, marble-dust and starch; absorbents such as fuller's earth and similar clays protective colloids such as gum tragacanth, gall-acids and their derivatives, agar-agar, glue, methyl cellulose, sulphite cellulose lyes, sodium cellulose phthalate, calcium saccharate, albumin, sodium cellulose glycollate, gelatin, natural and artificial resins, derivatives of cholesterine, phosphatides, gelloses, natural and artificial waxes, wool waxes, solvents and softening agents, organic bases and their salts such as alkylolamine salts and quaternary ammonium compounds, inorganic colloids and alkalis; and scouring materials such as kieselguhr, powdered pumice, sulphur, flour, and chinaclay salt. They may also be combined with terpenes and their derivatives, e.g. limonene, dipentene, terpinolene, terpinene, phellandrene, sylvestrene, pinene, bornylene, sabine and their alcoholic, ketonic and aldehydic derivatives, or with natural or artificial perfumes. According to examples: (1) 1-2 Octadecylene, obtained by dehydrating primary n-octadecyl alcohol, is dissolved in carbon tetrachloride, and a small amount of pyrolusite added.  The solution is cooled to about 0--5 DEG  C.  It is sulphonated with chlorsulphonic acid, the temperature being allowed to rise to 20--25 DEG  C.  It is then hydrolyzed with caustic soda.  (2) The same process is carried out using iodine as a catalyst.  (3) The reaction is repeated using cuprous chloride as catalyst.  The product obtained by neutralization of the sulphonation product is also stated to possess wetting and dispersing properties. Suitable olefines may also be obtained by dehydrating primary alcohols obtained by hydrogenating fatty acids or esters, e.g. from palm oil, tallow, coco-nut oil and olive oil, or by polymerizing short chain olefines or by dehydrating higher synthetic alcohols, e.g. those produced by the hydrogenation of carbon oxides. The reaction may also be carried out without the aid of a catalyst, but in this case, a bye-product oil is also present in the reaction product.ALSO:Olefines containing at least eight carbon atoms in the molecule and a double linkage at the end of the chain are treated with a p  halogen sulphuric acid in the presence of a halogenating catalyst and the products hydrolyzed.  The sulphonating agents are preferably chlorosulphonic and bromsulphonic acids and are employed in the proportions of 1-2 moles of acid for each double bond per mole of olefines.  The reaction is effected in a suitable liquid medium, preferably boiling below 100 DEG  C. e.g. carbon tetrachloride, ethylene-dichloride, trichlorethylene, tetrachlorethane, chloroform, liquid sulphur dioxide, diethyl ether, acetic anhydride, propionic acid and anhydride, and at a temperature within the range -10 to 35 DEG  C.  Suitable catalysts include antimony trioxide, antimony pentoxide, antimony trichloride, antimony pentachloride, antimony sulphate, cuprous chloride, cupric oxide, cuprous oxide, cupric sulphate, cupric acetate, manganese dioxide, pyrolusite, manganous sulphate, manganese oxide, ferric chloride, ferrous sulphate, ferric sulphate, ferric oxide, ferrous oxide, magnetite, vanadium pentoxide, sodium vanadate, vanadyl sulphate, aluminium chloride, aluminium sulphate, cuprous iodide, sodium iodide, potassium iodide and free iodine, and are used in proportions corresponding to about 0,1--5 per cent by weight of the reactants.  The sulphonation is continued until the product remains soluble in water on boiling with a hydrolyzing agent.  The hydrolysis of the product may be effected by diluting with water and boiling, or by boiling with mineral acids or alkalis, and is carried out at a temperature of about 100 DEG  C.  Any solvent or suspension medium should be removed prior to the hydrolysis.  The products are stated to be wetting and dispersing agents and to be stable in all acidic, alkaline, or neutral aqueous media.  They may be used as emulsifying agents for water immiscible solvents.  They may be employed together with alcohols ketones or other wetting agents, e.g. trisodium phosphate, turkey red oils, soaps, sulphonic acids, acid amides, sodium saponin or sodium taurochloate, and are used in the dye, paper, textile and leather industries.  They may also be used in combination with neutral, acid or basic salts which increase their wetting and dispersing power, e.g. sodium sulphate, sodium chloride, sodium acetate, mono-, di-, and tri-sodium phosphates, sodium carbonate, sodium bicarbonate, and similar compounds, magnesium sulphate, magnesium chloride, magnesium acetate, zinc chloride and zinc acetate.  The products may also be combined with bleaching and disinfectant agents such as persulphates, percarbonates and perborates; filling materials such as talc, marble-dust and starch; absorbents such as fuller's earth and similar clays; protective colloids such as gum tragacanth, gall-acids and their derivatives, agar-agar, glue, methyl cellulose, sulphite cellulose lyes, sodium cellulose phthalate, calcium saccharate, albumin, sodium cellulose glycollate, gelatin, natural and artificial resins, derivatives of cholesterine, phosphatides, gelloses, natural and artificial waxes, wool waxes, solvent and softening agents, organic bases and their salts such as alkylolamine salts and quaternary ammonium compounds, inorganic colloids and alkalis; and scouring materials such as kieselguhr, powdered pumice, sulphur, flour, and china-clay salt.  They may also be combined with terpenes and their derivatives e.g. limonene, dipentene, terpinolene, terpinene, phellandrene, sylvestrene, pinene, bornylene, sabine and their alcoholic, ketonic and aldehydic derivatives, or with natural or artificial perfumes.  According to examples (1) 1--2 octadecylene, obtained by dehydrating primary n-octadecyl alcohol, is dissolved in carbon tetrachloride, and a small amount of pyrolusite added.  The solution is cooled to about 0--5 DEG  C.  It is sulphonated with chlorsulphonic acid, the temperature being allowed to rise to 20--25 DEG  C.  It is then hydrolyzed with caustic soda.  (2) The same process is carried out using iodine as a catalyst.  (3) The reaction is repeated using cuprous chloride as catalyst.  The product obtained by neutralization of the sulphonation product is also stated to possess wetting and dispersing properties.ALSO:Wetting &c. agents obtained by treating olefines containing at least eight carbon atoms, and a double linkage at the end of the chain with a halogen sulphuric acid in the presence of a halogenating catalyst and hydrolyzing the product are mixed with disinfectant agents such as persulphates, percarbonates and perborates, and also with terpenes and their derivatives, e.g. limonene, dipentene, terpinolene, terpinene, phellandrene, sylvestrene, pinene, bomylene, sabine, and their alcoholic, ketonic and aldehydic derivatives.