Patent GB-689246-A (GB)
Title: Improvements in and relating to surface-active compounds
IPC: C11D1/22
Filed: 1950-04-20
Abstract: The invention comprises surface-active materials which are the acidic sulphonation products, or their water-soluble salts, of compounds of the general formula RCOXCnH2nCOX1Y where RCO represents acyl groups of saturated fatty acids having from 8 to 22 carbon atoms or acyl groups of mixed fatty acids having 8 to 22 carbon atoms such that the iodine value of the equivalent fats is not more than 20, n is an integer of from 1 to 3, X and X1 are each either oxygen or N(Z), where Z is either hydrogen or an alkyl radical of not more than 3 carbon atoms and Y is an alkenyl radical of 3-4 carbon atoms.  The sulphonated products may be true sulphonates, sulphuric esters or both.  Specified salts of these products are the sodium, ammonium, quaternary ammonium, magnesium and amine salts.  The diester starting materials may be prepared, for example, by esterifying glycollic acid, a lactic acid or a hydroxy butyric acid, with an olefinic monohydric aliphatic alcohol of 3 or 4 carbon atoms, e.g. allyl, methallyl or crotyl alcohol, 3-buten-1-ol or 3-butene-2-ol, and acylating the resulting hydroxy ester with, for example, an appropriate acid chloride.  The ester-amides may be made by forming the amide of the appropriate aliphatic monohydroxy monocarboxylic acid, e.g. by reacting the methyl ester of the acid with a suitable aliphatic primary or secondary amine containing an alkenyl group of 3-4 carbon atoms attached to the nitrogen, and acylating the resulting hydroxy amide, e.g. with an acid chloride.  The diamides can be made by amidifying a low molecular ester of an amino acid, e.g. the methyl ester, by treating it with a suitable fatty acid chloride and heating the resulting amide ester with the appropriate C3-4 alkenyl amine, e.g. allyl amine.  The amide-esters can be made by treating an appropriate amino acid, e.g. glycine, with a suitable fatty acid chloride to amidify the amino acid and then esterifying with an appropriate unsaturated alcohol, e.g. allyl alcohol.  The starting materials may be sulphonated with concentrated sulphuric acid, fuming sulphuric acid, sulphur trioxide, chlor-sulphonic acid and the like, preferably at temperatures not above 60 DEG  C. and, if desired, in the presence of organic solvents, diluents or thinning agents such as dioxane, hexane, heptane, carbon tetrachloride, ethylene dichloride, methyl and ethyl acetates and other saturated aliphatic hydrocarbons, chlorinated hydrocarbons and low molecular weight esters.  Neutralization of the sulphonation product is preferably effected at temperatures not substantially above 50 DEG C.; when carboxylic ester groups are present, splitting of these groups is largely avoided by neutralizing to a final pH (at 25 DEG C.) of about 5-8.  The sulphonation products may be treated to remove unsulphonated organic material and inorganic salts and may be dried, e.g. by drum, vacuum drum or spray drying methods.  The products may be used as detergents alone or in conjunction with anionic or non-ionic organic detergents and various detergent additives (see Group III).  The preferred products are obtained when the fatty acids are chiefly lauric or myristic acid or the fatty acids from an oil of the coconut oil group, viz. all vegetable acid oils or fats having an iodine value not exceeding 20 and wherein at least 50 per cent by weight of the combined fatty acids are lauric and/or myristic acid, reference being made to the mixed acids of tangkallak kernel oil, ucuhuba nut oil, dika nut oil, khakan kernel oil, murumura kernel oil, tucuma kernel oil, cohune nut oil, ouricoury nut oil, babassu kernel oil and palm kernel oil. In addition, there may be used unsaturated fatty acids whose iodine values have been reduced to 20 or less by complete or partial hydrogenation, catalytic rearrangement and/or graining and synthetic fatty acids obtained by oxidizing petroleum hydrocarbons or by hydrogenating carbon monoxide or oxidizing the hydrocarbons or oxygenated hydrocarbons resulting from the latter process.  In examples: (1) allyl glycollate is prepared by refluxing glycollic acid, allyl alcohol and benzene using, p-toluene sulphonic acid as catalyst and converted into lauroyl allyl glycollate by reaction with lauroyl chloride in ethereal solution in presence of pyridine, and then sulphonated with oleum in ethylene dichloride, the product poured on ice, neutralized with NaOH and extracted with petroleum ether, the product being a mixture of a monosulphonate and a sulphate-sulphonate; (2) N-allyl hydroxyacetamide is prepared by refluxing methyl hydroxy acetate with allylamine in methanol and reacted with lauroyl chloride in benzene in presence of pyridine and the resulting allyl amide of lauroyl glycollic acid is sulphonated, neutralized and extracted with petroleum ether as in (1); (3) the process of (2) is repeated, using methallylamine in place of allyl amine.  A list of other diamides, diesters, ester-amides and amide esters for use as starting materials is given.  Specification 511,043 is referred to.ALSO:Detergent compositions comprise the acidic sulphonation products, or their water-soluble salts, of compounds of the general formula RCOXCn H2n COX1Y, where RCO represents an acyl group of a saturated fatty acid having 8 to 22 carbon atoms or acyl groups of mixed fatty acids having 8 to 22 carbon atoms such that the iodine value of the equivalent fats is not more than 20. n is an integer of from 1 to 3, X and X1 are each either oxygen or N(Z), where Z is either hydrogen or an alkyl radical of not more than 3 carbon atoms, and Y is an alkenyl radical of 3-4 carbon atoms.  The sulphonation products may be true sulphonates or sulphuric esters or both; specified salts are the sodium, ammonium, magnesium, amine and quaternary ammonium salts. The preferred compounds are those in which the acyl group RCO is derived from lauric or myristic acid or the mixed fatty acids from oils of the coconut oil group viz. those vegetable seed oils or fats having an iodine value not exceeding 20 and wherein at least 50 per cent of the acids are lauric and/or myristic acid, e.g. tangkallak kernel oil, ucuhuba nut oil, dika nut oil, khakan kernel oil, murumura kernel oil, tucuma kernel oil, cohune nut oil, ouricoury nut oil, babassu kernel oil and palm kernel oil; in addition the acyl groups may be derived from unsaturated fatty acids whose iodine values have been reduced to 20 or less by hydrogenation, catalytic rearrangement or graining, or from synthetic fatty acids.  The sulphonated compounds may be used in conjunction with soap or other anionic organic detergents, e.g. alkyl sulphates and sulphonates, with non-ionic organic detergents, e.g. alkyl ethers of polyethylene glycol or alkyl phenol ethers thereof or corresponding thioethers, with inorganic salts, e.g. sodium sulphate, sodium chloride, sodium bicarbonate, sodium silicate or sodium pyro-, tri-, tetra- or metaphosphates, or with relatively unreactive organic compounds, e.g. fluorescing agents, carboxymethyl cellulose, starch, urea, high molecular aliphatic alcohols, fatty acid monoglycerides and fatty acid amides.  The compositions may be made in bar, flake, granule, powder, paste or liquid form.  Examples describe compositions comprising (1) the sodium salt of sulphonated allyl lauroyl glycollate, sodium sulphate and disodium hydrogen phosphate; (2) the sodium salt of sulphonated allyl amide of lauroyl glycollic acid (mixed monosulphonate and sulphate-sulphonate); and (3) the sodium salt of sulphonated methallyl amide of lauroyl glycollic acid, sodium sulphate, and disodium hydrogen phosphate.  The production of the sulphonated products is described (see Group IV(b)).  Specification 511,043 is referred to.