GB2152029A - Amine and alkali metal double salts of acylamidoalkylene (or acylamido-N-hydroxyalkyk-N-alkylene) sulphosuccinic acid process for preparing same and use thereof - Google Patents

Abstract

The title compounds have the general formula: <IMAGE> wherein R1 is a straight-chain hydrocarbon radical C9-C21, R2 is hydrogen, -CH3, -CH2CH3, -CH2-CH2-OH, <IMAGE> R4, R5, and R6 are each hydrogen and/or CH2-CH2-OH; Me is Na or K. The compounds are prepared from fish-processing industry wastes containing fatty acids and glycerides with an acid number of not more than 50 mg KOH/g, saponification number of 181-192 mg KOH/g and a bromine number of 60-70 g Br/100 g, which are treated at reflux with methanol in the presence of sulphuric acid to give glycerides and methyl esters of fatty acids which are separated and treated with methanol in the presence of sulphuric acid at 50-60 DEG C, an anhydrous fat layer being then separated and boiled with methanol in the presence of an alkali, the resulting methyl esters being separated and treated at 70 to 90 DEG C with alkylolamine in an amount of 25 to 55% by mass of the amount of the methyl esters in the presence of an alkali metal or an amide or an alcoholate thereof as catalyst. The alkylolamides of fatty acids obtained are treated with maleic anhydride at 60 to 90 DEG C to give maleates which are treated with sodium or potassium pyrosulphite and ethanolamine or ammonia at 60 to 90 DEG C in an aqueous medium, followed by separation of the desired product. The compounds are useful as surfactants and washing active substances in detergent compositions.

Description

SPECIFICATION Amine and alkali metal double salts of acylamidoalkylene (or-acylamido-N-hydroxyalkyl-N-alkylene) sulphosuccinic acid, method for preparing same and use thereof The present invention relates to surfactants and, more particularly, to novel compounds - amine and alkali metal double salts of an acylamidoalkylene (or acylamido-N-hydroxyalkyl-N-alkylene)-sulphosuccinic acid, a process for preparing same and use thereof as detergents.

The surfactants according to the present invention are novel and hitherto unknown in the literature.

The novel substances according to the present invention, i.e. amine and alkali metal double salts of an acylamidoalkylene (or acylamido-N-hydroxyalkyl-N-alkyle ne)sulphosuccinic acid have the following general formula:

wherein R1 is a straight hydrocarbon radical C9-C21 R2 is hydrogen CH3, -CH2-CH2, -CH2-CH2-OH;

R3 iS -CH2-CH2- -CH2-CH- or

R4, R5, R6 are each hydrogen and or -CH2-CH2-OH; Me is Na or K.

The novel compounds according to the present invention comprise dough-like substances fully soluble in cold water (40% solution is transparent has good flow characteristics at the temperature 20or, does not get turbid upon storage). The compounds feature a good heat-resistance. Furthermore, they have a mild dermatological effect and are readily biodegradable.

The structure of the compounds according to the present invention is determined by IR-spectroscopy. The spectra have characteristic bands of the following functional groups: alkyl radical -725-720 cm-', CH3-, OH2- groups 2,960; 2,940-2,910; 2,870 cm-7; -CO-NH- group 3,350-3,300 3,050-3,010 cm-1;

group 1,750-1,735 cm-l -CO2 ion 1,610-1,550; 1,450-1,300 cm-1; -OH group 3,500-3,250; 1,050-1,030 cm-l; -SO2-O- group 1,420-1,330; 1,200-1,145 cm-1; -NH4- ion 3,300-3,030 cm-1.

The presence of a double charge of the anion in the compounds according to the present invention is proven by the cation-exchange method in an aqueous-alcoholic solution.

The density of aqueous solutions of these compounds at a concentration thereof ranging from 24 to 32% by mass is within the range of from 1.0620 to 1.1020 kg/m3 at the temperature of 20"C; dynamic viscosity of these solutions at the temperature of 20"C is within the range of 20 to 34 mPas.

The novel compounds according to the present invention manifest surfactant properties.

The foam numbers of these substances determined by the Ross-Miles method at the temperature of 40"C and at the concentration of 0.25% by mass are characterized by an initial height of a foam column in distilled water of 180-196 mm and their foam stability H5/H1 is 0.96-0.98; in hard water with the concentration of calcium and magnesium salts of 5.35 mg-equiv/g the initial height of the foam column is 185-205 mm, foam stability is 0.96-0.97.

W2sEh test of the novel compounds according to the present invention was determined following a standard procedure (cf. F.V. Nevolin "Chemistry and Technology of Synthetic Detergents", Pischevaya Promyshlennost' (Food Industry) Publishers, Moscow, 1971, pp.405-415). At the concentration of these compounds of 0.25% by mass their detergency efficiency is within the range of from 90 to 96.

The surface tension of aqueous solutions of the compounds according to the present invention was determined by the stalagmometric method at the temperature of 20"C and at the concentration thereof in an aqueous solution of 0.1% by mass. It was within the range of 28.1 -31.6x 10-3 M/m.

The process for producing the novel compounds according to the present invention resides in that fat-containing waste effluents of fish-processing plants containing fatty acids and glycerides with an acid number of not more than 50 mg KOHlg, saponification number of 181-192 mg KOH/g, and bromide number 60-70 mg Br/100 g are treated with methanol in the presence of sulphuric acid upon heating at refluxto give a reaction mixture, wherefrom the fat layer consisting of glycerides and methyl esters of fatty acids is separated and treated with methanol in the presence of sulphuric acid at a temperature of 50-60"C to give a reaction mass, whernfrom the anhydrous fat layer is separated and treated with methanol in the presence of an alkali at the boiling temperature of methanol to give a reaction mixture containing methyl esters of fatty acids which are separated and treated with an alkylolamine taken in an amount of from 25 to 55% by mass of the amount of the methyl esters of fatty acids in the presence of a catalyst selected from the group consisting of an alkali metal, or an amide or alcoholate thereof at a temperature ranging from 70 to 90"C to give alkylolamides of fatty acids which are treated with maleic anhydride at a temperature of 60 to 90 C to produce maleates of fatty acid alkylolamides, followed by treatment of the latter with sodium or potassium pyrosulphite and ethanolamine or ammonia at a temperature of 60 to 90"C in an aqueous medium and isolation ofthe desired product.

To improve the quality of the desired product, methyl esters of fatty acids, prior to the above-mentioned treatment thereof with an alkylolamine in the presence of the above-indicated catalyst are preliminarily treated with an alkylolamine taken in an amount of from 5 to 10% by mass of the amount of the methyl esters of fatty acids at a temperature of 70-80'G, followed by the removal of the spent alkylolamine.

As the alkylolamine it is advisable to use monoethanolamine, diethanolamine, diisopropanolamine, N-methylethanolamine, N-ethylethanolamine, dibutanolamine.

To simplify the procedure at the stage of amidation of methyl esters of fatty acids, as the catalyst it is preferred to use sodium 2-aminoethoxylate.

As the ethanolamine it is advisable that mono-, di- andlor triethanolamine be used.

The process according to the present invention is performed in the following manner.

Fat-containing wastes in the form of effluents from plants of the fish-processing industry containing fatty acids and glycerides with an acid number of not more than 50 mg KOH/g, saponification number of 181-192 mg KOHlg, bromine number of 60-70 mg Br/100 g are treated with methanol in the presence of sulphuric acid as a catalyst. This results Its in acidicesterification of free fatty acids contained in fatty wastes of the effluents.

The reaction of esterification is conducted by stirring the reaction mixture at the boiling temperature of methanol for 1.5-2.5 hours. On completion of the reaction the mixture is settled, the upper layer (methanol) is separated and recycled to regeneration, while the lower layer- the fat-containing mixture- is treated with methanol in the presence of sulphuric acid at a temperature within the range of from 50 to 603C. After settling the upper layer (extraction methanol) is separated and recycled to the initial stage of the cycle for acidic esterification of free Ly acids of the fatty wastes of effluents. The lower layer - and purified fat mixture - is delivered to the aikaline reesterification of gl,/cerides.

To this end, the purified fat mixture is treated with methanol in the presence of an alkali. The mixture is stirred at the boiling temperature of methanol for 0.25 hour, whereafter it is cooled to room temperature, allowed to settle for 1.5-2.0 hours and the layers are separated. The lower layer, glycerol and methanol are delivered to regeneration of methanol. The upper layer of methyl esters of fatty acids is washed with hot water acidified with hydrochloric acid and dried. Methanol is regenerated from the washing water. The dried methyl esters are subjected to fractionating vacuum distillation at a temperature within the range of from 155 to 21 50C under a reduced pressure of 10-20 mm Hg. The yield of the desired fraction is 78-83% of the initial amount of fats of the fat-containing wastes of effluents.The purified methyl esters of fatty acids are treated with an alkylolamine taken in an amount of 25 to 55% by mass of the amount of methyl esters of fatty acids at a temperature of 70-90"C in the presence of a catalyst such as an alkali metal, an amide or an alcoholate thereof.

Alkylolarnides of fatty acids are thus produced.

To simplify the process, as the catalyst sodium 2-aminoethoxylate is used.

As the alkylolamine use is made of monoethanolamine, diethanolamine, diisopropanolamine, N methylethanol, N-ethylethanolamine and the bike.

To improve the quality of the desired product, methyl ester of fatty acids prior to the above-mentioned treatment thereof with the al'a!otamine in the presence of the above-specified catalyst are preliminarily treated with the alkylolamine taken in an amount of 5 to 10% by mass of the amount of methyl esters of fatty acids at a temperature within the range of from 70 to 80 C, followed by settling and removing the spent alkylolamine.

The yield of alkylolamides of fatty acids as calculated for the degree of conversion of the alkylolamines is 93 to 98% ofthetheoretical.

The resulting alkylolamides are mixed with maleic anhydride in an amount of 30-37% by mass of the alkylolamides at a temperature of 60 to 90 C for 1.5-3.5 hours. The yield as calculated for the degree of conversion of maleic anhydride is equal to the theoretical value.

The thus-produced alkylolamide maleates are treated with sodium or potassium pyrosulphite and ethanolamine or ammonia in an aqueous medium at a temperature within the range of from 60 to 90"C to give the desired product.The yield of the desired product is 70-82% of the starting alkylolamide.

The process according to the present invention makes it possible to fully utilize the waste soap-stocks resulting from plants of the fish-processing industry and, thereby, to replace expensive food-grade fats and oils, as well as synthetic petroleum raw materials currently employed for the production of surfactants.

Furthermore, it contributes to a lesser pollution of the environment.

The process is simple technologically and requires no special equipment. The waste soap-stock employed in the process according to the present invention hitherto found no use in fine organic synthesis die to an overconeamination thereof. Owing to the above-mentioned operations, the process according to the present invention makes it possible to produce, from these raw materials, high-quality desired products serving as the basis for the manufacture of detergents without using any special additives to improve their dermatological and washing effects. The present invention also covers the use of the novel compounds as a base of detergent compositions. It is preferable to use a double triethanolamine and sodium salt of acylamidoethylenesulphosuccinic acid.

The detergent composition according to the present invention comprising a surfactant, a perfume and water contains as the surfactant a double triethanolamine and sodium salt of an acylamidoethylenesulphosuccinic acid ofthefollowing general formula:

wherein R is a straight-chain hydrocarbon radical C15-Cqs, at the following proportions of the components, per cent by mass: triethanolamine and sodium double salt of acylamidoethylenesulphosuccinic acid 5.0 - 32.0 perfume 0.1- 1.5 water the balance.

The preferable embodiment of the detergent composition according to the present invention is a composition additionally containing diethanolamide of C9-C17 fatty acids, sodium chloride and ethanol at the following proporsions of the components, per cent by mass: triethanolamine and sodium double salt of acylamidoeshyleereslllphosuccinic acid 12.0 - 20.0 diethanolamide of CS-C17 fatty acids 0.5 - 3.5 sodium chloride 1.0- 3.5 ethanol 0.3- 1.5 perfume 0.1- 1.5 water the balance.

The detergent composition according to the present invention, as compared to the known compositions, does not require the use of additives lowering the defatting effect.

It has a good solubility in cold hard water, high foam numbers and can be readily washed off.

Furthermore, the detergent composition according to the present invention has mild dermatological properties and can be easily biodegraded.

For a better understanding of the present invention, some specific examples are given hereinbelow by way of illustration.

Example I Into a 500 ml flask provided with a reflux condenser and a thermometer there are placed 250 g of fat wastes of effluents resulting from plants of fish-processing industry (acid number 24 mg KOH/g, saponification number 187 mg KOH!g, bromine number 66.2 mg Br/100 g, density d420=0.914 kg/m3 congelation temperature 13.8 C) and 63 g of methanol acidified with 1.3 g (0.0125 g-mol) of a concentrated sulphuric acid. The mixture is heated at reflux for 1.5 hours and esterification of fatty acids takes place. The reaction mixture is settled for 0.25 hour, the upper layer (methanolic) is separated and the lower layer consisting of glycerides and methyl esters of fatty acids is treated at a tempeature of 58-60 C with 47.5 g of methanol acidified with 0.09 g (0.00086 g-mol) of a concentrated sulphuric acid.After settling for 0.25 hour the layers are separated. The upper layer (extraction methanol) is recyled to the initial stage of esterification of fatty acids.

The lower layer (245 g) is charged into a 500 ml flask provided with a reflux condenser, a stirrer and a thermometer and added with 1.66 g (0.0415 g/mol) of caustic soda in 35.6 g (1.113 g-mol) of methanol. The mixture is stirred at the boiling teniperature of methanol for 0.25 hour and an alkaline reesterification of glycerides occurs thereupon, whereafter the reaction mass is cooled to the temperature of 20 C. The reaction mixture is settled for 0.5 hour, whereafter the layer of glucerol-methanol (the lower layer) is separated.The upper layer- methyl esters of fatty acids - is washed with water acidified with hydrochloric acid (0.43% by mass) and distilled at a temperature within the range of from 155 to 215OC (15 mm Hg) to collect three fractions: I fraction: 155-193 C (acid number 2.51 mg KOH/g, saponiiication number 192 mg KOH/g, bromine number 52 mg Br/100 g, density d420=0.878 kg/m , congelation point 30'C, average molecular weight 290.0); II fraction: 1 93-202 C (acid number 1.57 mg KOH!g, saponification number 189 mg KOHIg, bromine number 71 mg Br/100 g, density d420= 0.870 kg/m3 congelation point -9.3 C, average molecular 295.0); III fraction: 202-215 C (acid number 1.32 mg KOH'g, saponification number 186 mg KOHIg, bromine number 68 mg Brí 100 g, density d20= 0.S67 kg/m congelation point 15.2 C, average molecular weight 299.0).

Into a 500 ml flask provided with a stirrer, a distiller unit and a thermometer 295 g (1.00 g-mol) of distilled methyl esters of fatty acids (II fraction) and 30 g of monoethanolamine (0.491 g-mol) are placed. The mixture is stirred for 0.25-0.3 hour at a temperature of 70-72 C, whereafter the stirrer is stopped and, after settling, within 0.25-0.3 hour the lower darkened layer of monoethanolamine is removed by means of a pipette. Into the flask 80 g (1.310 g-mol) of monoethanolamine is charged and the mixture is stirred at the temperature of 80 C, then 6.6 g of a 37.8% solution of a catalyst - sodium 2-aminoethoxylate in monoethanolamine is added.

The reaction time is 1.2 hour. At the reduced pressure of 200 mm Hg, the mixture is heated to the temperature of 90 C and methanol is distilled off. The excess of monoethanolamine is distilled off under a reduced pressure of 20-25 mm Hg and at a temperature in the reaction flask not over 125-C. There are thus obtained 328 g of monethanolamide of fatty acids with the average molecular weight of 324. The product yield as calculated for the degree of conversion of monethanolamide is 96% of the theoretical.

Into a 1,000 ml flash provided with a thermometer and a stirrer 324 g of the resulting monoethanolamide of fatty acids are placed, heated to the temperature of 70 C and, under stirring for 0.25-0.5 hour 108 g (1.10 g-mol) of maleic anhydride are added. Under these conditions the mixture is stirred for 1.5 hours to give 432 g of acidic monoethanolamine maleate (acylamidoethylene maleate).

In a 2,000 ml flask provided with a thermometer, a stirred and an addition funnel a solutions is prepared from 956 ml of water, 1 22 g (0.642 -m-ol) 7 S-;HUm pyrosulphite and 163 g (1.284 g-mol) of a mixture of di and tri-ethanolamine with the equivalent weigth of 127. The solution is heated to the temperature of 60 C and at this temperature for 0.3-0.5 hour the resulting acidic monoethanolaniide maleate is added for sulphuration and neutralization. Stirring is continued for 0.3-0.5 hour to give 1,670 g of an aqueous solution of the desired product- triethanolamine and sodium double salt of acylamidoethylenesulphosuccinic acid having the following general formula:

wherein R is C15-C19 with the content of the desired product of 31.2% by mass. The product has the average molecular weight of 650.

Total solids 40.2% Degree of conversion (desired product initial amide) 82.0% Solubility in CCIe 4.5% Viscosity at 20C 32.0 mPas.

Density d?? 1.098 kg/m3 pH (10% solution) 6.85.

Example 2 The synthesis of methyl esters of fatty acids is carried out in a manner similar to that described in the foregoing Example 1.

Into a 500 ml flask provided with a stirrer, a distillation unit and a thermometer 295 g (1.00 g-mol) of distilled methyl esters of fatty acids (II fraction), 30 g (0.285 g-mol) of diethanolamine are placed and a further treatment is conducted as described in Example 1. Then to the methyl esters of fatty acids 110 g (1.05 g-mol) of diethanolamine and 7.3 g of a 37.8% solution of sodium 2-aminoethoxylate in monoethanolamine are added; the mixture is stirred at the temperature of 70"C to obtain a homogeneous solution. The reaction time is 2 hours. Under the reduced pressure of 200 mm Hg, the mixture is heated to 90"C and methanol is distilled off to give 383 g of diethanolamide of fatty acids with the average molecular weight of 369.The product yield, as calculated for the degree of conversion of diethanolamine, is 87% of the theoretical.

Into a 500 ml flask provided with a stirrer and a thermometer 383 g of the resulting diethanolamides are placed, the mixture is heated to the temperature of 60"C and 142 g (1.45 g-mol) of maleic anhydride are portion-wise added for 0.5 hour. The solution is stirred at the temperature of 65"C for 3.5 hours and allowed to stand at room temperature for 12 hours. There are thus obtained 525 g of acidic diethanolamide maleate (acylamido-N-hydroxyethyl-N-ethyl maleate).

In a 2,000 ml flask provided with a thermometer, a stirrer and an addition funnel a solution is prepared from 918 ml of water, 158.5 g (0.834 g-mol) of sodium pyrosulphite and 199.2 g (1.66 g-mol) of a mixture of di- and triethanolamine with the equivalent weight of 120, heated to the temperature of 80"C and the above-prepared acidic diethanolamide maleate is added thereto through the addition funnel under stirring for 0.3-0.5 hour. The stirring is continued for 0.3-0.5 hour.

1,800 g of an aqueous solution of the desired product are thus obtained - triethanolamine and sodium double salt of acylamido-isl-hydroxyethyl-N-ethylenesulphosuccinic acid of the following general formula:

wherein R is C15-C19 with the content of the desired product of 27% by mass.

The product has the average molecular weight of 695.

Total solids 46.3% Degree of conversion (desired product/ini tial amide) 70.0% Solubility in CCI4 6.5% Viscosity at 20 C 28 mPas.

Density D420 1.088 kg/m3 pH (10% solution) 6.90 Example 3 The synthesis of methyl esters of fatty acids is conducted in a manner similar to that described in Example 1 hereinbefore.

Into a 500 ml flask provided with a stirrer, a distiller and a thermometer 133 g (1.00 g-mol) of diisopropanolamine, 7.5 g of a 37.8% solution of sodium 2-aminoethoxylate in monoethanolamine are placed.

295 g (1.00 g-mol) of distilled methyl esters of fatty acids (II fraction) preliminarily treated with diisopropanolamine are added into the flask and stirred at 80-820C for 2 hours. Under the reduced pressure of 200 mm Hg, the mixture is heated to the temperature of 90"C and methanol is distilled off. There are thus obtained 400 g of diisopropanolamide of fatty acids with the average molecular weight of 396. The product yield as calculated for the degree of conversion of diisopropanolamine is 92% of the theoretical. value.

To 3969 of the resulting diisopropanolamide at the temperature of 60 C 127 g (1.3 g-mol) of maleic anhydride are added and kept at this temperature for 2.5 hours to give 523 g of acidic diisopropanolamide maleate (acylamido-N-2-hydroxypropyi-N-propyiene maleate). Sulphuration and neutralization of the acidic diisopropanolamide maleate are carried out in a manner similar to that described in Example 1 hereinbefore by adding it into a solution containing 1,440 ml of water, 140 g (0.736 g-mol) of sodium pyrosulphite and 219 g (1.47 g-mol) of triethanolamine at a temperature of 78-80 C to give 2,290 g of an aqueous solution of triethanolamine and sodium double salt of acylamido-N-2-hydroxypropyl-N-propylenesulphosuccinic acid of the following formula::

wherein R is C16-C19, with the content of the desired product of 24.6% by mass.

The product average molecular weight is 747.

Total solids 34.7% Degree of conversion (desired product" initial amide) 75.6% Solubility in CCI 6.8% Viscosity at 20 C 16.0 mPas.

Density d420 1.082 kg, m3 pH (10% solution) 6.82 Example 4 The synthesis of methyl esters of fatty acids is carried out in a manner similar to that described in Example 1.

Into a 500 mi flask provided with a stirrer, a distiller and a thermometer 110 g (1.465 g-mol) of N-methylethanolamine, 7.0 g of a 37.8% solution of sodium aminoethoxylate in monoethanolamine and 265 g (0.893 g-molj of distilled methyl esters of fatty acids (II fraction) preliminarily treated with N methylethanolamine are charged the mass is stirred for 1.5 hours at a temperature of 80-83 C. Then methanol is distilled off under the reduced pressure of 200 mm Hg at the temperature of 90 C. The excess of N-methylethanolamine is distilled off at 15-15 mm Hg and at a temperature of 120-123 C to give 307 g of N-methylethanolamide of fatty acids with the average molecular weight of 338.The product yield as calculated for the degree of conversion of N-methylethanolamine is equal to 95% of the theoretical. To 306 g of the resulting IJ-merhyieihanolan7ide o; fatty acids 110 g (1.122 g-mol) of maleic anhydride are added at the temperature of 65 C and stirred at this temperature for 2 hours to give 416 g of acidic N-methylethanolamide maleate (acylamido-N-methyl-N-ethylene maleate).

Sulphuration and neutralization of the acid N-methylethanolamide maleate are carried out in a manner similar to that described in Example 1 by adding it into a solution containing 1,356 ml of water, 107 g (0.563 g-mol) of sodium pyrosulphite and 168 g (1.126 g-mol) of triethanolamine at the temperature of 70 C to give 2,045 g of an aqueous solution of triethanolamine and sodium double salt of acylamido-N-methyl-N ethylenesuiphosuccinic acid of the formula:

wherein R is C15-C15, with the content of the desired product of 27.6 by mass. The average molecular weight of the product is 6 3.

Total solids 31.5% Degree of conversion (desired product/ initial amide) 82.0% Solubility in CCid 5.7% Viscosity at 200C 34.0 mPas.

Density d420 1.094 kg/m3 pH (10% solution, 6.96.

Example 5 The synthesis of methyl esters of fatty acids is carried out in a manner similar to that described in Example 1.

Into a 500 ml flask provided with a stirrer, a distiller and a thermometer 290 g (1.00 g-mol) of distilled methyl esters of fatty acids (I fraction), 29 g (0.475 g-mol) of monoethanolamine are placed and the further treatment is conducted as in Example 1 hereinbefore.

Then to the methyl esters of fatty acids 72.5 g (1.187 g-mol) of monoethanolamine and 4.8 g of a 37.8% solution of sodium 2-aminoethoxylate in monoethanolamine are added. Temperature is elevated to 90"C and stirring at this temperature is confinued for 1.2 hour.

Methanol and excess of monoethanolamine are removed in a manner similar to that of Example 1, to give 322 g of monoethanolamide of fatty acids with the average molecular weight of 319. The product yield as calculated for the degree of conversion of monoethanolamine is 96% of the theoretical value.

To 319 g of the thus-produced monoethanolamide of fatty acids 102 g (1.04 g-mol) of maleic anhydride are added at the temperature of 80"C and stirred at this temperature for 1.5 hours to give 421 g of acidic monoethanolamide maleate (acylamidoethylene maleate). Sulphuration and neutralization of the acidic monoethanolamide maleate are conducted in a manner similar to that described in Example 1 by adding it into a solution containing 630 ml of water, 114 g (0.6 g-mol) of sodium pyrosulphite and 168 g of a 25% solution of ammonia hydroxide at the temperature of 70 C to give 1,330 g of an aqueous solution of sodium and ammonium double salt of acylamidoethylene sulphosuccinic acid having the following formula:

wherein R is Cg-C17 with the content of the desired product of 32% by mass.The average molecular weight of the thus-obtained product is 537.

Total solids 40.8% Degree of conversion (desired product/initial amide) 81.0% Solubility in CC14 4.9% Viscosity at 20 C 22.0 mPas.

Density d20 1.102 kg/m3 pH (10% solution) 6.95 Example 6 The synthesis of methyl esters of fatty acids is carried out in a manner similar to that described in Example 1.

Into a 500 ml flask provided with a stirrer, a distiller and a thermometer 223 g (1.00 g-mol) of distilled methyl esters of fatty acids (Ill fraction) and 20 g (0.327 g-mol) of monoethanolamine are charged and the treatment is conducted in a manner similar to that described in Example 1 hereinbefore. Then to the methyl esters of fatty acids 90 g (1.473 g-mol) of monoethanolamine and 8,2 g of a 37.8% solution of sodium 2-aminoethoxylate in monoethanolamine are added and stirred at the temperature of 90"C for 1.5 hours.

Methanol and the excess monoethanolamine are distilled off as in Example 1.

There are thus obtained 330g of monoethanolamide of fatty acids with the average molecular weight of 328. The product yield as calculated for the degree of conversion of monoethanolamine is equal to 95.5% of the theoretical.

At a temperature of 83-85"C to 328 g of the resulting monoethanolamide of fatty acids 121.4 g (1.238 g-mol) of maleic anhydride are added and stirred at this temperature for 2 hours to give 449 g of acidic monoethanolamide maleate (acylamidoethylene maleate). Sulphuration and neutralization of the acidic monoethanolamide maleate are carried out in a manner similarto that described in Example 1 by adding thereof into a solution containing 970 ml of water, 158.3 g (0.712 g-mol) of potassium pyrosulphite and 149.5 g (1.424 g-mol) of diethanolamine at the temperature of 90"C.There are obtained 1,720 g of an aqueous solution of diethanolamine and potassium double salt of acylamidoethylene sulphosuccinic acid of the following general formula:

wherein R is C17-C21 with the content of the desired product of 30.3% by mass. The average molecular weight of the thus-obtained desired product is 649.

Total solids 41.4% Degree of conversion (desired productiinitial amide) 80.5% Solubility in CCI4 4.2% Viscosity at 20"C 20.0 mPas.

Density d20 1.089 kg/m3 pH (10% solution) 7.05.

Example 7 The synthesis of methyl esters of fatty acids is carried out in a manner similar to that described in Example 1.

Into a 1,000 ml flask provided with a stirrer, a distiller and a thermometer 161.0 g (1.0 g-mol) of dibutanolamine, 8.0 g of a 37.8% solution of sodium 2-aminoethoxylate in monoethanolamine are charged.

Also added thereto are 295 g (1.00 g-mol) of distilled methyl esters of fatty acids (II fraction) pre-treated with dibutanolamine and stirred at the temperature of 80"C for 2 hours. Under the reduced pressure of 200 mm Hg, the mixture is heated to the temperature of 90C and methanol is distilled off to give 428 g of dibutanolamide of fatty acids with the average molecular weight of 424. The product yield as calculated for the degree of conversion of dibutanolamine is 88% of the theoretical.

To 424 g of the thus-produced dibutanolamide of fatty acids at the temperature of 75eC 127.5 g (1.30 g-mol) of maleic anhydride are added and stirred at this temperature for 3 hours to give 551 g of acidic dibutanolamide maleate [acylamido-NI(1-methyl,2-hydroxy)-propyl-N-(1,2-dimethyl)ethylenemaleate].Sulphuration and neutralization of the acidic dibutanolamide maleate are conducted as described in Example 1 by adding thereof into a solution consisting of 1,500 ml fof water, 142 g (0.747 g-mol) of sodium pyrosulphite and 222 g (1.49 g-mol) of triethanolamine at the temperature of 70"C to give 2,412 g of an aqueous solution of triethanolamine and sodium double salt of acylamido-N-(1 -methyl,2-hydroxy)propyl-N-(1 2-dimethyl)ethylenesulphosuccinic acid of the following formula:

wherein R is C16-C19 with the content of the desired product of 24.1 % by mass.

The average molecular weight of the desired product is 774.

Total solids 36.2% Degree of conversion (desired product'initial amide) 74.8% Solubility in CC14 7.2% Viscosity at 209C 28 mPas.

Density d420 1.062 kg/m3 pH !10 JG solution) 6.95 Example 8 The synthesis of methyl esters of fatty acids is conducted in a manner similar to that described in Example 1.

Into a 500 ml flask provided with a stirrer, a distiller and a thermometer 116 g (1.30 g-mol) of N-ethylethanolamine, 7.2 g of a 37.8% solution of sodium 2-aminoethoxylate in monoethanolamine and 295 g (1.00 g-mol) of distilled methyl esters of fatty acids (II fraction) pretreated with N-ethylethanolamine are charged and stirred at the temperature of 80"C for 1.5 hours. Methanol is distilled off under the reduced pressure of 200 mm Hg at the temperature of 90 C. The excess of ethylethanolamine is distilled off under the reduced pressure of 10-15 mm Hg at a temperature of 120-125 C to give 355 g of N-ethylethanolamide of fatty acids with the average molecular weight of 352. The product yield as calculated for the degree of conversion of N-ethylethanolamide is equal to 95% of the theoretical.

To 352 g of N-ethylethanolamide of fatty acids at the temperature of 90"C 108 g (1.10 g-mol) of maleic anhydride are added and stirred at this temperature for 2 hours to give 460 g of acidic ethylethanolamide maleate. Sulphuration and neutralization of the acidic ethylethanolamide maleate are conducted in a manner similar to that of Example 1 by adding thereof at the temperature of 70"C into a solution containing 1,400 ml of water, 120 g (0.63 g-mol) of sodium pyrosulphate and 77 g (1.26 g-mol) of monoethanolamine to give 2,052 g of an aqueous solution of monoethanolamine and sodium double salt of acylamido-N-ethyl-Nethylenesulphosuccinic acid of the following general formula::

wherein R is Cl5-C19 with the content of the desired product of 24.3% by mass.

The average molecular weight of the desired product is 614.

Total solids 31.2% Degree of conversion (desired product/initial amide) 81.6% Solubility in CC14 5.9% Viscosity at 20"C 32.0 mPas.

Density d420 1.086 kg/m3 pH (10% solution) 7.02.

Example 9 The synthesis of methyl esters of fatty acids is conducted in a manner similar to that described in Example 1.

Into a 500 ml flask provided with a stirrer, a distiller and a thermometer 295 g (1.00 g-mol) of distilled methyl esters of fatty acids (II fraction), and 15 g (0.246 g-mol) of monoethanolamine are charged and the further treatment is carried out in a manner similar to that described in Example 1 hereinbefore.

80 g (1.310 g-mol) of monoethanolamine are added to the methyl esters of fatty acids and the mixture is stirred at the temperature of 80"C, then 5.6g of a catalyst solution - 28% sodium methanolate in methanol is added. The reaction time is 1.2 hour. Methanol and the excess of monoethanolamine are removed as described in Example 1.

There are thus obtained 325 g of monoethanolamide of fatty acids with the average molecular weight of 324. The product yiels as calculated for the degree of conversion of monoethanolamine is 95.6% of the theoretical value. Further operations of the process are carried out following the procedure described in Example 1 to give the desired produce to that of Example 1 hereinbefore.

The quality characteristics of the compounds prepared as described in Example 1-9 are presented in Tables 1-3.

Example 10 A bubble bath comprises the following components, per cent by mass: triethanolamine and sodium double salt of acylamidoethylenesulphosuccinic acid 32 perfume 1.5 water the balance.

The quality characteristics of the bubble bath are given in table 4 hereinbelow.

Example 11 A baby champoo consists of the following components, per cent by mass: triethanolamine and sodium double salt of acylamidoethylenesulphosuccinic acid 5 perfume 0.1 water the balance.

The quality characteristics of the baby shampoo are given in Table 4 hereinbelow.

Example 12 A hair shampoo comprises the following components, per cent by mass: triethanolamine and sodium double salt of acylamidoethylenesulphosuccinic acid 20 C9-C17 fatty acid diethanolamide 3.5 ethanol 1.5 sodium chloride 2.0 perfume 1.0 water the balance.

The quality characteristics of the hair shampoo are given in Table 4 hereinbelow.

Example 13 A hair shampoo composition comprises the following components, per cent by mass triethanolamine and sodium double salt of acylamidoethylenesulphosuccinic acid 12 C9-C17 fatty acid diethanolamide 3.0 ethanol 0.75 sodium chloride 3.5 perfume 0.75 water the balance The quality characteristic of the shampoo are given in Table 4 hereinbelow.

Ross-Miles pour foam numbers at 40 C and the concentration of 0.25% by mass of the compound of the present invention

Examp- Amine and alkali Cations Distilled water Foam sta- Hard water (5.35 mg-equivll) le No. metal double foam column height, bility Foam column heigth, mm Foam stability H5/H1 salts of acylami- mm H3/H1 do alkylene (or H0 H1 H5 H0 H1 H5 acylamido-N-hyd- 0 sec 60 sec 300 sec 0 sec 60 sec 300 sec roxyalkyl-N-alkylene)sulphosuccinic acid 1 2 3 4 5 6 7 8 9 10 11 1 R1=C15-C19 Na/50% 195 180 175 0.97 205 180 180 0.97 TEA+ R2=hydrogen 50% DEA R3=-CH2-CH22 R1=C15-C19 Na/34%TEA+ 66% DEA 185 170 166 0.98 190 175 168 0.96 R2=-C2H4OH R3=-CH2-CH23 R1=C15-C19 Na/TEA 187 173 168 0.97 193 177 170 0.96 R2=-CH2-CH-OH CH3 R3=-CH2-CH CH3 4 R1=C15-C19, Na/TEA 193 183 177 0.97 202 186 180 0.97 R2=-CH3, R3=-CH2-CH25 R1=C9-C17 R2=hydrogen Na/NH4 183 170 166 0.98 190 177 172 0.97 R3=-CH2-CH2

TABLE 1 (cont.) 1 2 3 4 5 6 7 8 9 10 11 6 R1=C17-C21 K/DEA 180 167 160 0.96 185 170 165 0.97 R2=hydrogen R2=-CH2-CH27 R1=C15-C19 Na/TEA 182 167 163 0.98 188 173 165 0.96 R2=-CH-CH-CH3 CH3-CH R3=-CH-CH CH3 CH3 8 R1=C15-C19 Na/MEA 192 180 172 0.96 200 185 180 0.97 R2=-CH2-CH3 R3=-CH2-CH2 Note: TEA - triethanolamine; DEA - diethanolamine; MEA - monoethanolamine TABLE 2 Wash test on standard wool soil clotts at the concentration of 0.025% by mass of the compound according to the present invention.

Example Amine and alkali metal double Cations Detergency Whiteness No. salts of acylamidoalkylene efficiency retention succinic or (acylamido-Nhydroxyalkyl-N-alkylene)sulphosuccinic acid 1 2 3 4 5 1 R1=C15-C19, R-hydrogen; R3=-CH2-CH2- Na/50% TEA+ 95 98 50% DEA 2 R1=C15-C19, R2=-C2H4OH, R3=-CH2-CH2- Na/34% TEA+ 96 98 66% DEA 3 R1=C15-C19, R2=-CH2-CH-OH, R3=-CH2-CH- Na/TEA 96 98 CH3 CH3 4 R1=C15-C19, R2=-CH3, R3=-CH2-CH2- Na/TEA 94 98 5 R1=C8-C17, R2=hydrogen, R3=-CH2-CH2- Na/NH4 90 98 6 R1=C12-C21, R2=hydrogen, R3=-CH2-CH2- K/DEA 92 98 7 R1=C15-C12, R2=-CH-CH-CH3, R3=-CH-CH- Na/TEA 95 97 CH3 OH CH3 CH3 8 R1=C15-C19, R2=-CH2-CH3, R3=-CH2-CH2- Na/MEA 96 98 9 sodium dodecysulphate Na 96 98 Note: TEA - triethanolamine; DEA - diethanolamine; MEA - monoethanolamine TABLE 3 Surface tension, as determined by stalagmomentrical method, expressed in N/mx10-3 at 20 C for a 0.1% by mass aqueous solution of the compounds according to the invention.

Example Amine and alkali metal double Cations Distilled Hard water (5.35 mg-qauivll) No. salts of acylamidoalkylene or (acylamido-N-hydroxyalkyl-Nalkylene)sulphosuccinic acid 1 2 3 4 5 1 R1=C15-C19, R2=hydrogen R3=--CH2-CH2- Na/50% TEA+ 30.0 31.3 50% DEA 2 R1=C15-C19, R2=C2H4OH, R3=-CH2-CH2- Na/34% TEA 28.4 29.2 66% DEA 3 R1=C15-C19, R2=-CH2-CH-OH, R3=-CH2-CH- Na/TEA 28.1 28.5 CH3 CH3 4 R1=C15-C19=-CH3m R3=-CH2-CH2- Na/TEA 30.2 30.8 5 R1=C9-C17, R2=hydrogen R3=-CH2-CH2- Na/NH4 30.4 31.6 6 R1=C17-C21, R2=hydrogen, R3=-CH2-CH2- K/DEA 30.6 30.8 7 R1=C15-C19, R2=-CH-CH-CH3, R3=-CH-CH- Na/TEA 28.2 29.0 CH3 OH CH3 CH3 8 R1=C15-C19, R2=-CH2-CH3, R3=-CH2-CH2- Na/MEA 29.8 30.9 Note: TEA = triethanolamine, DEA - diethanolamine, MEA = monoethanolamine TABLE 4 Nos Characteristics ofthe Examples Nos.

detergent compositions 10 11 12 13 1 2 3 4 5 6 Foam numbers of Ho 205 201 198 196 1 0.25% solution of the compound of this in vention at 40oC, H1 186 184 174 176 according to Ross -Miles, mm, H5 180 178 171 173 2 Foam stability, H5/H1 0.97 0.98 0.98 0.98 3 Turbiditypoint, C -2to5 1-2 2-3 -1to1 4 Defatting effect compared with sodium laurylsul phate, % 56.3 51.5 54.2 54.0 5 Viscosity at 20"C, mPas. 32.0 3.0 1,200.0 430.0 6 Density at 20on, kg/m3 1.098 1.008 1,072 1.063 7 pH of 10% aqueous solu tion of the compound of this invention 6.80 6.85 6.75 6.85

Claims (5)

1. Amine and alkali metal double salts of an acylamido alkylene (or acylamido-N-hydroxyalkyl-Nalkylene)sulphosuccinic acid of the general formula:

wherein R1 is hydrogen -CH3, -CH2-CH3, -CH2-CH2-OH;

R4, R5, R6 are each hydrogen and or -CH2- CH2-OH; Me is Na or K

2.A process for preparing amine and alkali metal double salts of an acylamidoalkylene (or acylamido-N-hydroxyalkyl-N-alylene)sulphosuccinic acid according to Claim 1, consisting in that fatty wastes of effluents resulting from fish-processing plants containing fatty acids and glycerides with an acid number of not more than 50 mg KOH/g, saponification number of 181-192 mg KOH/g and bromine number of 60-70 mg Brim 00 are treated with methanol in the presence of sulphuric acid upon heating at reflux to give a reaction mixture, wherefrom the fat layer which consists of glycerides and methyl esters of fatty acids is separated and treated with methanol in the presence of sulphuric acid at a temperature of from 50 to 60"C to give a reaction mass, wherefrom an anhydrous fat layer is separated and treated with methanol in the presence of an alkali at the boiling temperature of methanol to give a reaction mixture containing methyl esters of fatty acids which are recovered and treated with an alkylolamine taken in an amount of 25 to 55% by mass of the amount of methyl esters of fatty acids in the presence of a catalyst selected from the group consisting of an alkali metal, or its amide or an alcoholate thereof at a temperature of 70 to 900C to give alkylolamides of fatty acids which are treated with maleic anhydride at a temperature of 60 to 90"C to give maleates of fatty acid alkylolamides, followed by treatment thereof with sodium or potassium pyrosuiphite and ethanolamine or ammonia at a temperature of 60 to 90"C in an aqueous medium to give the desired product.

3. A process according to Claim 2, wherein, in order to improve the quality of the desired product, methyl esters of fatty acids prior to said treatment thereof with an alkylolamine in the presence of said catalyst are preliminarily treated with an alkylolamine taken in an amount of 5 to 10% by mass of the amount of methyl esters of fatty acids at a temperature of 70 to 80"C, followed by the removal of the spent alkylolamine.

4. A process according to Claims 2-3, wherein as the alkylolamine use is made of monoethanolamine, diethanolamine, diisopropanolamine, N-methylethanolamine, N-ethylethanolamine, or dibutanolamine.

4. A process according to Claims 2-3, wherein as the alkylolamine use is made of monoethanolamine, diethanolamine, diisopropanolamine, N-methylethanol, N-ethylethanol, or dibutanolamine.

5. A process according to Claims 2-4, wherein, in order to simplify the process, as the catalyst sodium 2-aminoethoxylate is used.

6. A process according to Claims 2-5, wherein as the ethanolamine mono-, di- and/or triethanolamine is used.

7. A detergent consisting of a surfactant - triethanolamine and sodium double salt of an acylamidoethylenesulphosuccinic acid of the formula:

wherein R is C15-C21 according to Claim 1, a perfume and water, the components being present in the following proportions, percent by mass: triethanolamine and sodium double salt of acylamidoethylene sulphosuccinic acid

5.0-32.0 perfume 0.1-1.5 water the balance.

8. A detergent according to Claim 7, additionally containing diethanolamide of C9-C17 fatty acids, sodium chloride and ethanol at the following proportions of the components, per cent by mass: triethanolamine and sodium double salt of acylamidoethylenesulphosuccinic acid 12.0-20.0 C9-Ci7fatty acid diethanolamide 0.5-3.5 sodium chloride 1.0-3.5 ethanol 0.3-1.5 perfume 0.1-1.5 water the balance.

Superseded claims 1 & New or amended claims:- 1 & 4 as per attached sheets.

1. Amine and alkali metal double salts of an acylamido alkylene (or acylamido-N-hydroxyalkyl-N- alkylene)sulphosuccinic acid of the general formula:

wherein R1 is a straight-chain hydrocarbon C5-C21, R2 is hydrogen, -CH3, -CH2-CH3, -CH2-CH2 -OH;

R4, R5, Rs are each hydrogen and or -CH2- CH2-OH; Me is Na or K.