FI84262C - Surfactants useful in cosmetic products and detergents containing amine or ammonium alkali metal double salts of acylaminoalkylene (or acylamido-N-hydroxyalkyl-N-alkylene) sulfobaric acid - Google Patents

Description

84262

Surfactant mixtures for use in cosmetic products and detergents, containing amine or ammonium alkali metal double salts of acylamidoalkylene (or acylamido-N-hydroxyalkyl-N-alkylene) sulphosuccinic acid

The invention relates to surfactants and more particularly to mixtures containing amyl (or ammonium) alkali metal double salts of acylamidoalkylene (or acylamido-N-hydroxyalkyl-N-alkylene) sulfosuccinic acid, to a process for their preparation and to their use as cleaning agents.

These compounds are useful as anionic surfactants for the preparation of household chemicals, in particular cosmetics, hair cleaners, bath foams and washing soaps, as stabilizers in cosmetic preparations and as ingredients in carpet cleaning compositions and wool detergents, especially those used in cold water; in the manufacture of film and photographic materials as wetting agents when photographic emulsions are applied to films.

Modern surfactants 11a should have a high foam number and good foam stability in aqueous solutions as well as good solubility in cold, hard water and should have minimal skin irritation and only moderate skin degreasing effect as well as good biodegradability.

Previously known surfactants include e.g. disodium salts of acylamidoethylenesulfonic succinic acid prepared from cotton soap broth in oil extraction plants (Uzbek Chemical Journal, Uzb. SSR Academy of Sciences, No. 3, pp. 52-54, 1976) of the following general formula 0 0 i! Il

R - C - NH - CH- - CH - 0-C - CH - CH- - COONa λ λ \ A

SO 3 Na where R is a straight chain hydrocarbon group C 1 -C 4.

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However, these compounds have insufficient solubility in cold water and can only be used to make pasty cleaning compositions that are less suitable for cold washing.

Surfactants made from coconut oil, palm oil or other vegetable oils (see DE Patent 2,408,895) or synthetic fatty acids (see Uzbek Chemical Journal, No. 3, pp. 52-54, 1975) are also known.

Certain vegetable oils, synthetic fatty acids and animal fats used as raw materials, which contain at least 13 saturated carbon atoms, give surfactants that are poorly soluble in cold water and have low surfactant properties. Surfactants made from these raw materials are ill-suited for cosmetic purposes. Surfactants of this type prepared from fatty acids having up to 14 carbon atoms have an excessive degreasing effect.

The compounds of FR 3399M are ammonium, alkali metal, alkaline earth metal and / or organo-substituted ammonium salts of the triethanolamine derivatives of sulphosuccinic acid half-esters of the general formula

CH 2 -CH 2 -O-X N - CH 2 -CH 2 -O-Y

\ ch2-ch2-o- (ch2-ch2-o) z-co-ch2-ch-cooh so3h These compounds are comparable to eo. to the compounds according to the invention when X = R-CO-, Y = H and Z = O, in particular e.g. H, where X = -OC-C17H33 and sodium and triethanolamine are used as cations.

But although the compounds of the reference publication are triethanolamine derivatives, they have an oxyethylene group (between a -CH 2 -CH 2 -O-> acyl group, an R-CO- and a nitrogen atom, e.g.

3 84262 / "

R-CO-O-CHO CH ^ -N

^ \ X ...

In the compounds of the present invention, the acyl group is instead directly attached to a nitrogen atom, e.g.

R-CO-N

"T \ ...

The examples further show that the group R in the group X is a residue of a saturated or slightly unsaturated (1 double bond) natural fatty acid.

DE-1 115 398 discloses compounds of the general formula H H

I I

A.B.OOC-C-C a Z-SO

I I

H COOZ

where in a comparable case A = R-CO-N-

Y

R = alkyl residue having 10 to 20 carbon atoms, Y = hydrogen, alkyl or oxyalkyl group, B = (CH 2> x where x> 2 and Z = K, Na, NH 4 or a residue of an organic base.

The group R of these compounds represents a saturated or low-saturated (1-2 double bonds) residue of natural fatty acids, while R in the compounds of the present invention is derived from a fatty waste liquor and is highly unsaturated. In addition, the compounds of DE are disalts, while the compounds of the present invention are amine-alkali metal double salts, i.e. the cations in the -SO3Z and -COOZ groups are different.

The compounds of 4,84262 GB 1 018 302 are alkylolamine derivatives of undecylenic acid having the general formula

ClOH19 "-CO-N (CH 2) n" group (C m H 2m °) y 'CO-CHR 1 CHR 2-C00Y.

R

The compounds are comparable to the compounds of the present invention when R is hydrogen or a hydroxyl-substituted alkyl group having 1 to 4 carbon atoms; m, n and y are all integers 1; R1 and R2 are different; R1 = H and R2 = SO3H. According to the patent publication, X and Y may be different or similar, in which case they represent a hydrogen atom, an alkali metal, an ammonium group, an organic amino group or an alkylolamino group.

Group R of the compounds of GB discloses an undecylenic acid residue which is not highly unsaturated. In addition, eo. the raw material used in the invention does not contain an undecylene group because natural fatty acids have only an odd number of carbon atoms in the molecule.

Although the formula disclosed in GB 1 018 302 presents the possibility of using various cations, including amines and alkali metals, the publication does not suggest that such a combination would be useful. According to the publication, all cations are equivalent and the main focus is on the anionic part of the compounds (i.e. the antifungal and bacterial activity of the undecylene residue). In practice, only sodium salts are used.

Compounds according to U.S. Patent No. 2,976,209, comparable to the present compounds, have the general formula R-CO-NH-X-O-CO (Y-C 0 M) n, so 3m '5 84262 wherein R-CO- is a fatty acyl group having 8 -18 carbon atoms, X is a fully deaminated and dehydroxylated, water-soluble residue of a primary alcohol amine, Y is a fully decarboxylated residue of a water-soluble polycarboxylic acid having 4 carbon atoms, and n is an integer of 1. According to the patent, M is an alkali metal or lower organically substituted ammonium group, is a lower organically substituted ammonium group. M and M 'may be substituted and the lower organically substituted ammonium groups may be different.

The R group of the compound of the U.S. Patent is a saturated or slightly unsaturated (1-2 double bonds) residue of a natural fatty acid. The group R of the compound of the present invention is largely unsaturated and derived from a fatty waste liquor. With respect to cations, two types of salts are described with different salt-forming cations: double salts of alkali metal and lower alkylamines and double salts with various lower alkylamine cations. Compounds (a) comprise one of two distinct classes of compounds used in biologically toxic concentrates to prepare homogeneous and stable emulsions and dispersions. The U.S. publication states that unforeseen and unexpected results are due to a synergistic effect between two different classes of compounds.

Thus, U.S. Patent No. 2,976,209 relates to compounds other than the present invention and has a completely different field of application.

The present invention provides novel surfactants characterized by high foam numbers, good foam stability, good solubility in cold water and gentleness to the skin due to the use of waste liquors from the fishing industry for soap making.

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The surfactants according to the invention are new and have not been described in the literature so far.

The novel compounds according to the invention, i.e. the general formula for the amine (or ammonium) alkali metal double salts of acylamidoalkylene (or acylamido-N-hydroxyalkyl-N-alkylene) sulphosuccinic acid is as follows: ^ C ° 2 - / R4 ++

Ri - C - N - Ro - O - C - CH7 - CH MeN-Rc

Wherein R 1 is a straight chain hydrocarbon group C -C 1, R is hydrogen, -L yzlz -CH 3, -CH 2 -CH 3, -CH 2 "CH 2 -OH; 78462 -CH- -CH-OH or -CH-CH-CH-; II ί 3 CH3 CH3 oh R, is -CH - CH-, -CH_-CH- or -CH-CH-; j ZZZI || R 1, R 2, R 6 are each hydrogen and / or -CH 2 -CH 2 -OH, and Me is Na or K.

The compounds according to the invention are dough-like substances which are completely soluble in cold water (40% solution is translucent and has good flow properties at 20 ° C and does not become cloudy on storage). The compounds are highly heat resistant. In addition, they are gentle on the skin and readily biodegradable.

The structure of the compounds of the invention was determined by IR spectroscopy. The spectra have characteristic bands for the following functional groups: alkyl group 725-720 cm-1, CH3, C122 groups 2,960; 2,940-2,910; 2,870 cm -1; -CO-NH group 3,350-3,300; 3,050-3,010 cm -1; 0 11 -1 -C - O - group 1750-1 735 cm; -CO2 "ion 1610-1 550; 1450-1 300 cm-1; -OH group 3,500-3,250; 1,050-1,030 cm-1; -SO2-O group 1,420-1,330; 1 200-1 145 cm -1; -NH4 + group 3300-3 030 cm-1.

The presence of a double charge in the anions of the compounds of the invention was demonstrated by a cation exchange method in aqueous alcohol solution.

s 84262 The density of aqueous solutions of these compounds at a concentration of between 24 and 32% by weight is between 1,020 and 2020%. 103-1, 1020 · 103 kg / m3 at a western temperature of 20 ° C; the dynamic viscosity of these solutions at 20 ° C is between 20 and 34 mPas.

The compounds of this invention are characterized by surface activity.

The foam values of these substances, determined by the Ross-Miles method at 40 ° C and 0.25% by weight, are characterized by an initial foam column height in distilled water of 180-196 mm and a foam stability of 0.96- 0.98; in hard water, at a concentration of calcium and magnesium salts of 5.35 mg equivalents / l, the initial height of the foam column is 185-205 mm and the stability of the foam is 0.95-0.97.

The washing test of the novel compounds of the invention was performed by the following standard method (see F.V. Nevolin's "Chemistry and Technology of Synthetic Detergents", Pischevaya Promyshlennost '(Food Industry) Publishers, Moscow, 1971, pp. 405-415). At a stability of 0.25% by weight, the purification efficiency of these compounds was in the range of 90-96.

The surface tension of aqueous solutions of the compounds of the invention was determined by a stalagmometric method at 20 ° C with an aqueous solution concentration of 0.1% by weight. It ranged from 28.1 to 31.6 x 10 ~ 3 N / m.

The process for the preparation of the novel compounds according to the invention is based on fatty broths from fish processing plants containing fatty acids and glycerides with an acid value of up to 50 mg KOH / g, a saponification number of 181-192 mg KOH / g and a bromine value of 60-70 g Br / 100 g. refluxing with methanol in the presence of sulfuric acid to give a reaction mixture from which the fatty layer containing Glycerides and methyl esters of fatty acids is separated and treated with methanol in the presence of sulfuric acid at 50-60 ° C to 5 84262 to give a reaction mass from which the anhydrous fatty layer is separated and treated with methanol in the presence of an alkali at the boiling point of methanol to give a reaction mixture containing methyl esters of fatty acids which are separated and treated with an alkylolamine used in an amount of 25-55% by weight of methyl esters of fatty acids in the presence of a catalyst which may be alk. an almetal or an amide or alcoholate thereof, at a temperature between 70 and 90 ° C to give alkylolamides of fatty acids, which are treated with maleic anhydride at a temperature of 60 to 90 ° C to give maleates of alkylolamides of fatty acids, followed by treatment with sodium - or potassium pyrosulphite and ethanolamine or ammonia at 60-90 ° C in aqueous medium and the desired product is isolated.

In order to improve the quality of the desired product, the methyl esters of fatty acids are first treated with alkylolamine and only then the above alkylolamine treatment is carried out in the presence of the above catalyst using alkylolamine 5-10% by weight based on the weight of the methyl esters of fatty acids at 70-80 ° C the alkylolamine is removed.

Suitable alkylolamines include e.g. monoethanolamine, diethanolamine, diisopropanolamine, N-methylethanolamine, N-ethylethanolamine and di-butanolamine.

In order to simplify the amidation step of the fatty acid methyl esters, it is preferable to use sodium 2-aminoethoxylate as a catalyst.

It is preferred to use mono-, di- and / or triethanolamine as ethanolamine.

The method according to the invention is carried out in the following manner.

10 84262

Fatty effluents from fish processing plants containing fatty acids and glycerides with an acid value not exceeding 50 mg KOH / g, a saponification number 181-192 mg KOH / g and a bromine value 60-70 g Br / 100 g are treated with methanol in the presence of a sulfuric acid catalyst. This results in the esterification of the free fatty acids contained in the fatty waste broths under acidic conditions. The esterification reaction is carried out by stirring the reaction mixture for 1.5-2.5 hours at the boiling point of methanol. After the reaction, the mixture is allowed to settle and the upper layer (methanol) is separated and recycled for recovery, while the lower layer (fatty mixture) is treated with methanol in the presence of sulfuric acid at a temperature between 50-60 ° C. After settling, the upper layer (extraction methanol) is separated and recycled to the initial stage where the free fatty acids contained in the fatty waste solution are esterified under acidic conditions. The lower layer (purified fat blend) is passed to the alkaline transesterification of the glycerides.

For this purpose, the purified fat mixture is treated with methanol in the presence of alkali. The mixture is stirred at the boiling point of methanol for 0.25 hours, after which 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) is passed to methanol recovery. The upper layer (methyl esters of fatty acids) is washed with hot water acidified with hydrochloric acid and dried. Methanol is recovered from the wash water. The dried methyl esters are fractionated by vacuum distillation at a temperature in the range of 155-215 ° C under reduced pressure of 10-20 mm Hg. The yield of the desired fraction is 78-83% of the initial fat content of the fatty broth. The purified fatty acid methyl esters are treated with alkylolamine, which is used in an amount of 25 to 55% by weight based on the amount of the methyl ester of the fatty acids, at a temperature of 70 to 90 ° C in the presence of a catalyst such as an alkali metal, amide or alcoholate.

This gives alkylolamides of fatty acids.

,, 84262

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

Suitable alkylolamines include e.g. monoethanolamine, diethanolamine, diisopropanolamine, N-methylethanolamine, N-ethylethanolamine and the like.

In order to improve the quality of the desired product, the fatty acid methyl esters are pretreated with alkylolamine and only then the alkylolamine treatment is carried out in the presence of the above catalyst using 5-10% by weight of alkylolamine based on the weight of the fatty acid methyl esters at 70-80 ° C.

The yield of alkylolamides of fatty acids is 93-98% based on the theoretical degree of conversion of alkylolamines.

The alkylolamides obtained are mixed with maleic anhydride, which is used in an amount of 30 to 37% by weight, based on the alkylolamides, at a temperature of 60 to 90 ° C for 1.5 to 3.5 hours. The yield is the same as the theoretical value, calculated according to the degree of conversion of maleic anhydride. When the alkylolamide maleates thus obtained are treated with sodium or potassium pyrosulfite and ethanolamine or ammonia in an aqueous medium at a temperature of 60 to 90 ° C, the desired product is obtained. The yield of the final product is 70-82% based on the alkylolamide used as starting material.

The process according to the invention makes it possible to make full use of soap-making effluents from the fishing industry and thus to replace expensive food-grade fats and oils as well as synthetic petroleum raw materials currently used in the manufacture of surfactants. In addition, it reduces the impact of pollution on the environment.

The method is technically simple and does not require special equipment. To date, the soap-soup effluent used in the process of the invention has not been found to be used in organic fine chemical syntheses due to its over-contamination. Due to the above-mentioned measures, the method according to the invention makes it possible to produce high-quality end products from these raw materials, which serve as basic materials for the production of detergents without the need for special additives to improve the skin and washing effects. The invention also relates to the use of these new compounds as basic substances in detergent compositions. It is preferred to use the triethanolamine sodium double salt of acylamidoethylene sulfomeric resin acid.

The cleaning composition according to the invention, consisting of a surfactant, a perfume and water, contains, as a surfactant, a triethanolamine-sodium double salt of acylamidoethylenesulfosuccinic acid having the general formula as follows:

H II

R - C - NH - CH 2 - CH 2 - O - C - CH 2 - CH - COONH (C 1 OH) SO 2 Na where R is a straight chain hydrocarbon group C 1 -C 4 g, and the proportions of the components of the mixture are as follows in% by weight. : acyl idoethylene i sulfomer succinic acid triethanolamine sodium double salt 5.0 to 32.0 perfume 0.1 to 1.5 water rest

A preferred embodiment of the cleaning mixture according to the invention is a mixture which additionally contains diethanolamide, sodium chloride and ethanol of C8-C10 fatty acids in the following proportions by weight: triethanolamine sodium double salt of acylamidoethylene sulfosuccinic acid 12.0 to 20.0

Diethanolamide of C 8 -C 18 fatty acids 0.5 to 3.5 sodium chloride 1.0 to 3.5 ethanol 0.3 to 1.5 perfume 0.1 to 1.5 water remaining ib 84262

Compared to the previously known mixtures, the cleaning mixture according to the invention does not require such additives which have a degreasing-reducing effect.

It is very soluble in cold, hard water, has a high foam ratio and comes off easily when rinsed.

The cleaning composition according to the invention has mild dermatological properties and is readily biodegradable.

The invention is illustrated by the following examples.

Example 1 A 500 ml flask equipped with a reflux condenser and a thermometer was charged with 250 g of fatty broth from the fishing industry (acid number 24 mg KOH / g, saponification number 187 mg KOH / g, bromine number 66.2 g Br / 100 g, density d. - Λ g 4 0.914 · 10 kg / m and a pour point of 13.8 ° C) and 63 g of methanol to which 1.3 g (0.0125 mol) of concentrated sulfuric acid had been added. The mixture was refluxed for 1.5 hours at which time the esterification of the fatty acids occurred. The reaction mixture was allowed to settle for 0.25 hours, the upper layer (methanol) was separated and the lower layer (glycerides and fatty acid methyl esters) was treated at 58-60 ° C with 47.5 g of methanol supplemented with 0.09 g (0.00086 mol). concentrated sulfuric acid. Allow to settle for 0.25 hours and the layers were separated. The upper layer (extraction methanol) was recycled to the initial fatty acid esterification step. The lower layer (245 g) was placed in a 500 mL flask equipped with a reflux condenser, stirrer and thermometer, and 1.66 g (0.0415 mol) of sodium hydroxide in 35.6 g (1.113 mol) of methanol was added. The reaction mixture is stirred at the boiling point of methanol for 0.25 hours to give an alkaline transesterification of the glycerides, and then the mixture is cooled to 2 () ° C. The reaction mixture is allowed to settle for 0.5 hours and then the glycerol-methanol layer (lower layer) is separated. The upper layer (methyl esters of fatty acids) is washed with water to which hydrochloric acid (0.43% by weight) has been added, and distilled at 155-215 ° C (15 mm Hg) to give three fractions: 14 84262 I-fraction: 155- 193 ° C (acid number 2.51 mg KOH / g, saponification number 192 mg KOH / g, bromine number 52 g Br / 100 g, density d2 ^ = 0.878 · 102 kg / m2, solidification point 30 ° C and average molecular weight 290.0) ; Fraction II: 193-202 ° C (acid number 1.57 mg KOH / g, saponification number 189 mg KOH / g, bromine number 71 g Br / 100 g, density d 2 = 0.870 · 1CT kq / m, pour point 9.3 ° C and an average molecular weight of 295.0); Fraction III: 202-215 ° C (acid number 1.32 mg KOH / g, saponification number 186 mg KOH / g, bromine number 68 g Br / 100 g, density d2 ^ = 0.367 · 102 kg / m2, pour point 15.2 ° C and an average molecular weight of 299.0).

295 g (1.00 mol) of distilled fatty acid methyl esters (fraction II) and 30 g of monoethanolamine (0.491 mol) were charged to a 500 ml flask equipped with a stirrer, a distillation unit and a thermometer. The mixture is stirred for 0.25-0.3 hours at 70-72 ° C, the stirring is stopped and after a settling time of 0.25-0.3 hours the lower dark monoethanolamine is removed by pipette.

80 g (1.310 mol) of monoethanolamine are added to the flask and the mixture is stirred at 80 [deg.] C. and then 6.6 g of a 37.8% solution of monoethanolamine in the catalyst (sodium 2-aminoethoxylate) are added. The reaction time is 1.2 hours. The mixture is heated to 90 ° C under reduced pressure of 200 mm Hg and the methanol is distilled off. Excess monoethanolamine is distilled off under reduced pressure of 20-25 mm Hg and at a temperature not exceeding 125 ° C. This gives 328 g of fatty acid monoethanolamide with an average molecular weight of 324. The yield of the product is 96% of theory based on the degree of conversion of monoethanolamine.

Place in a 1000 ml flask equipped with a thermometer and a stirrer 324 g of the monoethanolamide of the fatty acids obtained are heated, heated to 70 [deg.] C. and 108 g (1.10 mol) of maleic anhydride are added with stirring over a period of 0.25 to 0.5 hour. Under these conditions, the mixture is stirred for 1.5 hours to give 432 g of acidic monoctanolamide maleate (acylamidoethylene maleate).

A solution of 956 ml of water, 122 g (0.642 mol) of sodium pyrosulfite and 163 g (1.284 mol) of a mixture of di- and triethanolamine (equivalent weight 127) is prepared in a 2000 ml flask equipped with a thermometer, stirrer and addition funnel.

The solution is heated to 60 ° C and at this temperature an acidic monoethanolamide maleate is added over 0.3 to 5 hours so that sulfurization and neutralization take place. Stirring is continued for 0.3-0.5 hours to give 1670 g of an aqueous solution of the desired product - acylamidoethylene sulfomeric resin triethanolamine sodium double salt having the following structural formula:

Il II

R - C - NH - CH 2 - CH 2 - O - C - CH 2 - CH - COONH (CO 2 OH) SO 3 Na wherein R is C 1 -C 3 g with a product content of 31.2% by weight of the solution. The average molecular weight of the product is 650.

Dry matter content 40.2%

Conversion rate (final product / original amide) 82.0%

Solubility in CCl 3 4.5%

Viscosity at 20 ° C 32.0 mPas

Density d2 ° 1.098 · 103 kg / m3 pH (10% solution) 6.85

Example 2

Methyl esters of fatty acids are synthesized as described in Example 1.

295 g (1.00 mol) of distilled methyl esters of fatty acids (fraction II) and 30 g (0.285 mol) of diethanolamine are placed in a 500 ml flask equipped with a stirrer, a distillation unit and a thermometer and the work-up is continued as described in Example 1. 110 g (1.05 mol) of diethanolamine and 7.3 g of a 37.8% solution of sodium 2-aminoethoxylate in monoctanolamine are then added to the methyl esters of fatty acids, the mixture being stirred at 70 ° C to obtain a homogeneous solution. The reaction time ie 84262 is 2 hours. The mixture is heated to 90 [deg.] C. under reduced pressure (200 mm Hg) and the methanol is distilled off to give 383 g of diethanolamide with an average molecular weight of 369. The yield of the product is 87% of theory, based on the degree of conversion of diethanolamine.

383 g of the diethanolamides obtained are placed in a 500 ml flask equipped with a stirrer and a thermometer, the mixture is heated to 60 [deg.] C. and 142 g (1.45 mol) of maleic anhydride are added in portions over 0.5 hours. The solution is stirred for 3.5 hours at 65 ° C and allowed to stand for 12 hours at room temperature. 525 g of acidic diethanolamide maleate (acylamido-N-hydroxyethyl-N-ethyl maleate) are thus obtained.

To a 2000 ml flask equipped with a thermometer, stirrer and addition funnel, prepare a solution of 918 ml of water, 158.5 g (0.834 mol) of sodium pyrosulphite and 199.2 g (1.66 mol) of a mixture of di- and triethanolamine ( equivalent weight 120), is heated to 80 ° C and the acidic diethanolamide maleate prepared above is added via addition funnel over 0.3-0.5 hours with stirring. Stirring is continued for 0.3-0.5 hours.

This gives 1800 g of an aqueous solution of the final product - acylamido-N-hydroxyethyl-N-ethylenesulphosuccinic acid, triethanolamine-sodium double salt, having the general formula: 0? R1-C - N - CH2 - CH2 - O - C - CH2 - CH - COONH (CH2OH) 3 CH2CH2OH SO3Na where R is C - ^ - - CH2 - and the final product content of the solution is 27% by weight. The average molecular weight of the product is 695.

Dry matter content 46.5 V,

Conversion rate (final yield / original amide) 70.0 'i

Solubility in CCl 6.5% 4

Viscosity at 20 ° C 28 mPas

Density d2 ° 1.088 · 103 kg / m3 pH (10% solution) 6.90 ”84262

Example 3

Methyl esters of fatty acids are synthesized as described in e.g. 1.

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

295 g (1.00 mol) of distilled methyl esters of fatty acids (fraction II) which have been pretreated with diisopropanolamine are added to the flask, and the mixture is stirred for 2 hours at 80-82 ° C. The mixture is heated to 90 ° C under reduced pressure of 200 mm Hg and the methanol is distilled off. This gives 400 g of diisopropanolamide fatty acids with an average molecular weight of 396. The yield of the product is 92% of theory, calculated as the conversion rate of diisopropanolamine.

To 396 g of the diisopropanolamide thus obtained are added 127 g (1.3 mol) of maleic anhydride at 60 ° C and the resulting mixture is kept at this temperature for 2.5 hours to give 523 g of acidic diisopropanolamide maleate (acylamido-N-2- hydroxypropyl-n-propyleenimaleaatti). The sulfurization and neutralization of the acidic diisopropanolamide maleate is carried out as described in Example 1 by adding it to a solution of 1440 ml of water, 140 g (0.736 mol) of sodium pyrosulphite and 219 g (1.47 mol) of triethanolamine at 78-80 ° C, 2290 g of an aqueous solution of the triethanolamine sodium double salt of acylamido-N-2-hydroxypropyl-N-propylene sulphosuccinic acid having the formula: O CH-, 0

Il I 3 II

R - C - N - CH2 - CH - O - C - CH_ - CH - COONH (CH.OH) _ I 2 2 \ 2 4 3 CH2-CH-OH SO ^ Na ch3 where R is 0. C 18 g and the solution has a final product content of 24.6% by weight. The average molecular weight of the product is 747.

, 8 84262

Dry matter content 34.7%

Conversion rate (final product / original amide) 75.6%

Solubility in CCl 6.8%

Viscosity at 20 ° C 26.0 mPas

Density d2 ° 1.082 · 103 kg / m3 pH (10% solution) 6.82

Example 4

Methyl esters of fatty acids are synthesized as described in e.g. 1.

To a 500 ml flask equipped with a stirrer, distillation apparatus and thermometer is charged 110 g (1.465 mol) of N-methylethanolamine, 7.0 g of a 37.8% solution of sodium 2-aminoethoxylate in monoethanolamine and 265 g of g (0.898 mol) of distilled methyl esters of fatty acids (fraction II) which had been pretreated with N-methylethanolamine and the resulting mixture is stirred for 1.5 hours at 80-83 ° C. The methanol is distilled off at 200 mm Hg under reduced pressure at 90 ° C. Excess N-methylethanolamine is distilled off at a pressure of 10-15 mm Hg at 120-123 ° C to give 307 g of N-methylethanolamide with an average molecular weight of 338. The yield of the product is 95% of theory based on the conversion rate of N-methylethanolamine. To 306 g of the obtained N-methylethanolamides of fatty acids is added 110 g (1.122 mol) of maleic anhydride at 65 ° C, and the mixture is stirred at this temperature for 2 hours to give 416 g of acidic N-methylethanolamide maleate (acylamido-N-methyl-N-ethylene maleate).

The sulfurization and neutralization of the acidic N-methylethanolamide maleate is carried out as described in Example 1 by adding it at 70 ° C to a solution of 1356 ml of water, 107 g (0.563 mol) of sodium pyrosulphite and 168 g (1.126 mol) of triethanolamine to give 2045 g of acylamido-N -methyl-N-ethylenesulfonic succinic acid triethanolamine sodium double salt solution of the following formula:

H II

R - C - N - CH 2 - CH 2 - O - C - CH 2 - CH - COONH (C 2 OH) 3 CH 3 SO 3 Na '9 84262 wherein R is C The average molecular weight of the product is 689.

Dry matter content 31.5%

Conversion rate (final product / original amide) 82.0%

Solubility in CCl. 5.7% 4

Viscosity at 20 ° C 34.0 mPas 20 3 3

Density d ^ 1.094 · 10 kg / m pH (10% solution) 6.96

Example 5

Methyl esters of fatty acids are synthesized as described in Example 1.

A 500 ml flask equipped with a stirrer, distillation apparatus and thermometer is charged with 290 g (1.00 mol) of distilled fatty acid methyl esters (fraction I), 29 g (0.475 mol) of monoethanolamine and the work-up is continued as described in Example 1. .

72.5 g (1.187 mol) of monoethanolamine and 4.8 g of a 37.8% solution of sodium 2-aminoethoxylate in monoethanolamine are then added to the methyl esters of fatty acids. The temperature is raised to 90 ° C and stirring is continued at this temperature for 1.2 hours. Methanol and excess monoethanolamine are removed as described in Example 1 to give 322 g of monoethanolamide with an average molecular weight of 319. The yield of the product is 96% of theory based on the degree of conversion of monoethanolamine.

To 319 g of the monoethanolamide of fatty acids thus obtained is added 102 g (1.04 mol) of maleic anhydride at 80 ° C, and the resulting mixture is stirred at this temperature for 1.5 hours to give 421 g of acidic monoethanolamide maleate (acylamidoethylene maleate). Sulfurization and neutralization of the acidic monoethanolamide maleate is carried out as described in Example 1 by adding it at 70 ° C to a solution of 630 ml of water, 114 g (0.6 mol) of sodium pyrosulphite and 168 g of 25% ammonium hydroxide solution to give 1330 g of an aqueous solution of sodium ammonium double salt of acylamidoethylenesulphosuccinic acid having the formula:

0 O

li II

R - C - NH - CH '- CH-O-C-CH - CH - COONH.

2 2 2 | 4 SO 3 Na where R is C 1 -C 3, the final product content of the solution 3a is 32% by weight. The average molecular weight of the product obtained is 537.

Dry matter content 40.8%

Conversion rate (final product / original amide) 81.0%

Solubility in CCl 4 4.9%

Viscosity at 20 ° C 22.0 mPas 20 3 3

Density d ^ u 1.102 · 10 kg / m pH (10% solution) 6.95

Example 6

Methyl esters of fatty acids are synthesized as described in Example 1.

299 g (1.00 mol) of distilled fatty acid methyl esters (fraction III) and 20 g (0.327 mol) of monoethanolamine are placed in a 500 ml flask equipped with a stirrer, a distillation apparatus and a thermometer and the work-up is continued as described in Example 1. 90 g (1.473 mol) of monoethanolamine and 8.2 g of a 37.8% solution of sodium 2-aminoethoxylate in monoethanolamine are then added to the methyl esters of fatty acids and the resulting mixture is stirred at 90 ° C for 1.5 hours. Methanol and excess monoethanolamine are distilled off according to Example 1.

This gives 330 g of monoethanolamide of fatty acids with an average molecular weight of 328. The yield of the product is 95.5% of theory based on the conversion rate of monoethanolamine.

To 2184262 328 g of the obtained monoethanolamide of fatty acids are added at 83-85 ° C 121.4 g (1.238 mol) of maleic anhydride and the resulting mixture is stirred at this temperature for 2 hours to give 449 g of acidic monoethanolamide maleate (acylamidoethylene maleate). The sulfurization and neutralization of the acidic monoethanolamide maleate is carried out according to Example 1 by adding a solution of 970 ml of water, 158.3 g (0.712 mol) of potassium pyrosulphite and 149.5 g (1.424 mol) of diethanolamine at 90 ° C. 1720 g of an aqueous solution of the diethanolamine-potassium double salt of acylamidoethylenesulfosuccinic acid of the general formula are thus obtained: 0 0 0 .mu.l of R - C - NH - CH2 - CH2 - O - C - CH2 - CH - C0NH2 (C The product content of the C 1 -C 6 solution is 30.3% by weight. The final product thus obtained has an average molecular weight of 649.

Dry matter content 41.4%

Conversion rate (final product / original amide 80.5%

Solubility in CCl 4 4.2%

Viscosity at 20 ° C 20.0 mPas

Density d2 ° 1.089 · 103 kg / m3 pH (10% solution) 7.05

Example 7

The synthesis of fatty acid methyl esters is carried out according to Example 1.

To a 1000 ml flask equipped with a stirrer, distillation apparatus and thermometer are placed 161.0 g (1.0 mol) of di-butanolamine and 8 g of a 37.8% solution of sodium 2-aminoethoxylate in monoethanolamine. 295 g (1.00 mol) of distilled fatty acid methyl esters (fraction II), pretreated with dibutanolamine 11a, are then added and the mixture is stirred for 2 hours at 80 ° C. The mixture is heated to 90 [deg.] C. under reduced pressure (200 mm / l) and the methanol is distilled off to give 428 g of dibutanolamide of fatty acids 22,84262 with an average molecular weight of 424. The yield of the product is 88% of theory based on the degree of dibutanolamine conversion.

To 424 g of the dibutanolamide of fatty acids thus obtained is added 127.5 g (1.30 mol) of maleic anhydride at 75 ° C, and the resulting mixture is stirred for 3 hours at this temperature to give 551 g of acidic dibutanolamide maleate / acylamido-N- (1-methyl- 2-hydroxy) propyl N- (1,2-dimethyl) ethylene maleate.

Sulfurization and neutralization of the acidic dibutanolamide maleate is carried out according to Example 1 by adding it at 70 ° C to a solution of 1500 ml of water, 142 g (0.747 mol) of sodium pyrosulphite and 222 g (1.49 mol) of triethanolamine to give 2.412 g of acylamido An aqueous solution of N- (1-methyl-2-hydroxy) propyl-N- (1,2-diethyl) ethylenesulfosuccinic acid triethanolamine sodium double salt having the formula:

O CH CU O

Il I J I II

R-C-N-CH-CH-O-C - CH2 - CH - COONH (CH2OH) 3 CH-CH-CH-, SO3Na i i 3 3

CH30H

wherein R is C 1 -C 6 g, and the final product content of the solution is 24.1% by weight. The average molecular weight of the final product is 774.

Dry matter content 36.2%

Conversion rate (final product / original amide) 74.8%

Solubility in CCl 2 7.2%

Viscosity at 20 ° C 28 mPas

Density d ^ 1.062 · Ι03 kq / m3 pH (10% solution) 6.95

Example 8

The methyl esters of fatty acids are synthesized in Example 1 on the stage.

To a 500 ml flask equipped with a stirrer, distillation apparatus and thermometer add 116 g (1.30 mol) of N-23 84262 ethylethanolamine, 7.2 g of a 37.8% solution of sodium 2-aminoethoxylate in monoethanolamine and 295 g of (1.00 mol) of distilled fatty acid methyl esters (fraction II) pretreated with N-ethylethanolamine and stirred for 1.5 hours at 80 ° C. The methanol is distilled off under 200 mm Hg under reduced pressure at 90 ° C. The excess N-ethylethanolamine is distilled off under a reduced pressure of 10-15 mm Hg at 120-125 ° C to give 355 g of N-ethylethanolamide of fatty acids with an average molecular weight of 352. The yield of the product is 95% of the theoretical conversion of N-ethylethanolamine.

To 352 g of N-ethylethanolamide of fatty acids at 108 ° C is added 108 g (1.10 mol) of maleic anhydride and the mixture is stirred for 2 hours at this temperature to give 460 g of acidic N-ethylethanolamide maleate. The sulfurization and neutralization of the acidic N-ethylethanolamide maleate is carried out according to e.g. 1 by adding it at 70 ° C to a solution of 1400 ml of water, 120 g (0.63 mol) of sodium pyrosulphite and 77 g (1.26 mol) of monoethanolamine, whereby 2.052 g of an aqueous solution of the monoethanolamine sodium double salt of acylamido-N-ethyl-N-ethylenesulphosuccinic acid having the general formula: O 0? 1 'R - C - N - CH2 - CH2 - O - C - CH2 - CH - COONH2H2H CH2-CH3 SO3Na wherein R is having a final product content of 24.3% by weight.

The average molecular weight of the final product is 614.

Dry matter content 31.2%

Conversion rate (final product / original amide) 81.6%

Solubility in CCl4 5.9%

Viscosity at 20 ° C 32.0 mPas

Density d2 ^ 1.086 -10 ^ kg / m2 pH (10% solution) 7.02

Example 9

The methyl esters of fatty acids are synthesized as described in Example 1.

2454262 295 g (1.00 mol) of distilled fatty acid methyl esters (fraction II) and 15 g (0.246 mol) of monoethanolamine are placed in a 500 ml flask equipped with a stirrer, a distillation apparatus and a thermometer, and further work-up is carried out as described in Example 1. way.

To the methyl esters of fatty acids is added 80 g (1.310 mol) of monoethanolamine and the mixture is stirred at 80 ° C and then 5.6 g of a solution of 29% sodium methanolate in methanol are added as a catalyst. The reaction time is 1.2 hours. Methanol and excess methanol-amine are removed as described in Example 1.

This gives 325 g of monoethanolamide of fatty acids with an average molecular weight of 324. The yield of the product is 95.6% of theory, based on the degree of conversion of monoethanolamine. The other steps of the process are carried out according to e.g. 1, to give the product according to Example 1.

The quality characteristics of the products prepared in Examples 1-9 are shown in Tables 1-3.

Example 10

The foam bath mixture contains the following ingredients in% by weight:

Triethanolamine sodium double salt of acylamidoethylenesulphosuccinic acid 32

Scent 1.5

Water the rest

The properties of the foam bath mixture are shown in Table 4.

Example 11

Children's shampoo consists of the following ingredients in% by weight: 25 84262

Triethanolamine sodium double salt of acylamidoethylenesulphosuccinic acid 5

Scent 0.1

Water the rest

The properties of the children's shampoo are shown in Table 4.

Example 12

The hair shampoo consists of the following ingredients in% by weight: Acetamidoethylene sulfomeric resin triethanolamine sodium double salt 20

C8-C4-fatty acid diethanolamide 3.5

Ethanol 1/5

Sodium chloride 2.0

Scent 1/0

Water the rest

The properties of the hair shampoo are shown in Table 4.

Example 13

The hair shampoo consists of the following ingredients in% by weight: Acetamidoethylene sulfomeric resin triethanolamine sodium double salt 12

C 8 -C 18 diethanolamide 3.0

Ethanol 0.75

Sodium chloride 3.5

Scent 0.75

Water the rest

The properties of the shampoo are shown in Table 4.

26 84262

table 1

Ross-Miles pouring foam numbers at 40 ° C when the concentration of the compound of the invention is 0.25% by weight.

Eg Acylamidoalkylene- Cations Distilled water Foam No. (or acylamido-N- ",.... Stability hydroxyalkyl-N-foam column corkylene) sulfonylene, nm-resin acid amine-Hq alkali double salts _ _0 s 60 s 300 s_ 1 2 3 4 5 6 7 1 * 1 ^ 15 ^ 19 Na / TEA + 195 180 175 ° '97 R2 = hydrogen 50% R3 = -ch2-ch2- dea 2 ^ 15 ^ 19 Na / TEA + 185 170-16 ° '98 Rf = -CH.OH 66%

1 Δ 4 DEA

V -ch2-ch2- 3 ^ ^ 15 ^ 19 Na / TEA 187 173 168 0.97 R- = -CH „-CH-OHH 2, CH3 r3 = -CH2-CH- ch3 4 ^^ 15 ^ 19 Na / TEA 196 183 177 0.97 v - ° ¾ R3 = -CH2-CH2- 5 R1 = C9-C17 R2- hydrogen Na / NH4 183 170 166 0.98 V ^ H2 ^ H2-

Table 1 (continued)

Ross-Miles pouring foam values at 40 ° C at a concentration of 0.25% by weight of a compound of the invention 84262

Hard water (5.35 mg equivalent / l) ττ,,,

Height of the foam column, mm bisability HH, Hc H5 // Hl oi 5 _0 s_60 s_300 s_ _L_8_9_10___11____ 1 205 186 180 0.97 2 190 175 168 0.96 3 193 177 170 0.96 4 202 186 180 0.97 5 190 177 172 0.97 28 84262

Table 1 (continued) 1_2_3_4_5_6_7_ 6 R1 = C17-C21 K / DEA 180 167 160 0.96 R2 = hydrogen V -ch2-ch2- 7 R, = Clc-C Na / TEA 182 167 163 0.98 1 15 19 R -, = -CH-CH-CH- 2 1 I 3 CH3 oh R -, = -CH-CH-

3 I I

ch3 ch3 8 R1 = C15-C19 Na / MEA 192 180 172 0.96 r2 = -ch2-ch3 r3 = -ch2-ch2-

Table 1 (continued) 1_8_9_10_11_ 6 185 170 165 0.97 7 188 173 165 0.95 8 200 185 180 0.97

Whore: TEA - triethanolamine; DEA - diethanolamine; MEA - monoethanolamine 29 84262

Table 2

Washing test for dirty standard wool garments when the concentration of the compound of the invention is 0.25% by weight.

Example Acylamido alkali metal double salt of acylamidoalkylene (or acylamido-N-cations No. hydroxyalkyl-N-alkylene) sulfosuccinic acid 1-2_ 3 1 R = Clt, -C10, R = hydrogen; Rf = -CH9-CH2 - Na / 50% TEA +

1 Z J i 50% DEA

2 R 1 = C, C-C, n; R "= -CoH.0H, R- = -CH" -CHO- Na / 34% TEA +

1 15 19 2 2 4 3 22 66% DEA

3 R1 = C15-C19 'R2 = -CH2-ch-OH; R3 ~ -CH2-CH- Na / TEA

ch3 ch3

4 R1 = ci5 ~ cig, R2 = -CH3, R3 = -CH2-CH2- Na / TEA

R 1 = c 6 -C 17, R 2 = hydrogen, R 3 - CH 2 -CH 2 -Na / NH 4

6 R1 = C17 ~ C21 'R2 = hydrogen' R3 ~ _CH2 "CH2- K / DEA

7 R = Clr-Cln, R = -CH-CH-CH2, R = -CH-CH- Ma / TEA

i 15 19 2 f) 3 3, | CH3OH CH3CH3

8 R = C, c-C, n, R "= -CH_-CH", R = -CH "-CH" - Na / MEA

115 19 2 2 3 3 2 9 Sodium dodecyl sulphate Na

Note: TEA - triethanolamine; DEA - diethanolamine; MEA - monoethanolamine 30 84262

Table 2 (continued)

Cleaning power Whitening _preservation_ 1 4 5 1 95 98 2 96 98 3 96 98 4 94 98 5 90 98 6 92 98 7 95 9 7 8 96 98

Note: TEA - triethanolamine; DEA - diethanolamine; MEA - monoethanolamine 31 84262

Table 3

Surface tension determined by the stalagmometric method (N / m x 10) at 20 ° C when the concentration of the aqueous solution of the compound of the invention is 0.1% by weight

For example, the amine alkali metal double salt of acylamidoalkylene (or acylamido-N-cations No. hydroxyalkyl-N-alkylene) sulfosuccinic acid 1 R. = C. r - C. n, R = hydrogen, R0 = -CH "-CH" - Na / 50% TEA +

1 15 19 2 322 5Q% DEA

2 R1 "C15" C19 'R2 ~ -C2H4OH' r3 = "CH" CH - Na / 34% TEA +

66% DEA

3 R1-C15-C18, R2 = -CH2-CH-OH, R3 = -CH2-CH- Na / TEA

ch3 ch3

4 R 1 = C 15 -C 19 / r 2 = -CH 3, R 3 = -CH 2 -CH 2 - Na / TEA

5 R1 = C9-C17 'R2 = hydrogen' R3 = -CH2 ~ CH2 ~ Na / NH4

6 R1 = C17-C21 'R2 ~ hydrogen' r3 = -CH2-CH2- K / DEA

7 R1 = C15_C19 'R2 = -CH-CH-CH3, R3 = -CH-CH- Na / TEA

ch3oh ch3ch3

8 R1 = C15-C19 'R2 = -CH2_CH3' R3 = ~ CF2_CH2- Na / MEA

Note: TEA - triethanolamine, DEA - diethanolamine, MEA - monoethanolamine 84262

Table 3 (continued)

Distilled Hard water (5.35 mg equivalent / l) 14 5 1 30.0 31.3 2 28.4 29.2 3 28.1 28.5 4 30.2 30.8 5 30.4 31.6 6 30.6 30.8 7 28.2 29.0 8 29.8 30.9 33 84262

Table 4 No. Properties of washing compositions Examples No. _10 11_12_13 1 2 3 4 5 6

Foam numbers H 205 201 198 196 o 1 0.25% solution of a compound of the invention 184 174 176 at 40 ° C, Ross-1

According to Miles, among others; B,. 180 178 171 173 2 Foam stability 0.97 0.97 0.98 0.98 3 Turbidity point, ° C; -2-5 1-2 2-3 -1-1 4 Degreasing effect compared to sodium lauryl sulfate; 56.3 51.5 54.2 54.0 Viscosity at 20 ° C, mPas; 32.0 3.0 1200.0 430.0 6 Density at 20 ° C, 103 ka / m3; 1,098 1,008 1,072 1,063 7 pH of a 10% aqueous solution of a compound of the invention 6.80 6.85 6.75 6.85

Claims (7)

34 84262 Surfactant compositions for use in cosmetic products and detergents, characterized in that they contain amine or ammonium alkali metal double salts of acylamidoalkylene (or acylamido-N-hydroxyalkyl-N-alkylene) sulphosuccinic acid with the general formula: CC> 2 - R4 ++ Ri -CN-Rq-OC-CHo - CH MeN-Rc II IIO R2 O SO3 H Rg wherein R1 is a straight chain C8-C21 hydrocarbon group derived from fatty acids and glycerides from the fatty effluent of fish processing plants, which the broth has an acid number of up to 50 mg KOH / g, a saponification number of 181-192 mg KOH / g and a bromine number of 60-70 g Br / 100 g, R 2 is hydrogen, -CH 3, -CH 2 -CH 3, -CH 2 -CH 2 -OH; -CHo-CH-OH or -CH-CH-CHq; I II ch3 ch3oh R3 is -CH2-CH2-, -CH2-CH or -CH-CH-; CH 3 CH 3 CH 3 R 4, r 5 3a r 6 may be the same or different and are each hydrogen and / or -CH 2 -CH 2 -OH; Me = Na or K. Process for the preparation of surfactant mixtures according to Claim 1, characterized in that the fatty waste liquors from fish processing plants, which contain fatty acids and glycerides and have an acid number of at most 50 mg KOH / g, a saponification number of 181-192 mg KOH / g and a bromine number of 60 to 70 g Br / 100 g, treated at reflux with methanol in the presence of sulfuric acid to give a reaction mixture from which a fat layer containing glycerides and methyl esters of fatty acids is separated and treated with methanol in the presence of sulfuric acid at 50 to 60 ° C to give a reaction mass from which the anhydrous fat layer is separated and treated with methanol in the presence of alkali at the boiling point of methanol to give a reaction mixture containing fatty acid methyl esters which are separated and treated with alkylolamine using 25-55% by weight of fatty acid methyl esters. läsnäolless a, which may be an alkali metal or an amide or alcoholate thereof at 70-90 ° C to give alkylolamides of fatty acids, which is treated with maleic anhydride at 60-90 ° C to give maleates of alkylolamides of fatty acids, followed by treatment at 60-90 ° C in aqueous medium with sodium or potassium pyrosulfite and ethanolamine or ammonia to give the desired product. Process according to Claim 2, characterized in that, in order to improve the quality of the final product, the fatty acid methyl esters are pretreated with alkylolamine and only then the alkylolamine treatment is carried out in the presence of said catalyst. ° C and then the excess alkylolamine is removed. Process according to Claims 2 to 3, characterized in that sodium 2-aminoethoxylate is used as catalyst for simplifying the process. Process according to Claims 2 to 4, characterized in that mono-, di- and / or triethanolamine is used as the ethanolamine. The use of the surfactant compositions according to claim 1 in a cleaning agent together with perfumes, water 36 84262 and other additives such that the composition of the cleaning agent, expressed as a percentage by weight: acylamidoethylene sulfosuccinic acid triethanolamine and sodium double salt 5.0-32.0 perfume 0.1-1, 5 water remaining. Use according to claim 6, wherein the composition of the detergent, expressed as a percentage by weight, is: triethanolamine and sodium double salt of acylamidoethylenesulfosuccinic acid 12.0-20.0 Cg-Ciy fatty acid diethanolamide 0.5-3.5 sodium chloride 1.0-3.5 ethanol 0 , 3-1.5 perfume 0.1-1.5 water the rest.