FR2558157A1 - DOUBLE SALTS OF ALKALINE METAL AND AMINO ACYLAMIDOALCOYLENESULFOSUCCINIC ACIDS, PROCESS FOR THEIR PREPARATION AND THEIR APPLICATIONS - Google Patents

Abstract

NEW TENSIO-ACTIVE DERIVATIVES RESPONDING TO THE GENERAL FORMULA: (CF DRAWING IN BOPI) R BEING A HYDROCARBON RADICAL IN C-C; R BEING H, ALKYL OR HYDROXYALCOYL; R BEING AN ALCOYLENE; R, R, R BEING H ETOU -CH-CH-OH; AND I AM NA OR K. THE PROCESS FOR THE PREPARATION OF THE COMPOUNDS CONSISTS OF TREATING THE WASTE WATER FROM INDUSTRIAL FISH FARMERS. APPLICATION IN HOUSEHOLD PRODUCTS.

Description

The present invention relates to surfactants

  assets and relates more specifically to new compounds

  calves: double salts of an amine and an alkali metal of

  acylamidoalkylenec (or acylamido-N-hydroxyalkyl) -N-

  alkoyl) sulfosuccinic acid, process for their preparation and

  their applications, as detergents.

  The aforementioned compounds find applications as anionic surfactant derivatives which are used for the manufacture of household chemicals, in particular for the preparation of cosmetic products, for example foaming detergent shampoos for

  baths, soaps, stabilizers used for

  cosmetics, as well as compositions for cleaning carpets, for washing woolen fabrics, particularly in cold water, and in the photography and cinematography industry as agents.

  wetting agents when applying the photosensitive emulsions

films.

  The cosmetic surfactants used

  currently have to show strong

  high stability of foam in aqueous solutions.

  its, a good solubility in cold hard water; they

  must show good skin tolerance and good

  moderate degreasing and biodegradability

easy.

  Surface-active derivatives of the disodium salt type of acylamidoethylenesulphosuccinic acid are known.

  obtained from the cotton soapstock in the oil-

  (Uzbekski khimnitskiy journal Akademii naouk Uzbek-

  skoi sevetskoï sotsialisticheskoi respubliki, N 3, pp. 52-54, 1975) which may be represented by the following formula: ## STR2 ##

2558157,

  in which R is a C7-C17 hydrocarbon radical.

  However, these compounds are characterized by insufficient solubility in cold water and can be obtained from them only pasta-shaped detergents poorly suited for use in cold washing. Surfactants derived from coconut oil, palm oil and other vegetable oils are also known (FRP patent).

  N 2 408 895) as well as starting from synthetic fatty acids

  ticks (Uzbekski khimitcheski newspaper Akademii naouk Uzbekistan sovetskol sotsialisticheskoi respubliki,

No. 3, pp. 52-54, 1975).

  When implemented as primary materials

  some vegetable oils, synthetic fatty acids

  animal fats containing saturated carbon chains

  With a length of more than 15 carbon atoms, surface-active derivatives which are poorly soluble in cold water are obtained.

  lower detergency indices. The surfactants

  Active ingredients based on these raw materials are unlikely to be used for cosmetic purposes. Moreover,

  surfactant derivatives of this type, made from

  fats with a number of carbon atoms not exceeding 14,

  have excessive degreasing effects.

  It was therefore proposed to create surfactants

  new active ingredients possessing a high foaming power and a high stability of foam, a high solubility in cold water, a good skin tolerance obtained by recovery of soapstccks (disintegration pastes) from the industrial fishmonger. The claimed substances are new and

  have not been described in the literature.

  According to the invention, the novel compounds are double salts of an alkali metal and an amine of acids

  acylamidoalkylene (or acylamido-N-hydroxyalkyl-N-alkyl)

  ne) sulfosuccinic compounds having the general formula:

C 2 4 R41 +

I i I / -

  R1 -C-N-R3-O-C-CH2-CH MeN-R5 [uI n i [\ Rj

O R2 O SH3R6

  R1 being a C9-C21 hydrocarbon radical of linear structure, R2 being hydrogen or a group - CH3, - CH2 - CH3, - CH2 - CH2 - OH, - CH2 CH - Og or - CH - CH - CH3 , I i I

CH3 CH3 OH

  R3 being - CH2 - CH2 -, - CH2 - CH - or - CH - CH -

f I I

CH3 CH3 CH3

  R4, R5, R6 being hydrogen and / or - CH2 - CH2 - OH; and Me being Na or K. The claimed new compounds are

  pasty, entirely soluble in cold water (their solution

  40% is clear and fluid at 200C,

  it does not become cloudy during storage. Said components

  its are very heat resistant. In addition, these compounds

  have a good skin tolerance and are easily

to biodegradation.

  The constitution of the claimed compounds is

  confirmed by the results of infrared spectroscopy. The characteristic bands of the following functional groups are observed in the spectra: alkyl radical 725-720 cm-1 groups CH3-, -CH2- 2960, 29402910, 2870 cm1 group -CO-NH-1680-1630, 1570-1515 cm

O

Ii -

Grouping -C-O- 1750-1735 cm1

C0O ion 1610-1550, 1450-1500 cm-

2 -1

  grouping -OH 3500-3250, 1050-1030 cm

  grouping -S02-0- 1420-1330, 1200-1145 cm-

-1 ion -NH4 3300.-3030 cm

2558157,

  The existence of the double charge of the anion in

  the claimed compounds is confirmed by the method of

  cationic age in aqueous-alcoholic solution.

  The density of the aqueous solutions of said compounds when their concentration is 24 to 32% by

  mass is between 1,0620 and 1,1020 kg / m3 at a time

  20 C temperature; the dynamic viscosity of said solutions

  at a temperature of 20 C is between 20 and 34 mPa.s.

  The claimed substances have the properties of

surfactant derivatives.

  The foaming power of these compounds determined by the method of RossMiles at the temperature of 40 C and their

  mass concentration of 0.25% is characterized by the

  initial column of the foam column in distilled water 180--196 mm and a foam stability of 0.96-0.98; in hard water with a concentration of calcium and magnesium salts of 5.35 milligrams / liter, the initial height of the foam column is

  -205 mm while the foam stability is 0.95-

0.97.

  The detergency of the new compounds was determined by the standardized method (see F. V. Névoline, La

  chemistry and synthetic detergent technology. Edi-

  Pistchevala promychlennost, Moscow, 1971, pp. 405-

  415, in Russian). When the concentration of these compounds is 0.25% by weight, their detergency is 90 to 96. The surface tension of the aqueous solutions of the claimed compounds was determined by the method.

  stalagmometrically at a temperature of 200C and at a concentration

  solutions in these compounds of 0.1% by weight.

  It is equal to (28.1 to 31.6.10-3) N / m.

  According to the invention, the process for the preparation of the new claimed compounds consists in treating the

  residues (wastes) from fish waste water

  industrial products containing fatty acids and glycerides with an acid number not exceeding 50 mg of KOH / g,

  with a saponification number of 181-192 mg KOH / g and

  bromine dice of 60-70 mg Br / 100 g, with methanol in the presence of sulfuric acid to boiling, to obtain a reaction mixture from which the fatty layer composed of glycerides and methyl esters (methylates) is separated off )

  fatty acids; said fat layer is treated with

  thanol in the presence of sulfuric acid at a temperature of 50-60 ° C to obtain a reaction mass from which an anhydrous fatty layer is separated which is treated with

  methanol in the presence of an alkali at the boiling point

  The methanol is obtained by obtaining a reaction mixture containing methyl esters (methylates) of fatty acids which are isolated and treated with an aolaydismin taken at a rate of 25-55% by weight of the amount of methyl esters of fatty acids in the presence of a catalyst chosen from

  group comprising an alkali metal or its amide or a

  coolate at a temperature of 70 to 9o00C with

  coylolanides of fatty acids which are treated with maleic anhydride at the temperature of 60-90OC thereby obtaining maleinololamides of malinates of fatty acids which are then treated with sodium or potassium pyrosulfite and by ethanolamine or by ammonia at room temperature

  60-90 ° C. in an aqueous medium and the finished product is isolated.

  In order to improve the quality of the finished product, before applying the treatment indicated by the alkylamine,

  the methyl esters of the fatty acids b are treated with

  beforehand in the presence of said catalyst by the alkyl

  olamine taken at 5 to 10% by weight of the methyl esters

  thylics of fatty acids at a temperature of 70 to 90oC with

  subsequent removal of spent alkylolamine.

  As alkylolamine, it is recommended to use

  monoethanolamine, diethanolamine, N-methyl

  ethanolamine, N-ethylethanolamine, dibutanolamine,

diisopropanolamine.

  In order to simplify the process technology at the amidation stage of the fatty acid methyl esters,

  it is advantageous to use as the catalyst the amino-2-

sodium ethoxylate.

  As ethanolamine, it is recommended to use

  use mono-, di- and / or triethanolamine.

  The claimed method of the apparatus is

next.

  Fat residues (wastes) are treated in waste water from industrial fish farms containing fatty acids and glycerides, with an acid number not exceeding 50 mg KOH / g, a saponification value of 181 to 192 mg KOH / g, a bromine number of 60 to 70 mg

  bromine / 100 g, with methanol in the presence of sulfuric acid

  as a catalyst. Then the esterification takes place

  acid cation of free fatty acids that are contained in the waste residues (waste) of waste water. We drive

  the esterification reaction by stirring the reaction mixture

  at the boiling point of methanol for 1.5 to 2.5 hours. After the reaction is complete, the mixture is allowed to settle, the upper layer (methanol) is separated and is directed to regeneration while the lower layer, which is a mixture of fatty substances, is treated with methanol in the presence of sulfuric acid. at a temperature of 50 to 60 C. After the

  demixing, the upper layer (methanol from

  traction) and is directed at the beginning of the technological cycle for esterification of fatty free fatty acids from waste residues (waste) in wastewater. The lower layer, which is a mixture of purified fatty substances, is directed to the

  alkaline transesterification of glycerides.

  For this purpose, the purified fatty substance mixture is treated with methanol in the presence of an alkali. We are beating

  the mixture at the boiling point of the methanolic

  0.25 h after which it is cooled to room temperature

2558157,

  At room temperature, it is demixed for 1.5 to 2.0 hours and the layers are separated. We direct the lower layer,

  glycerin and methanol to the recovery of methanol.

  The top layer of methyl esters of fatty acids is washed with hot water acidified with hydrochloric acid and dried. We recover the methanol contained in the waters of

  washing. The dried methyl esters are distilled

  vacuum fractionation at a temperature of 155 to 215oC

  and under a residual pressure of 10 to 20 mmHg.

  The target fraction is 78 to 83% calculated on the fat content of the waste residues (waste) in waste water. The purified methyl esters of the fatty acids are treated with an alkylolamine taken in a proportion of 25 to 100% by mass of the amount of the methyl esters of the acids.

  at a temperature of 70 to 900C in the presence of a cat-

  lyser by which an alkali metal or

his amides or alcoholates.

  Alkylolamides of fatty acids are obtained.

  In order to simplify process technology,

  uses as the catalyst the amino-2-ethoxylate of

dium.

  As alkylolamine, monoethanol is used.

  nolamine, diethanolamine, diisopropanolamine, N-

  methylethanolamine, etc. In order to improve the quality of the finished product, the methyl esters of the fatty acids are subjected before said

  treatment with an alkylolamine in the presence of said

  prior treatment with alkylolamine

  at a rate of 5 to 10% by weight of the mass of the methyl esters

  fatty acids (methylates) at a temperature of 70 to

   C with subsequent settling and removal of the alkyl

  used olamine. The yield of alkylololamides of fatty acids calculated in degree (rate) of conversion of alkylolamines is

  figure by 93 to 98 X of the theoretical output.

  The alkylamolamides obtained are stirred with

2558157 7

  maleic anhydride taken from 30 to 37% by weight of the alkylolamide at a temperature of 60 to 900C and during

  1.5 to 3.5 hours. The yield calculated in degree (rate) of conversion

  maleic anhydride is equal to the theoretical yield.

  The alkylololamide maleainates obtained are treated with sodium or potassium pyrosulphite and with ethanolamine or ammonia at a temperature of 60 to 900.degree.

in an aqueous medium.

  In this way the finished product is obtained.

  The finished product yield is 70 to 82% cal-

  based on alkylololamide.

  The claimed process makes it possible to valorise the soapstocks of the industrial fishmonger and to replace

  in this way the fats and oils onion food

  as well as synthetic raw materials of origin

  oil, which are currently being implemented to

  the preparation of surfactant derivatives. In addition,

  environmental pollution and reduce the costs of

  purification of manufacturing residues. The process is sim-

  from the point of view of industrialization and does not require the use of special equipment. The soapstocks that are used in the claimed process had not been valued until now for fine organic synthesis at

  because of their degree of excessive pollution. Thanks to the opera-

  the above-mentioned technological processes, the claimed process makes it possible to obtain, from the raw materials mentioned, high quality finished products on the basis of which detergents without special adjuvants have been created,

  improve skin tolerance and detergency effect. We are

  also sells the applications of the said novel compounds

  calves claimed as a basis for detergents. It is preferable

  the use of the triethylamine and sodium salt of acylamidoethylenesulphosuccinic acid. The

  detergent which comprises a surfactant derivative, a substance

  this aromatic and the water according to the invention contains as surfactant derivative a double salt of triethanolamine and

  acylamidoethylenesulfosuccinear acid sodium

following mule:

O O

He l

  R - C - NH - CH2 - CH2 - O - C - CH2 - CH - C (, OONH (C2H4OH) 3

  SO3Na R representing a linear hydrocarbon radical C15-C19, for the following proportions of said components,% by weight: triethanolamine double salt

and acylamido acid sodium

  Ethylenesulfosuccinic 5,0 to 32,0

aromatic substance 0,1 1,5 -

water the complement to 100

  The preferred version of detergent is a

  which also contains the diethanolamide of C9-C17 fatty acids, the sodium chloride and the ethyl alcohol have the following proportions of the constituents taken in% by weight: double salt of triethanolamine

and acylamido acid sodium

  ethylenesulphosuccinic 12.0 to 20.0 diethenolamide of C9C17 fatty acids 0.5 to 3.5 sodium chloride 1.0 to 3.5 ethyl alcohol 0.3 to 1.5 aromatics 0.1 to 1.5 water the complement to 100

  The claimed detergent, compared to

  known tergents, does not require the use of adjuvants that reduce the effect of degreasing. This product manifest

  high solubility in cold water lasts, a strong

  see foaming and easily removed by washing.

  In addition, the detergent shows good

2558 1 57

  skin tolerance and lends itself easily to. biological degradation.

  Other features and advantages of the

  will be better understood by reading the description

examples of implementation.

Example 1

  500 g capacity of a flask equipped with a reflux condenser and a thermometer, 250 g

  of residues (waste) of fish waste water

  (acid value 24 mg KOH / g, saponification number 187 mg KOH / g, bromine index 66.2 mg bromine / 100 g density d4 = 0.914 kg / m3, freezing temperature 13.8 C ) and 63 g of acidified methanol with 1.3 g (0.0125 mol) of concentrated sulfuric acid. The mixture is boiled during

  1.5 h. during this time, the fatty acids are esterified.

  The reaction mixture is left standing for 0:25 h,

  the upper layer (the layer of methanol, while

  the lower layer which consists of glycerides and es-

  methyl esters of fatty acids undergoes treatment at a temperature of 58 to 600C with 47.5 g of acidified methanol

  with 0.09 g (0.00086 mol) of concentrated sulfuric acid.

  After decantation for 0.25 h, the mixture is separated. The upper layer (methanol extraction) is recycled at

  initial stage of esterification of fatty acids.

  The bottom layer (245 g) was placed in a 500 ml capacity flask equipped with a reflux condenser, stirrer and thermometer and 1.66 g (0.0415 mol) added thereto. of caustic soda in 35.6 g (1,113

  mole) of methanol. The mixture is stirred at the boiling point

  methanol for 0.25 hours and the trans-

  alkaline esterification of the glycerides, then

  colder up to the temperature of 20 C.

  reaction mixture for 0.5 h, then the

  glycerine-methanol (lower layer). The top layer of the fatty acid methyl esters is washed

2558 1 5? 7

  water acidulated with hydrochloric acid (0.43% by weight) and distilled at a temperature of 155 to 2150C (15

  mm Hg) by taking three fractions.

  The first fraction 155-193 C (acid number 2.51 mg KOH / g, saponification number 192 mg KOH / g, bromine number 52 mg Br / 100 g density d420 0.878 kg / m3

  freezing point 30 C, average molecular weight 290.0).

  The second fraction 193-202 <'C (acid number 1.57 mg KOH / g, saponification number 189 mg KOH / g, bromine number 71 rng Br 100 g density d20,870 kg / m3, freezing point 9.3 C, average molecular weight

295.0).

  The third fraction 202-215 C (acid number 1.32 μg KOH / g, saponification number 186 mg of OR / g, bromine number 68 mg Br / 100 g density 0.867 ka / m3, point freezing 15.2 C, average molecular weight

299, O)

  A 500-ml flask equipped with a stirrer, a distillation nozzle and a thermometer is placed in a 295 g (1.00 mole) distilled fatty acid methyl ester (second fraction). and 30 g (0.491 moles) of monoethanolamine. The mixture is stirred at a temperature of

  at 72 ° C. for 0.25-0.3 h, then the stirring is stopped.

  After 0.25 - 0.3 h of decantation, the bottom layer which has become darker with monoethanolamine is pipetted off. 80 g (1.310 moles) of monoethanolamine are added to the flask and the mixture is stirred at a temperature of 800 ° C. Then 6.6 g of a 37.8% solution is added

  of catalyst (sodium amino-2-ethoxylate in the mono-

  étharolamine). The reaction time is 1.2 h. The system is depressurized to a residual pressure of 200 mmHg, the mixture is heated to 90.degree.

  distilling the methanol. Excess monoethanol is removed

  under a residual pressure of 20 to 25 mmHg and

  at a temperature of the liquid mixture subjected to distillation

not exceeding 125 C.

  328 g of an acid monoethanolamide are obtained

* fat with an average molecular weight of 324.

  Calculated from the conversion rate of the mono-

  ethanolamine, the yield is 96% of the theoretical yield. Place in a 1000 ml capacity flask

  equipped with a thermometer and an agitator, 324 g of monoethane

  nolamide of fatty acids obtained. It is brought to a temperature of 70 ° C. and with stirring for 0.25 to 0.5 h, 108 g (1.10 mol) of maleic anhydride are added. Under these conditions, the mixture is stirred for 1.5 h.

  432 g of monoethane acid maleate are obtained.

  nolamide (acylamidoethylenemaléinate).

  A solution consisting of 956 ml of water, 122 g (0.642 mole) of sodium pyrosulfite and a solution containing a thermometer, a stirrer and a measuring device are prepared in a 2000 ml flask. 163 g (1.284 moles) of a mixture

  di- and triethanolamine with an equivalent weight of 127.

  The solution is brought to 60 ° C. and poured at this temperature

  for 0.3 to 0.5 h by the metered dose monoethane maleate

  nolamine acid which had been obtained by sulfonation and neutralization of the latter. Brewing is continued for a further 0.3 - 0.5 h. 1670 g of an aqueous solution of finished product is obtained which is the double salt of trietharolamine and sodium of acylaminoethylenesulfosuccinic acid of following form:

O O

He He

  R - C - NH - = CH2 - CH2 - O - C - CH2 - CH - COONH (C2H40H) 3

I

  SO3Na R being a C15-C19 linear hydrocarbon radical with

  a finished product content of 31.2% by weight.

  The average molecular weight of the finished product is

of 650.

  dry matter 40.2% conversion (finished product / starting amide) 82.0 X solubility in CCl4 4.5% Viscosity at 20 C 32.0 mPa.s Density d40 1.098 kg / m3 pH (10 X solution) 6 85

Example 2

  The methyl esters are synthesized

  (methylates) of fatty acids in a manner similar to that

described in Example 1.

  Place in a 500 ml capacity flask

  equipped with an agitator, a nozzle (a tubing) for

  and a thermometer, 295 g (1.00 mole) of fatty acid distilled methyl esters (second fraction),

  (0.285 moles) of diethanolamine and the treatment is carried out.

  In a manner similar to that described in Example 1, 110 g (1.05 moles) of diethanolamine and 7.3 g of a 37% strength solution were then added to the fatty acid methyl esters. 8X of sodium amino-2-ethoxylate in monoethanolamine, the mixture is stirred at a temperature of 70C until a homogeneous solution is obtained. The reaction time is 2 hours. The system is depressurized to a residual pressure of 200 mmHg, the mixture is heated to 90.degree. C. and the methanol is distilled off. 383 g of fatty acid dietharolamide having an average molecular weight of 369 are obtained.

  the degree of conversion of diethanolamine, the

  is 87% of the theoretical return.

  Place in a 500 ml capacity flask

  equipped with a thermometer and stirrer 383 g of diethanol-

  amide obtained, the mixture is brought to 600C and 142 g (1.45 mol) of maleic anhydride are added portionwise during 0.5 h while stirring. The solution is stirred at 650 ° C. for 3.5 hours and left at room temperature for 12 hours.

2558157,

hours.

  525 g of diethanol maleate are obtained.

  amide (acylamido-N-hydroxyethyl-N-ethylenemaléinate).

  A 2000 ml capacity flask equipped with a thermometer, a stirrer and a doser, a solution of 918 ml of water, 158.5 g (0.834 moles) of sodium pyrosulfite is prepared in a flask. and 199.2 g (1.66 moles) of a mixture of di- and triethanolamine with an equivalent weight of 120, is brought to 80 ° C. and introduced into it for 0.3 to 0.5 hours.

  by the agitated doser the acid maleate of diethanol

  obtained nolamide. Brewing continues for another 0.3

at 0.5 hours.

  1800 g of aqueous solution of finished product are obtained: double salt of triethanolamine and sodium of acid

  acylamido-N-hydroxy-ethyl-N-ethylene sulfosuccinic acid

to the following formula:

O O

He He

  R - C CH2 - CH2 0 - C - CH2 - CH - COONH (C2H4OH) 3

2 CH 20H S03Na

  R being a C15-C19 linear hydrocarbon radical, with

  in finished product of 27% by weight. Molecular weight

average of finished product 695.

  dry matter 46.3% conversion (finished product / starting amide) 70.0% solubility in CC14 6.5% viscosity at 200C 28.0 mPa.s density d20 1.088 kg / m3 pH (10% solution) 6, 90

Example 3

  The methyl esters (methylates) of the fatty acids are synthesized in a manner analogous to that

  which has been described in Example 1.

  A flask of 500 ml capacity equipped with a stirrer, a distillation nozzle and a thermometer was charged with 133 g (1.00 mole) of diisopropanolamine, 7.5 g of , 8% of sodium amino-2-ethoxylate in

monoethanolamine.

  295 g (1.00 mol) of fatty acid methyl esters pretreated with diisopropanolamine and distilled (second fraction) are added to the flask and the mixture is stirred at a temperature of 80-82 ° C. for 2 hours. The system is depressurized to the residual pressure of 200 mmHg, the mixture is heated to 90 ° C. and the mixture is heated.

  methanol by distillation. 400 g of diisopropanol are obtained.

  fatty acid glamid with an average molecular weight of 396. Based on the average degree (rate) of conversion of diisopropanolamine, the yield is 92% of the yield.

theoretical.

  To 396 g of diisopropanolamide obtained at a temperature of 60 ° C., 127 g (1.3 moles) of maleic anhydride is added and maintained at the thermostat at this temperature for

  2.5 hours. 523 g of diisopropanol maleate are obtained.

  panolamide (acylamido-N-hydroxy-2-propyl-N-propylenemalein

  you). The sulfonation and neutralization of the

  diisopropanolamide acid ester in a manner analogous to that described in Example 1 by its determination in a solution containing 1440 ml of water, 140 g (0 736 mol)

  of sodium pyrosulphite and 23.9 g (1.47 mole) of triethanolamine at a temperature of 78-80 ° C.

  aqueous solution of triethanolamine and sodium salt

  Acylamido-N-hydroxy-2-propyl-N-propylenesulfonic acid dium

  succinic formula corresponding to the following formula:

O CH3 O

He I1l

  R - C - N - CH2 - CH - O - C - CH2 - CH - COONH (C2H40H) 3

2 I

CH2-CH-OH SO3Na CH3

2558157.

  in which R is a linear hydrocarbon radical in

  C15-C19 with a finished product content of 24.6% by weight.

  Average molecular weight of finished product 747.

  dry matter 34.7 X conversion (finished product / starting amide) 75.6% solubility in CCl4 6.8 X viscosity at 20 C 26.0 mPa.s density d20 1.082 kg / m3 pH of the 10% solution 6 82

Example 4

  The methyl esters (methylates) of fatty acids are synthesized in a manner analogous to that

  which has been described in Example 1.

  500 g (1.465 mole) of methylethanolamine, 7.0 g of a 37 solution are placed in a 500 ml capacity flask equipped with a stirrer, a distillation nozzle and a thermometer. 8% sodium amino-2-ethoxylate in

  monomethanolamine and 265 g (0.898 mole) of methyl esters

  distilled liquids previously treated with methylethanol-

  fatty acid amine (second fraction) and stirred at a temperature of 80-83 C for 1.5 hours. Then, the methanol is distilled off from the reaction mixture under a vacuum of 200 mm Hg (pressure

  residual) and at a temperature of 90 ° C.

  tillation the excess of N-methylethanolamine under pressure

  residual of 10-15 mm Hg and at a temperature of

  123 C and 307 g of N-methylethanolamide of acids are obtained.

  average molecular weight of 338. According to

  According to the (conversion) rate of N-methylethanolamine, the yield is 95% of the theoretical yield. We add to

  306 g of fatty acid methylethanolamide obtained at room temperature

  650 ° C. 110 g (1.122 moles) of maleic anhydride and

  brews at this temperature for 2 hours.

  416 g of methylethacrylate maleate are obtained.

  nolamide (acylamido-N-methyl-N-ethylenemalAinate).

  The sulfonation and neutralization of the N-methylethanolamide acid maleainate is carried out in a similar manner

  to that described in Example 1 by its dosage in a solution.

  containing 1356 ml of water 107 g (0.563 mole) of sodium pyrosulphite and 168 g (1.126 mole) of triethanolamine

  the temperature of 70 C. 2045 g of aqueous solution are obtained.

  sol of triethanolamine and of acylamido-N-methyl-N-ethylenesulfosuccinic acid, corresponding to the following formula

O O

He He

  R - C - N - CH2 - CH2 - O - C - CH2 - CH - COONH (C2H40H) 3

I 1

  Wherein R is a C15-C19 linear hydrocarbon radical with a finished product content of 27.6% by weight. The

  Average molecular weight of the finished product is 689.

  dry matter 31.5% conversion (finished product / starting amide) 82.0% solubility in CCl4 5.7% viscosity at 200C 34.0 mPa.s density d20 1.094 kg / m3 pH (10X solution) 6 96

Example 5

  The methyl esters (methylates) of fatty acids are synthesized in a manner analogous to that

described in Example 1.

  500 g (1.00 moles) of distilled fatty acid methyl esters (first fraction) are placed in a 500 ml capacity flask equipped with a stirrer, a distillation nozzle and a thermometer. , 29 g (0.475 mol) of monoethanolamine and performs the treatment in a manner

  similar to that described in Example 1.

  Then, to the methyl esters of

2558157.

  fat 72.5 g (1.187 mol), monoethanolamine and 4.8 g of a 37.8% solution of sodium amino-2-ethoxylate in monoethanolamine. We bring to 90 C and we brew at this same

temperature for 1.2 hours.

  Methanol and excess monoethanol are removed.

  amine in a manner analogous to that of Example 1.

  contains 322 g of large acid monoethanolamide with an average molecular weight of 319. According to the degree (conversion) of the monoethanolamine, the yield is

96% of the theoretical yield.

  319 g of fatty acid monoethanolamide are added at a temperature of 80 ° C. to 102 g (1.04 mol) of anhydride.

  maleic and stir at this temperature for 1.5 hours.

  421 g of monoethanolamide acidic maleate (acylamidoethylenemaléinate) are obtained. The sulfonation and neutralization of the monoethanolamide acid maleate is carried out

  in a manner similar to that described in the

  1 by measuring it in a solution containing 630 ml of water, 114 g (0.6 mole) of sodium pyrosulphite and 168 g of a 25% solution of ammonia at a temperature of 70 ° C. 1330 g of an aqueous solution of a double salt of

  sodium and ammonium salts of acylamidoethylenesulfosuccinic acid

  that satisfying the following formula:

O O

R l - he

  * R -C NH - CH2 - C - C CH2 CH - C2OONH4

  SO3Na R being a C9-C17 linear hydrocarbon radical with a

  finished product content of 32% by weight. The molecular mass

  the average finished product is 537.

  dry matter 40.8% conversion (finished product / starting amide) 81.0% solubility in CCl4 4.9% viscosity at 200C 22.0 mPa.s density d20 1.102 kg / m3 pHI (10% solution) 6, 95

Example 6

  The methyl esters of fatty acids are synthesized in a manner similar to that described

in example 1.

  It is placed in a 500 ml capacity flask equipped with a stirrer, a nozzle for distillation and a stirrer.

  thermometer, 299 g (1.00 mol) of distillate methyl esters

  fatty acid strips (third fraction), 20 g (0.327 mol) of monoethanolamine and the treatment is carried out in a manner analogous to that of Example 1. Then, 90 g of methyl fatty acid esters are added ( 1.473 moles) of

  monoethanolamine and 8.2 g of a 37.8 x solution of amino-2-

  sodium ethoxylate in monoethanolamine and the mixture is stirred at a temperature of 90 ° C. for 1.5 hours. The methanol and the excess monoethanolamine are removed in a similar manner

to that of Example 1.

  330 g of fatty acid monoethanolamide having an average molecular weight of 328 are obtained. According to the degree (the degree of conversion of the monoethanolamine, the yield is

95.5% of the theoretical yield.

  At a temperature of 83 to 85 ° C., 328 g of fatty acid monoethanolamide obtained are added 121.4 g (1.238 mol).

  of maleic anhydride and stir at this temperature

  2 hours. 449 g of monoacidic acid maleate are obtained.

  ethanolamide (acylamidoethylenemaléinate). We make the

  sulfonation and neutralization of the acid maleate of mono-

  ethanolamide in a manner analogous to that described in Example 1 by its determination in a solution containing

  970 ml of water, 158.3 g (0.712 mnol) of potassium pyrosulphite

  and 149.5 g (1.424 moles) of diethanolamine at room temperature.

  90 ° C. 1720 g of aqueous salt solution are obtained.

  twice the amount of acylamido acid diethanolamine and potassium

  ethylenesulfosuccinic acid corresponding to the following formula:

0 0

He He

  R - C - NH - CH2 - CH2 - O - C - CH2 - CH - COONH2 (C2H40H) 2

  Wherein R is a C17-C21I linear hydrocarbon radical, finished product content of 30.3% by weight. The

  Average molecular weight of the finished product is 649.

  dry matter 41.4 X conversion (finished product / starting amide) 80.5% solubility in CCl4 4.2% viscosity at 20 C 20, G mPa s density d 42 1.089 Hg / m3 pH (10 X solution) 7.05

Example 7

  The methyl esters of fatty acids are synthesized in a manner analogous to that indicated in

Example 1

  1000 g (1.0 mole) of dibutanolamine, 8.0 g of a 37% solution are placed in a 1000 ml capacity flask equipped with a stirrer, a distillation nozzle and a thermometer. 8% sodium amino-2-ethoxylate in monoethanolamine. 295 g (1.00 mol) of methyl esters of fatty acids pretreated with dibutanolamine and distilled (second fraction) are added to the flask and the mixture is stirred at a temperature of 80 ° C. for 2 hours. The pressure in the system is reduced to the residual pressure of 200 mmHg, the mixture is heated to

  900 C and methanol is distilled off.

  428 g of dibutanolamide of fatty acids with an average molecular mass of 424 are obtained. According to the degree (rate) of conversion of the dibutanolamine, the yield is

  figure by 88% of the theoretical yield.

  To 424 g of fatty acid dibutanolamide is added

  obtained at the temperature of 75 C 127.5 g (1.30 mol) of anhy-

2 558157

  maleic dride and one brews at this temperature for 3

  hours. 551 g of dibutanol acid malinate are obtained.

  a: dmide / a4cylamido-N- (1-methyl-2-hydroxypropyl) -N- (dimethyl)

  1,2) ethylenemalinate]. The sulfonation and neutralization of the dibutylamide acid malinate is carried out in a manner analogous to that of Example 1 by metering it in a solution containing 1500 ml of water, 142 g (0.747 mol).

  sodium pyrosulphite and 222 g (1.49 mole) of triethanol-

  amine at a temperature of 70 ° C. 2412 g of an aqueous triethanolamine solution of

  sodium of facylamido-N- (1-methylhydroxv-2) propyl-

  N- (1,2-dimethyl) ethylenesulfosuccinic acid having the following formula:

O CH3 CH3 O

l 3 l

R - C - CN - CH - C - OONH (C, H40H) 3

I I

CH - CH - CH3 SO3Na

I I

CH3 OH

  wherein R is a C15-C19 linear hydrocarbon radical having a finished product content of 24.1% by weight;

average molecular weight 774.

  dry matter 36.2% conversion (finished product / starting amide) 74.8% solubility in CC14 7.2% viscosity at 200C 28.0 mPa.s density d20 1.062 kg / m3 pH (10% solution) 6, 95

EXAMPLE 8

  The methyl fatty acid methyl esters are synthesized in a manner analogous to that which

was described in Example 1.

  500 g of a 500 ml capacity flask equipped with a stirrer, a distillation nozzle and a thermometer were placed in the oven. 7.2 g (1.30 moles) of methylethanolamine , 8% of sodium amino-2-ethoxylate in

  monoethanolamine and 295 g (1.00 mol) of methyl esters

  distilled fatty acids (second fraction)

  treated with N-ethylethanolamine and stirred at the temperature of 800C for 1.5 hours. The methanol is then distilled off from the reaction mixture under a vacuum of 200 mm Hg residual and at a temperature of 900 ° C. The excess of ethylethanolamine is distilled off under a reduced pressure of 10 to 15 mmHg at the temperature of 120-125 ° C. 355 g of N-ethylethanolamide are obtained

  of fatty acids with an average molecular weight of 352.

  According to the degree (rate) of conversion of ethyl-

  ethanolamide, the yield is 95% of the

theoretical.

  To 352 g of ethylethanolEmide of fatty acids at a temperature of 90 ° C., 108 g (1.10 mol) of anhydride are added.

  maleic and stir at this temperature for 2 hours.

  460 g of N-ethylethanolamide acid maleainate are obtained.

  The sulfonation and neutralization of the ethyl maletinate of ethylethanolamide is carried out in a similar manner to that of Example 1 by its determination at a temperature of 700.degree.

  solution containing 1400 ml of water, 120 g (0.63 mole) of pyro-

  sodium sulphite and 77 g (1.26 mol) of monoethanolamine.

  2052 g of aqueous solution of double salt are obtained

  of monoethanolamine and sodium of acylamido-N-ethyl-

  N-ethylenesulfosuccinic compound corresponding to the following formula:

O O

  R - C - N - CH2 - CH2 - O - C - CH2 - CH - COONH3C2H4OH

2I4

  CH-CH3 SO3Na wherein R is a linear hydrocarbon radical in

  C15-C19, with a finished product content of 24.3% by weight.

  Average molecular weight of the product 614.

  dry matter 31.2 t conversion (finished product / starting amide) 81.6 X solubility in CCl4 5.9 XS viscosity at 20 C 32.0 mPa.s density d420 1, 086 kg / m3 pH (10 X solution ) 7.02

EXAMPLE 9

  The methyl esters (methylates) of fatty acids are synthesized in a manner analogous to that

  had been described in Example 1.

  It is placed in a 500 ml capacity flask equipped with a stirrer, a nozzle for distillation and a stirrer.

  thermometer 295 g (1.00 mol) of methyl esters (distillate)

  fatty acid (second fraction), 15 g (0.246 mol) of monoethanolamine and the treatment is carried out in a

  similar to that described in Example 1.

  Methyl esters of fatty acids are added

  g (1.310 moles) of monoethanolamine and the mixture is stirred

  at a temperature of 800 ° C., then 5.6 g of a catalyst solution are added: solution of 29% sodium methanolate in methanol. The reaction time is 1.2 hours. The excess monoethanolamine is removed and the

  methanol in a manner analogous to that of Example 1.

  325 g of fatty acid monoethanolamide having an average molecular weight of 324 are obtained. According to the degree of conversion of the monoethanolamine, the yield is 95.6% of the theoretical yield. The operations are carried out in the following manner in a manner analogous to that of Example 1. A product similar to that which is obtained is obtained.

is described in Example 1.

  The qualitative characteristics of the claimed compounds described in Examples 1-9 are combined in the

Tables 1-3.

Example 10

  Foaming detergent for baths

  addition of the following constituents, X by weight: double triethanolamine and sodium salt of acylamido-ethylene sulfosuccinic acid 32 aromatic substance 1.5 water the complement to 100

  The qualitative characteristics of the product de-

  Foaming tergent for baths are combined in Table 4.

Example 11

  The shampoo for children consists of

  following killers, X by weight: double salt of triethanolamine and

sodium of acylamido acid

* ethylene sulfosuccinic 5 aromatic substance 0.1 water the complement to 100 The qualitative characteristics of the shampoo

  for children are shown in Table 4.

Example 12.

  The shampoo consists of the following constituents,% by weight: double triethanolamine salt

of acylamido acid

  ethylenesulfosuccinic C9-C17 fatty acid diethanolamide 3,5 ethyl alcohol 1,5 sodium chloride 2.0 aromatic substance 1,0 water the complement to 100 The qualitative characteristics of the shampoo

are shown in Table 4.

Example 13

  The shampoo consists of the following constituents, er. oids: double salt of sodium and triethanolamine of acylamidoethylene sulfosuccinic acid 12 diethanolamide of C9-C17 fatty acids 3.0 ethylene glycol 0.75 sodium chloride 3.5 aromatic substance 0.75 water the complement to 100 O10 The qualitative characteristics of shampoo

are shown in Table 4.

TABLE 1

  Foaming power following Ross-Miles at a temperature of 40 ° C and a concentration of claimed compounds of 0.25% by weight

weight.

  NO of double salts of a Cations Distilled water ex. alkali metal and amine acid Acylamidoalcoylarre column height of foam, nmm

(or acylamido-N-

  hydroxyalkyl-N-H H1 H5 alkylene) sulfo-Os 60s 300s succinic

1 2 3 4 5 6

1 R1 = C15 C19 50% TEA + 195 180 175

R2 = hydrogen Na / 50% DEA

R3 = - CH2 - CH2

R1 = C15 - C19 34STEA + 185 170 166

R2 = - C (2H40H Na / 66% DEA

R3 = - CH2 - CH2

TABLE 1 (continued)

1 2 3 4 5 6

3 R1 = C15 - C19 Na / TEA 187 173 168

R2 = - CH2 - CH - OH

CH3

R3 = - CH2 - CH -

  CH3 4 R1 = C15-C19 Na / TEA 196 183 177

R2 = - CH3

3 - CH2 - CH2 -

  R1 = C9-C17 Na / NH4 183 170 166 R2 = hydrogen

R3 = - CH2 - CH2 -

6 R1 = C17 - C21 K / DEA 180 167 160

R2 = hydrogen

R3 = - CH2 - CH2 -

7 R1 = C15 - C19 Na / TEA 182 167 163

R2 = - CH - CH - CH3

CH3 OH

R = - CH - CH -

3 1 t

CH3 CH3

8 R1 = C15 - C19 Na / MEA 192 180 172

R2 = CH2 - CH3

R3 = CH2 - CH2-

  N-tes: TEA: triethanolamine, DEA: diethanolamine,

MEA: mnionethanolamine.

2558 1 5 7

  TABLE 1 (cont.) N Water Hard water (5.35 milligram equivalents / ex tare liter) Stability Foam Stability column height, foam mm H5 Ho Hi H5 H5 H1 Bone 60s 300s H 3. i

7 8 9 10 11

1 0.97 205 186 180 0.97

2 0.98 190 175 168 0.96

3 0.97 193 177 170 0.96

4 0.97 202 186 180 0.97

0.98 190 177 172 0.97

6 0.96 185 170 165 0.97

7 0.98 188 173 165 0.95

8 0.96 200 185 180 0.97

TABLE 2

  Detergent power on standardized wool fabric for a

  claimed compound concentration of 0.25% by weight.

  N of Double Salts of Cations Conservative Power ex. alkali metal and detergent acid amine acylamidoalkylene acylation

(or acylamido-N-

hydroxyalkyl-N-

alkylene) sulfo-

succinic

1 2 3 4 5

1 R1 = C15 - C19 50% TEA + 95 98

R2 = hydrogen Na / 50% DEA

R3 = - CH2 - CH2 -

2 R1 = C15-C19 34% TEA 96 98

R2 = - C2H40H Na / 66% DEA

2 24

R3 = - CH2 -CH2

R1 = C15-C19 Na / TEA 96 98

R2 = - CH2 - CH - OH

CH3

R3 = - CH2 - CH -

CH3 4 R1 = C15-C19 Na / TEA 94 98

R2 = - CH3

R3 = CH2 CH2

1 2 3 4 5

  R1 = C9-C17 Na / NH4 90 98 R2 = hydrogen

R3 = - CH2 - CH2-

6 R1 = C17 - C21 K / DEA 92 98

R2 = hydrogen

R3 - CH2 - CH2-

R1 = C15 - C19 Na / TEA 95 97

R2 = - CH - CH - CH3

CH3 OH

R = - CH - CH -

3 I I

CH3 CH3

R1 = C15 -C19 Na / MEA 96 98

R2 = - CH2 - CH3

R3 = - CH2 - CH2 -

  9 Na Dodecylsulfate 96 98 sodium Notes: TEA: triethanolamine, DEA: diethanolamine,

MEA: monoethanolamine.

2558157.

TABLE 3

  Surface tension of the determined aqueous stalagmometric solution (in N / m 3) at the temperature of 200C and the concentration of the claimed compound of 0.1% by weight. N of double salts of a Cations Water Hard water

  the ex. alkali metal and dis- (5,35 equi-

of the amine of

acylamidoalcoy-milligram

ler (or acylamido-N-mes / liter)

hydroxyalkyl-N-al-

covlène) sulfosucci-

picnic

1 2 3 4 5

  1 R1 = C15-C19 50% TEA + 30.0 31.3 R2 = hydrogen Na / 50% DEA

R3 = - CH2-CH2 -

  2 R1 = C15 - C19 34% TEA + 28.4 29.2 R2 = - C2H40H Na / 66% DEA

R3 C2 - C2 -

3 R1 = C1 C19 Na / TEA 28.1 28.5

R2 = - CH2 - CH - OH

CH3

R3 = - CH2 - CH -

CH3

4 Ri = C 1 -C19 Na / TEA 30.2 30.8

R2 = - CH

RL 3

R3 = - CH3

TABLE 3 (continued)

1 2 3 4 5

  R1 = C9-C17 Na / NH 30.4 31.6 R2 = hydrogen

R3 = - CH2 - CH2

6 R1 C17 K 21 / DEA 30.6 30.8

R2 = hydrogen

R3 = - CH2 - CH2-

7 R1 = C15 - C19 Na / TEA 28.2 29.0

R2 = - CH - CH - CH3

L!

CH3 OH

R = - CH - CH -

3 1 1

CH3 CH3

8 R1 = C15 - C19 Na / MEA 29.8 30.9

R2 = - CH2 - CH3

R3 = - CH2 - CH2

  Notes: TEA: triethanolamine, DEA: diethanolamine,

MEA: monoethanolamine.

TABLE 4

  N of gold- D detergent indices of the example dre

10 11 12 13

1 2 3 4 5 6

  1 Generation of foam H 205 201 198 196 O of a 0.25% solution of the compound claimed in H1 186 184 174 176 C according to Ross-Miles, mm H5 180 178 171 173 2 Foam stability H5 / H1 0, 97 0.97 0.98 0.98 3 Cloud point, C -245 1 * 2 2 + 3 -1 + 1 4 Degreasing effect by

comparison laurylsul-

  sodium fate,% 56.3 51.5 54.2 54.0 Viscosity at 20 C, mPa.s 32.0 3.0 1200.0 430.0 6 Density at 20 C, kg / m 1,098 1,008 1,072 1,063 PH of the aqueous solution

at 10% of the compound

6,80 6,85 6,75 6,85 e558157

Claims (8)

  1. Double salts of an alkali metal and an amine of acylamidoalkylene sulfosuccinic acids having the general formula: IIII! 1H   Co R2R S iC2 -4 + R1. - C - N - R3 - O - C - CH2 - CH Ie X5 O R2 O SQ3 H R6   R1 being a C9-C21 hydrocarbon radical of linear constitution, R2 being hydrogen, - CH3, - CH2 - CH3, - CH2 - CH2 - OH, - CH2 - CH - OH or - CH - CH - CH3, CH3 CH3 OH   R3 being - CH2 - CH2 -, CH2 - CH - or - CH - CH - - CH3 CH3 CH3   R4, R5, R6 being hydrogen and / or - CH2 - CH2 - OH, and Me being Na or K. Process for the preparation of alkali metal double salts and the amine of acylamidoalkylene (or acylamido-N-hydroxyalkyl-N-alkylene) sulfosuccinic acid according to claim 1, characterized in that one   treats the fatty residues of the fish   containing fatty acids and glycerides with an acid number not exceeding 50 mg KOH / g, saponification value 181 to 192 mg KOH / g and bromine value 60 to 70 Br / 100 g by methanol in the presence of sulfuric acid while operating at the boil and obtaining   a reaction mixture from which the fatty layer   layer of glycerides and methyl esters (methylates) of fatty acids which are treated with methanol in the presence of sulfuric acid at a temperature of 50 to 600C to obtain a reaction mass from which the anhydrous fatty layer is separated off that is treated with methanol in the presence of alkali at the boiling temperature of methanzl to obtain a reaction mixture containing the methyl esters (methylates) of fatty acids that are separated and treated with an alkylolamine taken a 25 to 30% by weight of the quantity of methyl esters of fatty acids   in the presence of a catalyst selected from. the group   an alkali metal or its amide or alcoholate at a temperature of 70 to 90 ° C to obtain fatty acid alkylolamides which are treated with maleic anhydride at a temperature of 60 to 90 ° C. to obtain maleinates of alkylololamides of fatty acids and which are then treated   by sodium or potassium pyrosulphite and ethanol-   amine or ammonia at a temperature of 60 to 900C in   aqueous medium by obtaining the finished product.   3. Process according to claim 2, characterized in that, to improve the quality of the finished product,   subject the fatty acid methyl esters prior to   by an alkylolamine in the presence of the indi-   prior treatment with an alkylolamine   at 5 to 10% by weight of the weight of the methyl esters   fatty acids at a temperature of 70 to 80 C with eli-   subsequent removal of the used alkylolamine.   4. Process according to any one of the claims   2 and 3, characterized in that as alkylolamine,   monoethanolamine, diethanolamine, diiso-   propanclamine, N-methylethanolamine, N-ethylethanol- amine, dibutanolamine.   5. Process according to one of Claims 2 to 4,   characterized in that to simplify the technology of the   As a catalyst, the amino-2-ethoxy sodium xylate.   6. Process according to one of Claims 2 to 5,   characterized in that as ethanolamine the   mono-, di- and / or triethanolamine.   7. Detergent comprising a surfactant derivative, a scented substance and water, characterized in that, as a surfactant derivative, it contains a double salt of   triethanolamine and sodium acylamidoethylene acid   sulphosuccinic acid corresponding to the following formula: O - O 0 O There He1   R - C - NH - CH2 - O - C - CH2 - CH - COONH (C2HOH) 3 I   SO3Na in which R is a linear C15-C21 hydrocarbon radical of linear constitution according to claim   1, the proportions of the aforementioned constituents being the following   vines,% by weight: triethanolamine double salt and sodium acyl acid   amidoetylenesulfosuccinic acid 5.0-32.0 aromatic substance 0.1 to 1.5 water complement to 100   8. Detergent according to claim 7, characterized   in that it also contains the diethanolamide   C9-C7 fats, sodium chloride and ethyl alcohol.   at the following proportions of the constituents,% by weight: double triethanolamine salt and sodium acyl acid   amidoethylesulfosuccinic 12.0-20.0 C9C17 fatty acid diethanolamide 0.5-3.5 sodium chloride 1.0-3.5 ethyl alcohol 0.3-1.5 aromatic substance 0.1-1.5 water the complement to 100