DD253615A1 - METHOD FOR PRODUCING DEFINED MONOMERER ALKYLAMMONIOBISALKYLSULFOSUCCINATE - Google Patents

Abstract

The invention relates to a process for the selective production of monomeric Alkylammoniobisalkylsulfosuccinate with the aim to win well Wasserloesliche and mild and gentle to the skin products. This is achieved according to the invention by reacting N-alkyldialkanolamines or longer-chain N-alkyl-bis-polyoxyalkyleneamines in a molar ratio of 1: 1.8 to 1: 2.2 with maleic anhydride to give a bismaleate intermediate which is 1: 1.8 to 1: 1 in molar ratio 2.2 is reacted with an aqueous solution of alkali metal sulphite of the general formula M2uHuSO3, where u0.45 to 0.55 and M represents an alkali metal or a tri or tetraalkylammonium group. There are selectively defined Alkylammoniobisalkylbissulfosuccinate with surfactant properties and particularly good skin compatibility, which are suitable as a cosmetic and Körberpflegemittelbestandteil.

Description

Field of application of the invention

The invention relates to a process for the selective preparation of defined monomeric Alkylammoniobisalkylsulfosuccinate which are suitable for application in detergents and cleaners and as emulsion and suspension formers for cosmetics and personal care products.

Characteristic of the known state of the art

More recently, in the formulations for detergents and cleaners as well as cosmetics and personal care products in addition to nonionic and anionic surfactants, being used as anionic surfactants especially ethylene oxide-based polyether compounds in the form of sulfates and sulfosuccinates in order to increase the colloid chemical activity and to achieve skin-friendly effects also nitrogen-containing ampholytic compounds with surfactant properties used.

In a known manner, such nitrogen-containing ampholytic compounds according to US Pat. Nos. 3,927,073, 39,284,222 and DE-OS 2,258,564 are known by reacting long-chain alkylene oxides and diethanolamine with cyclic dicarboxylic acid anhydrides to give mixtures of mono-, di- and triesters which are reacted with sulfite solutions. produced. In these processes, in particular due to the undefined reaction conditions in the sulfonation reaction, undefined sulfosuccinate mixtures which have good washing and also softening properties in detergents in a basic medium are unsuitable for use in cosmetic surfactant formulations because of their mixture character and the olefin oxides used as raw materials.

It is also known to synthesize fatty acid monoethanolamide sulfosuccinates from fatty acids (L.D.Volkova, Maslozirov, prom., Moskwa 36 [1970], 29-31).

These products have a different surfactant structure than those mentioned above and are highly pH-dependent in stability and surface chemical activity. In the slightly acidic environment, they have quite good washing and foaming power and can also be used for the preparation of shampoos. The disadvantage here, however, is the instability and also a severely limited solubility in water of this type of compound in the alkaline medium. Although the sodium bis (2-stearoylaminoethyl) sulfosuccinate (PL-PS 85071) obtained on the same basis shows good fat dissolving behavior, it is insoluble in water.

Object of the invention

, It is the object of the invention _t nitrogenous, ampholytic compounds having sulfosuccinate structural units to produce, which are water soluble and have a mild skin-protecting effect.

Explanation of the essence of the invention

The object of the invention is to provide a novel process for the preparation of such compounds from readily available starting materials.

The object is achieved by a process for the preparation of monomeric Alkylammoniobisalkylsulfosuccinaten of the general formula I.

MO-CO. f- ^ CO-OM

^ CH-CH ₂ -C0- (OCH ₂ CH ₂ ) _n -gH- (CH ₂ CHO) -GO-CH ₂ -CH ^

MO ₃ S SO ₃ "

(I) or the position isomers II and III

MO-CO-CH ₀ . F / CH ₂ -CO-Of-

OCH-CO- (OCH ₀ CH ₀ J _n -NH- (CH ₉ CH ₉ O) -CO-CH

MO ₃ S

(II)

MO-CO-CH ₀ . '? ^ CO-OM

O CH-CO- (OCH CH _{0 0) n} -NH- (CH ₀ CH ₀ O) _-CO-CH? -CH _ft

MO ₃ S ^^ ² & ^S0 3

(III),

in which R represents a saturated or unsaturated aliphatic hydrocarbon radical of C number 4 to 25, η and m are independent numbers from 1 to 20 and M represents an alkali metal or a tri or tetraalkylammonium grouping customary in surfactant formulations, according to the invention by N-alkyldialkanolamines or longer-chain N Alkyl bispolyoxyalkyleneamines of the general formula IV,

R-N, (IV)

in which R, η and m have the same meaning as above, with maleic anhydride in a molar ratio of 1: 1.8 to 1: 2.2 to defined intermediates of the general formula V,

^. (CH ₀ CH ₀ O) _n -CO-CH = CH-COOH

φ^ r G. c. \\

R-NH (V)

in which R, η andjri have the same meaning as above, if appropriate with the addition of an aprotic solvent, by intensive mixing at a reaction temperature of 20 to 110 ° C implemented and these intermediates then with stirring at a reaction temperature of 0 to 8O ⁰ C, preferably at 20 to 45 ⁰ C, with an aqueous solution of alkali Barren ammonium sulfite having the empirical formula Vl,

M ₂ . _U H _U SO ₃ (Vl)

in which M is an alkali metal, preferably sodium, or a tri- or tetraalkylammonium compound and u is 0.45 to 0.55, in a molar ratio of 1: 1.8 to 1: 2.2 are sulfonated.

According to the invention, this process leads to substantial avoidance of the formation of polymeric by-products, since during the entire sulfonation the reaction proceeds in a pH-controlled manner and a hydrolytic attack on the intermediate V during the addition reaction is suppressed. The formation of the by-products can be limited according to the invention to a maximum of 15%, whereby the surface-chemical effect is not adversely affected for the desired applications. According to the invention, the process includes the selective recovery of trisodium N-alkylammoniobisethylsulfosuccinate according to formulas I to III in which η and m are 1 and M is Na by reaction of the starting materials in the molar ratio N-alkyldiethanolamine (IV): maleic anhydride: VI of 1: 2 : 2, where M is sodium and u is exactly 0.50. As a result, hydrolytic attack and polymerization during the addition reaction are almost completely suppressed. The reaction to the intermediate of formula V can according to the method in aprotic solvents, in particular chlorinated hydrocarbons, are performed. For them and for the reaction with alkali metal sulfite according to formula VI in aqueous solution, according to the invention, the reaction temperature between 0 and 8O ⁰ C, preferably between 20 and 45 ⁰ C, are.

According to a further variant of the process, the first stage of the reaction of N-alkyldiethanolamine according to formula V can also be carried out without solvent in the melt at higher temperatures between 60 and 110 ⁰ C, if for the 'subsequent reaction of the sulfonation, the intermediate product is sufficiently finely divided and is reacted in suspension with alkali metal sulfite according to formula VI.

Furthermore, the sulfonating agent used according to the invention can be prepared by mixing aqueous disodium sulfite solution with aqueous sodium bisulfite solution in the stoichiometric ratio of 1: 1 or to obtain the same effect a Natriumhydrogensulfitlösung known alkalinity by adding calculated amounts of sodium hydroxide solution to the stoichiometric composition according to formula VI are brought. A further variant for preparing the formula VI according to the composition of the sulfonating agent in particularly high purity is the solution of disodium pyrosulfite and disodium sulfite in a stoichiometric ratio of 1: 2 in water.

embodiments example 1

Preparation of N-dodecyl diethanolamine bismaleate

10.32 g (37 mmol) of N-dodecyldiethanolamine (98% pure) are dissolved in 100 ml of chloroform and heated to reflux. To the dissolving solution, a solution of 7.26 g (74 mmol) of maleic anhydride in 50 ml of chloroform is added with stirring.

The reaction solution begins to foam easily. After boiling for 6 hours, the chloroform is removed. There remains as a residue a colorless, viscous product which is soluble in water, acetone and ethanol.

Preparation of N-dodecyl-ammoniobisethylsulfosuccinate

The N-dodecyl-diethanolamine-bismaleate is mixed with 100 ml of water and heated with stirring to 45 ⁰ C. Subsequently, the solution of a sulfite mixture of 4.77 g (37 mmol) of disodium sulfite Na ₂ SO ₃ and 3.52 g (18.5 mmol) of disodium pyrosulfite Na ₂ S ₂ O ₅ in 50 ml of water is added with stirring. The reaction temperature should not exceed 45 ° C. The reaction mixture is stirred for 3 hours at 45 ° C, producing a clear colorless, foaming solution. The water is removed in vacuo on a rotary evaporator. The aqueous product foams strongly, therefore, the water is removed to the end of evaporation by means of repeated addition of pure ethanol. The residue is dried in a desiccator over Na ₂ SO ₄ and finely ground. For further purification, the reaction product in Soxhlet with abs. Ethanol is extracted for 25 hours. In this case, a readily water-soluble product is obtained which gives a dense foam in aqueous solution and is completely free of hydrophobic impurities. The yield is 85% d. Th.

The screening test gave the following application-related values:

Max. Surface tension reduction to y _max = 38.1 mN / m

Surface tension lowering water / heptane to y _Os = 5.5mN / m

Foaming power (according to Ross-Miles) 73.4%

Foam resistance 98.5%

The elemental analysis has the following composition:

88.7% N-dodecyl-ammoniobisethylsulfosuccinate, 2.3% water and 9.0% sodium sulfate.

Example 2

Preparation of N-tetradecyldiethanolamine bismaleate ......... ..

The reaction of 8.39 (25 mmol) of N-tetradecyldiethanolamine (89%) with 4.90 g (50 mmol) of maleic anhydride is carried out according to Example 1. The residue remains a colorless viscous product which is readily soluble in water, acetone and ethanol

Preparation of N-tetradecyl-ammoniobisethylsulfosuccinate

The resulting N-Tradecyldiethanolamin bismaleate is mixed with 70 ml of water and heated with stirring to 45 ⁰ C. Then, the solution of a Sulfitgemisches of 3,20g (25 mmol) disodium and 2.38 g (12,5mmol) Dinatriumpyrosulfit Na ₂ S ₂ O ₅ is added in 35ml water and maintained the reaction temperature at 45 ⁰ C constant. The further course of the reaction is carried out according to Example 1. The end product is extracted four times with 100 ml of dry acetone and is then present as a solid, readily water-soluble compound.

The yield is 93% d. Th.

Example 3

Preparation of N-alkyldiethanolamine-bismaleate mixture based on rofamine KD The reaction of 8.81 g (30 mmol) of N-alkyldiethanolamine (95%) based on a technical fatty amine mixture of the average gross composition of C ₁₅₄ H _35-8 O ₂ N ₁ with 5.90 g (60 mmol) of maleic anhydride is carried out according to Example 1. The residue obtained is a colorless viscous product which is readily soluble in acetone and ethanol but poorly soluble in water

Preparation of N-alkyl-ammoniobisethylsulfosuccinate mixture

The reaction of the N-alkyldiethanolamine bismaleate is carried out within 12 hours of a solution of 2.85 g (15 mmol) of disodium pyrosulfite and 3.78 g (30 mmol) of disodium sulfite in 40 ml of water at room temperature. The reaction mixture is isolated by concentrating the solution and then cleaned with 300 ml of dry acetone. The product obtained is solid and readily soluble in water. The yield is 6.95 g = 91% of theory.

Example 4

Preparation of N-octadecyldiethanolamine bismaleate

The reaction of 9.57 g (25 mmol) of N-octadecyldiethanolamine (93%) with 4.90 g (50 mmol) of maleic anhydride is carried out by introducing maleic anhydride into the heated to 60 ° C N-Octadecyldiethanolamin. The temperature rises to 80 ° C. After cooling, the residue obtained is a waxy, water-insoluble product which is readily soluble in acetone and ethanol.

Preparation of N-octadecyl-ammoniobisethylsulfosuccinate

The reaction of N-octadecyldiethanolamine bismaleate to bissulfosuccinate is carried out according to Example 3, but with a slightly excess molar amount of 2.85 g (15 mmol) of sodium pyrosulfite and 3.47 g (30 mmol) of disodium sulfite. The product obtained is solid and water-soluble, forms colloidal solutions with water.

The yield is 85% d. Th., Based on surfactant.

Example 5

Preparation of a technical N-alkyldiethanolamine-bismaleate mixture of rofamine T-oxethylate Rofamin-T ₂₀ -oxethylate is a technical product, essentially consisting of a mixture of N-hexadecyldiethanolamine, N-octadecyldiethanolamine and N-oleyldiethanolamine (about 4% by weight) : 6: 1).

The reaction of 8.88 g (25 mmol) rofamine T ₂ o-oxyethylate (2 mol EO / mol) with 4.90 g (50 mmol) maleic anhydride is carried out according to Example 2. The residue obtained is a waxy and water-insoluble product, but which is readily soluble in acetone and ethanol.

Preparation of a technical mixture of N-alkyl-ammoniobisethylsulfosuccinates The reaction of the technical N-alkyl-diethanolamine-bismaleate mixture is carried out according to Example 3 with a solution of 2.85 g (15 mmol) disodium pyrosulfite and 3.78 g (30 mmol) disodium sulfite. After 3xigem extracting the final product with 100 ml of dry acetone, a solid water-soluble product is obtained which forms colloidal solutions with water, the yield is 80% d. Th., Based on surfactant.

Example 6

Preparation of a Technical N-Alkenyl Diethanolamine Bismaleate Mixture of Rofamine T ₈₀ Oxyethylate Rofamine T ₈₀ oxethylate is a technical product of long-chain N-alkenyl diethanolamines containing 71% N-oleyldiethanolamine and 2 moles of ethylene oxide per mole 11.5 g (25 mmol) Rofamin T ₈₀ -ethylate with 4.90 g (50 mmol) of maleic anhydride is carried out according to Example 1. The residue obtained is a viscous product which is poorly soluble in water but readily soluble in acetone and ethanol.

Preparation of a technical mixture of N-alkenylammoniobisethylsulfosuccinates The reaction of a mixture of technical N-alkenyldiethanolamine bismaleate based on rofamine T ₃₀ -oxoate-2EO with the aqueous solution of a mixture of 2.38 g (12.5 mmol) of disodium pyrosulfite and 3 , 15 g (25 mmol) of disodium sulfite is carried out according to Example 2 and the final product is extracted 6 times with 100 ml of dry acetone. This produces a solid, very water-soluble product.

The yield is 91% d. Th.

Claims (2)

1. A process for preparing defined monomeric Alkylammoniobisalkylsulfosuccinate of the general formula I. MO-CO. R ^ CO-OM ^ CH-CH ₀ -CO- (OCH CH _{0 0)} -NH- (CH ₀ CH ₀ O) -CO-CH ₀ -Ch. ^ MO ₃ S ' ^{2 2 2 n} ® ^{2 2 m 2} S0 ₃ ^@ or the position isomers MO-CO-CH ₀ I ^ CHp-CO-OM ^2N CH-CO- (OCH ₂ CH ₂ ) _n -NH- (CH ₂ CH ₂ O) _m -CO-CH MO ₃ S - "^ *"" ^e SO ₃ ^ (II) and f ^ CO-OM 'CH-CO- (OCH CH ₀₎ -NH- (CH CH ₀ O) -CO-CH -CH _{o 0} CH ₀₎ -NH- (CH ₀ CH ₀ O) _1n -CO-CH ₀ MO ₃ S> ^ 2 2 η $ 22m X 2 O _{3 5} ⁶ ' (in) ; in which R is a saturated or unsaturated aliphatic hydrocarbon of C number 4 to 25, η and m are independent numbers from 1 to 20 and M is an alkali metal or a tri or tetraalkylammonium grouping customary in surfactant formulations, characterized in that N-alkyldialkanolamines or longer-chain N-alkyl-bis-polyoxyalkyleneamines of the general formula IV, R-N in which R, η and m have the abovementioned meaning, with maleic anhydride in a molar ratio of 1: 1.8 to 1: 2.2 to defined intermediates of the general formula V © ^ CH ₂ CHg) _n -CO-CH = CH-R-NH _& (V) ^ (CH ₀ CH ₀ O) -CO-CH = CH-COO ^
^v 2 2 m ι in the R, η and m have the same meaning as above, optionally with the addition of an aprotic solvent, by intensive mixing at a reaction temperature of 20 to 11O ⁰ C reacted and these intermediates then with stirring at a reaction temperature of 0 to 8O ⁰ C, preferably at 20 to 45 ⁰ C, with an aqueous solution of alkali metal or ammonium sulfite of the empirical formula Vl M ₂ . _U H _U SO ₃ ,. (Vl) in which M is an alkali metal, preferably sodium, or a tri- or tetraalkylammonium compound and u is 0.45 to 0.55, in a molar ratio of 1: 1.8 to 1: 2.2 are sulfonated. 2. The method according to claim 1, characterized in that the aqueous solution of alkali metal or ammonium sulfide of the empirical formula VI by dissolving a mixture of disodium pyrosulfite and disodium sulfite in water, preferably in the stoichiometric ratio of 1: 2, or by mixing an aqueous disodium sulfite solution with a aqueous sodium bisulfite solution, preferably in the stoichiometric ratio of 1: 1, is prepared.