RU2780017C2 - Hydroxy-acid alkoxylation - Google Patents

Abstract

FIELD: chemistry.

SUBSTANCE: present invention concerns alkoxylated hydroxycarboxylic acids, a method for their production, and their use. A mixture with surface-active properties of compounds of the formula (I') is proposed, in which R¹ is selected from alkyl with 1-10 carbon atoms, branched saturated or unsaturated aliphatic hydrocarbon residue with 1-30 carbon atoms, linear unsaturated aliphatic hydrocarbon residue with 1-30 carbon atoms, saturated or unsaturated cycloaliphatic hydrocarbon radicals with 3-10 carbon atoms, and aryl; R² is -CR^aR^b-CR^cR^d-, in which each R^a, R^b, R^c, and R^d is independently selected from hydrogen, unsubstituted alkyl with 1-30 carbon atoms, unsubstituted cycloalkyl with 5-7 carbon atoms, and cycloalkyl with 5-7 carbon atoms, which contains 1, 2, or 3 substituents, which are independently selected from alkyl with 1-6 carbon atoms and alkenyl with 2-6 carbon atoms, wherein two residues R^a and R^c, together with the group -CR^b-CR^d-, to which they are attached, can be cycloalkyl with 5-7 carbon atoms, which is unsubstituted or contains 1, 2, or 3 substitutes, which are independently selected from alkyl with 1-6 carbon atoms and alkenyl with 2-6 carbon atoms; R³ is selected from hydrogen and methyl; X in each case is a bond, or a divalent linear or branched saturated or unsaturated aliphatic hydrocarbon residue with 1-30 carbon atoms, or a divalent saturated or unsaturated cycloaliphatic hydrocarbon residue with 3-10 atoms carbon; k is a number from 2 to 100; n is a number from 1 to 10; and A is hydrogen or cationic equivalent; with the exception of 2-[2-(2-hydroxyethoxy)ethoxy]propanoic acid.

EFFECT: obtaining alkoxylated hydroxycarboxylic acids.

18 cl, 6 ex

Description

The present invention relates to alkoxylated hydroxycarboxylic acids, a process for their preparation and their use.

Surfactants belong to the class of the most common surface-active compounds and, in addition to detergents and cleaning agents, are widely used in the field of cosmetics. Common surfactants, such as those used primarily in cosmetics, are alkoxylated hydroxycarboxylic acids (alkoxylated hydroxyacids). If the carboxylic acid group(s) is/are not yet in the esterified state, the alcohol and carboxylic acid groups react equally during alkoxylation. The resulting esters and ethers are characterized by high foaming power, high cleaning power and low sensitivity to hardness and fat, and are widely used for the production of cosmetic products such as hair shampoos, bath foams or shower gels, as well as detergents for hand washing dishes.

Ethercarboxylates are known as anionic surfactants. They are obtained from the corresponding alcohol ethoxylates as a result of interaction with chloroacetic acid. The disadvantage of this synthesis is that a high content of sodium chloride is formed.

For many modern applications, surfactants have additional requirements in addition to good surfactant performance. Particularly in cosmetics, a high level of dermatological compatibility is essential. In addition, sufficient solubility in water, good compatibility with as many active and excipients as possible used in cosmetics, good foaming power and good rheological characteristics are generally desirable. Further, there is also a need for surfactants that can be obtained at least in part from biogenic sources, and especially from renewable raw materials. In addition, there is also a need for surfactants which, on the one hand, contain free carboxylic acid groups, ie. strongly hydrophilic groups and, on the other hand, have dispersion active groups, especially oligo- and polyalkylene oxide groups. Therefore, in particular, there is a need for selective alkoxylation reactions of hydroxycarboxylic acids while maintaining the acid function.

Alkoxylation reactions of hydroxycarboxylic acids have been known for a long time.

Chinese Patent CN 102850538 describes a polylactic acid whose terminal hydroxyl groups do not belong to lactic acid, and a method for producing them. This method allows functionalization of the end groups by adding an end capping agent during or after the polymerization of the polylactic acid in a solid phase polymerization or melt polymerization process.

WO 2013/014126 describes esterified lactate esters and their use in plant protection products. Alkoxylated free polylactic acid is not described in this document.

European patent application EP 0017059 describes the alkoxylation of carboxylic acids which additionally contain one or more hydroxyl groups. Interaction with ethylene oxide is subjected to monohydric fatty acids. However, this reaction is not selective. In addition to alkoxylation of the carboxylic acid function, an esterification reaction also occurs. In addition, hydroxyl groups are also alkoxylated. The resulting products have a very low acid number of less than 5 mg KOH/g. On the contrary, the resulting esters, depending on the degree of alkoxylation, have a high saponification number.

WO 2008/015381 describes cleaning compositions for surfaces. Among others, compounds of the formula R ₁ (OC ₂ H ₄ ) _n -OCH ₂ COO ^- M ⁺ are disclosed, where R ₁ represents alkyl with 4-18 carbon atoms, i.e. these compounds have a hydroxyl-capped end group.

Until now, it has not been possible to selectively alkoxylate hydroxycarboxylic acids. In addition to preferential alkoxylation at the acid function, hydroxyl functions are also alkoxylated. In addition, transesterification reactions occur. Therefore, a complex mixture of products is obtained.

The object of the present invention was to provide novel compounds which are preferably suitable for various applications as surfactants. Specifically, they must be suitable to cover the complex spectrum of requirements that has been described above. In particular, a method should be provided that allows selective alkoxylation of hydroxycarboxylic acids while maintaining the acidic function.

Surprisingly, it has been found that this problem is solved with the compounds according to the invention and the method according to the invention.

The first object of the present invention are the compounds of General formula (I)

wherein

R is an organic residue which has at least one substituent -O-[R ₂ -O] _k -H; wherein

R ² means -CR ^a R ^b -CR ^c R ^d -, in which each R ^a , R ^b , R ^c and R ^d is independently selected from hydrogen, unsubstituted alkyl with 1-20 carbon atoms, unsubstituted cycloalkyl with 5 -7 carbon atoms and cycloalkyl with 5-7 carbon atoms, which contains 1, 2 or 3 substituents, which are independently selected from alkyl with 1-6 carbon atoms and alkenyl with 2-6 carbon atoms,

wherein the two residues R ^a and R ^c , also together with the -CR ^b -CR ^d - group to which they are attached, may represent a cycloalkyl of 5 to 7 carbon atoms which is unsubstituted or has 1, 2 or 3 substituents which independently selected from alkyl with 1-6 carbon atoms and alkenyl with 2-6 carbon atoms; and

k means a number between 1 and 100, and

And means hydrogen or cationic equivalent.

The compound 2-[2-(2-hydroxyethoxy)ethoxy]propanoic acid (CAS 1604403-13-5 (S), 1604453-64-6 (R)) is excluded from the compounds of general formula (I).

A preferred embodiment are compounds of formula (I')

wherein

R ¹ is selected from hydrogen, a linear or branched saturated or unsaturated aliphatic hydrocarbon residue with 1-30 carbon atoms, saturated or unsaturated cycloaliphatic hydrocarbon radicals with 3-10 carbon atoms and aryl,

R ³ is selected from hydrogen and methyl,

X in each case means a bond or a divalent linear or branched saturated or unsaturated aliphatic hydrocarbon residue with 1-30 carbon atoms, or a divalent saturated or unsaturated cycloaliphatic hydrocarbon residue with 1-30 carbon atoms;

n means a number between 1 and 10, and

A, R ² and k, in each case independently, such as defined previously or hereinafter.

Another object of the present invention is a process for the preparation of compounds of general formula (I), according to which

a) at least one salt of hydroxycarboxylic acid of general formula (III),

wherein

R' means an organic residue which contains at least one hydroxyl group and in which all acid groups, if necessary, are completely deprotonated; and

each A' is independently a cationic equivalent;

subjected to interaction with at least one epoxide of general formula (IV)

wherein

each R ^a , R ^b , R ^c and R ^d are independently selected from hydrogen, unsubstituted C 1-20 alkyl, unsubstituted C 5-7 cycloalkyl and C 5-7 cycloalkyl which contains 1, 2 or 3 substituents independently selected from alkyl with 1-6 carbon atoms and alkenyl with 2-6 carbon atoms,

wherein the two residues R ^a and R ^c , also together with the -CR ^b -CR ^d - group to which they are attached, may be a 5-7 carbon cycloalkyl which is unsubstituted or has 1, 2 or 3 substituents, as selected independently from alkyl with 1-6 carbon atoms and alkenyl with 2-6 carbon atoms; and

b) if necessary, the reaction product from step a) is treated with acid.

The subject of the invention is also the compounds of the general formulas (I) and (I') obtainable by this method.

Another object of the invention is also a cosmetic or pharmaceutical composition which contains at least one compound of the general formula (I) or (I') as defined above and below.

Another object of the invention is the use of compounds of general formula (I) or (I'), as defined above and below, as surfactants, especially as a surfactant for detergents and cleaners, cosmetics, pharmaceuticals.

The compounds of general formula (I) may be present in the form of mixtures or as pure compounds. Suitable for applications according to the invention are, as a rule, mixtures of compounds of general formula (I), such as are obtained, for example, by means of the method of preparation described in the following. The individual components of these mixtures may differ, for example in terms of the degree of alkoxylation k. The individual components of these mixtures can also differ, for example with respect to the degree of oligomerization n. Of course, it is also possible to separate the reaction mixtures obtained with the method according to the invention by conventional separation methods, for example by distillation or chromatography.

In the context of the present invention, cationic equivalent means a monovalent cation or the monovalent part of the charge of a multivalent cation. If A or A' is a cationic equivalent, it is preferably selected from alkali metal cations, NH ₄ ⁺ and cations of the formula HNE ¹ E ² E ³⁺ , where E ¹ , E ² and E ³ are independently selected from hydrogen, linear and branched alkyl with 1-6 carbon atoms and linear and branched hydroxyalkyl with 1-4 carbon atoms, provided that one of the residues E ¹ , E ² and E ³ is other than hydrogen. Preferably the cationic equivalent is selected from Na ⁺ , K ⁺ , NH ₄ ⁺ , Mg ²⁺ /2, HN(CH ₃ ) ₃ ⁺ , HN(C ₂ H ₅ ) ₃ ⁺ , HN(C ₂ H ₄ OH) ₃ ⁺ , H ₂ N (C ₂ H ₄ OH) ₂ ⁺ etc. In particular, the cationic equivalent is an alkali metal cation or an equivalent of an alkaline earth metal cation.

Suitable linear or branched saturated or unsaturated aliphatic hydrocarbon residues with 1-30 carbon atoms are the corresponding alkyl residues with 1-30 carbon atoms and alkenyl residues with 1-30 carbon atoms and 1, 2, 3, or more than 3, CC-double connections.

Unsaturated aliphatic hydrocarbon residues with 1-30 carbon atoms, as a rule, have 1, 2 or 3 double bonds.

In a specific embodiment, we are talking about predominantly linear alkyl radicals, such as also occur in natural or synthetic fatty alcohols and oxo alcohols, or, respectively, predominantly linear alkenyl radicals, such as also occur in natural or synthetic fatty alcohols and oxo alcohols, which may be singly, 2-fold, 3-fold, 4-fold, 5-fold or 6-fold unsaturated.

If one of the radicals R, R ¹ , R ³ , R ^1' and R ^3' is alkyl or alkenyl, said radicals are preferably derived from natural raw materials, particularly preferably from renewable raw materials.

Suitable alkyl groups with 1-25 carbon atoms, alkyl groups with 1-20 carbon atoms and alkyl groups with 1-6 carbon atoms in each case are linear and branched alkyl groups.

Suitable alkenyl groups with 2-25 carbon atoms, alkenyl groups with 2-20 carbon atoms and alkenyl groups with 2-6 carbon atoms in each case are linear and branched alkenyl groups in each case with 1, 2, 3, or more 3, CC-double bonds.

Suitable alkenyl groups with 2-10 carbon atoms, alkenyl groups with 10-30 carbon atoms and alkenyl groups with 10-20 carbon atoms in each case are linear and branched alkenyl groups.

In the context of the present invention, "alkyl with 1-6 carbon atoms" means a linear or branched alkyl radical with 1-6 carbon atoms. Examples of these are methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, pentyl, hexyl and their positional isomers.

Alkyl with 1-20 carbon atoms means the aforementioned alkyl radicals with 1-6 carbon atoms, as well as linear or branched alkyl radicals with 7-20 carbon atoms. These include, for example, n-heptyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl, 2-propylheptyl, n-undecyl, n-dodecyl, n-tridecyl, iso-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl (stearyl), iso-stearyl, n-nonadecyl, n-eicosyl (araquinyl), and their position isomers.

Alkyl with 1-25 carbon atoms means the aforementioned alkyl radicals with 1-20 carbon atoms, as well as a linear or branched alkyl radical with 21-25 carbon atoms. These include, for example, n-geneicosyl, n-docosyl (behenyl), n-tricosyl, n-tetracosyl (behenyl), n-pentacosyl and their positional isomers.

Alkyl with 1-30 carbon atoms means the aforementioned alkyl radicals with 1-25 carbon atoms, as well as linear or branched alkyl radicals with 26-30 carbon atoms.

In the context of the present invention, "alkenyl with 2-6 carbon atoms" means a linear or branched alkenyl residue with 1 or 2 CC double bonds. Examples of these are ethenyl, n-propenyl, allyl, n-butenyl, n-butadienyl, n-pentenyl, n-pentadienyl, n-hexenyl, n-hexadienyl and their structural isomers.

Alkenyl with 2-25 carbon atoms means the aforementioned alkenyl residues with 2-6 carbon atoms, as well as a linear or branched alkyl residue with 7-25 carbon atoms and with 1, 2, 3, or more than 3, CC-double bonds. Examples of these are n-heptenyl, n-octenyl, n-octadienyl, n-octatrienyl, n-nonenyl, n-nonadienyl, n-nonatrienyl, n-decenyl, n-decadienyl, n-decatrienyl, n-dodecenyl, n-dodecadienyl , n-dodecatrienyl, n-tridecenyl, n-tridecadienyl, n-tridecatrienyl, n-tetradecenyl, n-tetradecadienyl, n-tetradecatrienyl, n-hexadecenyl, n-hexadecadienyl, n-hexadecatrienyl, n-heptadecenyl, n-heptadecadienyl, n -heptadecatrienyl, n-octadecenyl, n-octadecadienyl, n-octadecatrienyl, n-nonadecenyl, n-nonadecadienyl, n-nona-decatrienyl, n-eicozenyl, n-eicosadienyl, n-eicosatrienyl, n-geneicozenyl, n-geneicosadienyl, n -geneicosatrienyl, n-docosenyl, n-docosadienyl, n-docosatrienyl, n-tricosenyl, n-tricosadienyl, n-tricosatrienyl, n-tetracosenyl, n-tetracosadienyl, n-tetracosadienyl, oleyl, linolenyl and their structural isomers.

Alkenyl with 2-30 carbon atoms means the aforementioned alkenyl residues with 2-25 carbon atoms, as well as a linear or branched alkyl residue with 26-30 carbon atoms and with 1, 2, 3, or more than 3, CC double bonds.

Alkenyl with 2-10 carbon atoms is preferably linear or branched, and is preferably selected from -CH ₂ CH ₂ -, -CH(CH ₃ )-, -CH ₂ CH ₂ CH ₂ -, -CH(CH ₃ )CH ₂ - , -CH ₂ CH ₂ CH ₂ CH ₂ -, -CH ₂ CH (CH ₃ ) CH ₂ -, -CH (CH ₃ ) CH (CH ₃ ) -, -C ₅ H ₁₀ -, -C ₆ H ₁₂ - , -C ₇ H ₁₄ -, -C ₈ H ₁₆ -, -C ₉ H ₁₈ -, -C ₁₀ H ₂₀ - and their structural isomers.

Within the scope of the present invention, a saturated or unsaturated cycloaliphatic hydrocarbon residue with 3 to 10 carbon atoms means cycloalkanyl or cycloalkenyl, respectively, the ring having 3 to 10 carbon atoms. These cycloaliphatic hydrocarbon residues may in each case be unsubstituted or substituted. Saturated unsubstituted cycloaliphatic hydrocarbon residues are preferably cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl and cycloctyl. Saturated substituted cycloaliphatic hydrocarbon residues preferably contain 1, 2 or 3 substituents, which are independently selected from alkyl with 1-6 carbon atoms and alkenyl with 2-6 carbon atoms. Unsaturated unsubstituted cycloaliphatic hydrocarbon residues are preferably cyclopropenyl, cyclobutenyl, cyclopentenyl, cyclohexenyl, cycloheptenyl and cycloctenyl. The unsaturated substituted cycloaliphatic hydrocarbon radicals preferably contain 1, 2 or 3 substituents which are independently selected from C 1 -C 6 alkyl and C 2 -C 6 alkenyl.

In the context of the present invention, "cycloalkyl with 5-7 carbon atoms" means a monocyclic saturated or unsaturated hydrocarbon cycle with 5-7 carbon atoms. Examples of unsubstituted cycloalkyl with 5-7 carbon atoms are cyclopentyl, cyclohexyl, cycloheptyl. Examples of substituted C5-C7 cycloalkyl are methylcyclopentyl, ethylcyclopentyl, n-propylcyclopentyl, isopropylcyclopentyl, methyl cyclohexyl, ethyl cyclohexyl, n-propylcyclohexyl, isopropylcyclohexyl, isopropenylcyclohexyl and isobutenylcyclopropyl.

Within the scope of the present invention, a divalent saturated or unsaturated cycloaliphatic hydrocarbon residue with 3 to 10 carbon atoms means cycloalkanediyl or cycloalkenediyl, respectively, the ring having 3 to 10 carbon atoms. Examples of divalent saturated cycloaliphatic hydrocarbon residues are cyclopropan-1,2-diyl, cyclobutane-1,3-diyl, cyclopentane-1,2-diyl, cyclohexane-1,4-diyl, cycloheptan-1,3-diyl.

In the context of the present invention, "aryl" means a carbocyclic aromatic residue having from 6 to 14 carbon atoms. Examples of these are phenyl, naphthyl, fluorenzyl, azulenyl, anthracenyl and phenanthrenyl. Preferably aryl means phenyl or naphthyl, in particular phenyl. These aryl residues may in each case be unsubstituted or substituted. Substituted aryl residues preferably have 1, 2 or 3 substituents which are independently selected from C 1 -C 6 alkyl and C 2 -C 6 alkenyl. These include, for example, tolyl, xylylenyl, ethylphenyl, n-propylphenyl, isopropylphenyl, isopropenylphenyl and isobutenylphenyl.

A preferred embodiment of the invention are compounds of formula (I')

wherein

R ¹ is selected from hydrogen, a linear or branched saturated or unsaturated aliphatic hydrocarbon residue with 1-30 carbon atoms, saturated or unsaturated cycloaliphatic hydrocarbon radicals with 3-10 carbon atoms and aryl,

R ³ is selected from hydrogen and methyl,

X in each case means a bond or a divalent linear or branched saturated or unsaturated aliphatic hydrocarbon residue with 1-30 carbon atoms, or a divalent saturated or unsaturated cycloaliphatic hydrocarbon residue with 1-30 carbon atoms;

n means a number between 1 and 10, and

And means hydrogen or cationic equivalent;

k means a number between 1 and 100, and

R ² means a divalent linear or branched saturated aliphatic hydrocarbon residue having from 2 to 30 carbon atoms.

Preferably R ² is -CR ^a R ^b -CR ^c R ^d - wherein each R ^a , R ^b , R ^c and R ^d are independently selected from hydrogen, alkyl with 1-20 carbon atoms, unsubstituted cycloalkyl with 5 -7 carbon atoms, cycloalkyl with 5-7 carbon atoms and with 1, 2 or 3 alkyl substituents with 1-6 carbon atoms. In particular, each R ^a is independently hydrogen, C 1 -C 20 alkyl, unsubstituted C 5 -C 7 cycloalkyl.

Preferably R ^b independently means hydrogen or alkyl with 1-6 carbon atoms, in particular hydrogen or methyl, especially hydrogen.

Preferably each R ^c is independently hydrogen or C 1 -C 6 alkyl, in particular hydrogen or methyl, especially hydrogen.

Preferably, each R ^d is independently hydrogen or C 1 -C 6 alkyl, in particular hydrogen or methyl.

In a preferred embodiment, R ² is -CR ^a R ^b -CR ^c R ^d - wherein each R ^a is independently selected from hydrogen, C 1-20 alkyl, unsubstituted C 5-7 cycloalkyl, cycloalkyl with 5-7 carbon atoms and with 1, 2 or 3 alkyl substituents with 1-6 carbon atoms, each R ^b and R ^d means hydrogen and each R ^c means hydrogen or methyl.

If in the groups -O-[R ² -O] _k H the residue R ² means -CR ^a R ^b -CR ^c R ^d -, in which CR ^a R ^b and CR ^c R ^d do not have the same meaning (i.e. two carbon atoms are differently substituted), the orientation of each residue in the main -CR ^a R ^b -CR ^c R ^d - basically can be any. In other words, each R ² can mean -CR ^a R ^b -CR ^c R ^d - or -CR ^c R ^d -CR ^a R ^b -. As a rule, all residues R ² alkoxylate chain have the same orientation. Whether the most substituted carbon atom of the end of the alkoxylate chain bearing the hydroxycarboxylic acid is turned to the edge or inside the chain depends on the conditions of the alkoxylation reaction and especially on the catalyst used. Without wishing to be bound by theory, it is believed that the nucleophilic ring-opening reaction under acidic conditions generally follows the S _N 1 mechanism, i. the oxygen atom of the hydroxycarboxylic acid or, respectively, the terminal oxygen atom of the growing end of the chain binds to the more substituted carbon atom of the -CR ^a R ^b -CR ^c R ^d - residues, since a more stable one is intermediately formed, i.e. the most substituted, carbocation.

Since the variable n in the groups of the formula -(R ² -O) _n -R ³ is at least 2, the R ² residues of the individual repeating units may have the same or different values. In principle, the sequence of alkylene oxide units (R ² -O) is arbitrary.

In particular, k means a number from 1 to 50, in particular from 1 to 20, especially from 1 to 10.

Preferably A is hydrogen or an alkali metal cation or an equivalent of an alkaline earth metal cation, in particular hydrogen, K ⁺ , Na ⁺ , 1/2Mg ²⁺ .

Especially R ¹ is selected from hydrogen, alkyl with 1-25 carbon atoms, alkenyl with 1-25 carbon atoms and phenyl.

Particularly preferably R ¹ is selected from hydrogen, methyl, ethyl, propyl, isopropyl, n-butyl, 2-butyl, sec-butyl, tert-butyl, n-pentyl, 2-pentyl, 2-methylbutyl, 3-methylbutyl, 1, 2-dimethylpropyl, 1,1-dimethylpropyl, 2,2-dimethylpropyl, 1-ethylpropyl, n-hexyl, 2-hexyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1,2-dimethylbutyl, 1,3- dimethylbutyl, 2,3-dimethylbutyl, 1,1-dimethylbutyl, 2,2-dimethylbutyl, 3,3-dimethylbutyl, 1,1,2-trimethylpropyl, 1,2,2-trimethylpropyl, 1-ethylbutyl, 2-ethylbutyl, 1-ethyl-2-methylpropyl, n-heptyl, 2-heptyl, 3-heptyl, 2-ethylpentyl, 1-propylbutyl, n-octyl, 2-ethylhexyl, 2-propylheptyl, n-nonyl, n-decyl, n- undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, n-nonadecyl, arachinyl, behenyl, lignocerinyl, melissinyl, isotridecyl, iso-stearyl, oleyl, linoleyl, linolenyl, etc., in particular methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-buty la, n-pentyl, isoamyl, n-hexyl, 2-ethylhexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, 2-propylheptyl, n-undecyl, n-dodecyl, n-tridecyl, n- tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, n-nonadecyl, arachinyl, behenyl, lignocerinyl, melissinyl, isotridecyl, isostearyl, oleyl, linoleyl, linolenyl.

In particular, R ¹ is selected from hydrogen and alkyl with 1-10 carbon atoms.

Preferably X is a bond, C 1-20 alkylene and C 2-20 alkenylene, in particular a bond, C 1-15 alkylene and C 2-15 alkenylene, especially a bond, C 1-12 alkylene carbon and alkenylene with 2-12 carbon atoms.

Preferably R ³ means hydrogen.

Preferably n is 1 or 2, in particular 1.

The compounds of formula (I) according to the invention have a saponification number of less than 10 mg KOH/g, preferably less than 9 mg KOH/g, especially less than 8 mg KOH/g.

Another object of the present invention is a process for the preparation of compounds of general formula (I), according to which

a) at least one salt of hydroxycarboxylic acid of general formula (III),

wherein

R' means an organic residue which contains at least one hydroxyl group and in which all acid groups, if necessary, are completely deprotonated; and

each A' is independently a cationic equivalent;

subjected to interaction with at least one epoxide of general formula (IV)

wherein

each R ^a , R ^b , R ^c and R ^d are independently selected from hydrogen, unsubstituted alkyl with 1-30 carbon atoms, unsubstituted cycloalkyl with 5-7 carbon atoms and cycloalkyl with 5-7 carbon atoms, which contains 1, 2 or 3 substituents independently selected from alkyl with 1-6 carbon atoms and alkenyl with 2-6 carbon atoms,

wherein the two residues R ^a and R ^c , also together with the -CR ^b -CR ^d - group to which they are attached, may be a 5-7 carbon cycloalkyl which is unsubstituted or has 1, 2 or 3 substituents, as selected independently from alkyl with 1-6 carbon atoms and alkenyl with 2-6 carbon atoms; and

b) if necessary, the reaction product from step a) is treated with acid.

Stage a)

The alkoxylation reaction in step a) can be carried out in multiple steps, first, at least one salt of hydroxycarboxylic acid (III) is reacted with one epoxide of general formula (IV), and then the resulting reaction mixture, if necessary after separation and/or purification, in additional alkoxylation reactions are reacted with at least one additional epoxide of general formula (IV).

Preferably, the alkoxylation reaction to obtain compounds of general formula (I) is carried out in a one-pot reaction in which at least one hydroxycarboxylic acid salt of general formula (III) is subjected to alkoxylation in the presence of at least one epoxide of general formula (IV).

The compounds of formula (III) may optionally contain acidic groups. The acid groups contained are in a fully deprotonated form.

Compound (I) is obtained by reacting a hydroxycarboxylic acid salt of general formula (III) or (III') with an epoxide of general formula (IV). The choice of reaction conditions for the interaction of alcohol with alkylene oxide can be performed by methods known to the person skilled in the art.

Alkoxylation can proceed randomly, alternatively or blockwise.

In step a) of the process according to the invention, the compound R'-C(=O)-O-A' (III) is provided.

Preferred compounds (III) for use in step a) are salts of hydroxycarboxylic acids, the salt of formula (III') being used as the salt of hydroxycarboxylic acid.

wherein

R ¹ ' has one of the meanings given above for R ¹ ;

R ³ ' has one of the meanings given above for R ³ ;

X' has one of the values given above for X;

n has one of the above values; and

A' means cationic equivalent.

For suitable and preferred definitions of R ¹ ', R ³ ', X', A' and n, reference is made in full to the previous statements regarding these residues and variables.

In a preferred embodiment, the hydroxycarboxylic acid salt is selected from lactic acid, glycolic acid, 12-hydroxystearic acid, ricinoleic acid, 3-hydroxybutyric acid, 4-hydroxybutyric acid, mandelic acid, and mixtures thereof.

In a particularly preferred embodiment, the hydroxycarboxylic acid salt is selected from lactic acid, 12-hydroxystearic acid and ricinoleic acid salts.

In a preferred embodiment, the alkylene oxide is selected from ethylene oxide, propylene oxide, 1,2-butylene oxide, 2,3-butylene oxide, C10-C30 alkylene oxides, and mixtures thereof. In particular, the alkylene oxide is selected from ethylene oxide, propylene oxide, 1,2-butylene oxide, 2,3-butylene oxide, hexadecene epoxide and dodecene epoxide.

In general, 1 to 8 moles, preferably 2 to 7 moles of epoxide (IV) are used per mole of compound (III). Any remaining residues of unreacted epoxide (IV) may be removed by distillation or removed by stripping with an inert gas such as nitrogen or argon.

In the first step of step a), 1 to 7 moles, preferably 2 to 6 moles of epoxide (IV) are used per mole of compound (III). In the second step of step a), 0.5 to 2 mol, preferably 1 to 1.5 mol of epoxide (IV) is used per mol of compound (III).

The reaction in step a) usually takes place at a temperature of 50°C to 180°C, preferably 85°C to 160°C, particularly preferably 95°C to 150°C.

Alkoxylation is preferably carried out at normal pressure or reduced pressure. In the case of carrying out the alkoxylation under reduced pressure, the pressure is preferably in the range from 1 mbar to 1.1 bar, in particular from 5 mbar to 1 bar, in particular from 10 mbar to 900 mbar. This is true for both one-step and two-step alkoxylation reactions. Preferably, the reaction is carried out at normal pressure.

The compound (III) from step a) can be heated together with the epoxide (IV) until the desired reaction temperature is reached. Another possibility is that the compound (III) is first heated to the desired reaction temperature. Epoxide (IV) is added thereto at the desired reaction temperature.

Preferably the compound (III) is heated to the reaction temperature. Epoxide (IV) is added thereto at the reaction temperature. This can be done in one or more steps at different temperatures. The addition can also take place over a longer period of time, and the temperature can be kept constant or continuously increased. After the epoxide (IV) has been completely added, the mixture may be kept at the reaction temperature or other temperature for a certain time.

Preferably, the addition of epoxide (IV) is carried out in several steps. In this case, two different epoxides (IV) are preferably used at different stages. In the first step in step a), the hydroxycarboxylic acid salt (III) reacts with at least one first epoxide (IV). For the reaction in the first step in step a), the first epoxide (IV) is preferably selected from ethylene oxide, propylene oxide, 1,2-butylene oxide, 2,3-butylene oxide. The product obtained in the first stage reacts with the second epoxide (IV) in the second stage. The second epoxide (IV) is preferably selected from epoxides (IV) with 10-20 carbon atoms, in particular selected from hexadecene epoxide and dodecene epoxide.

Alkoxylation can proceed autocatalytically or in the presence of a catalyst.

Alkali metals, alkali or alkaline earth metal hydroxides, alkali or alkaline earth metal alcoholates, alkali or alkaline earth metal acetates, alkali or alkaline earth metal hydrides, phosphines, double metal cyanides, Lewis acids or tertiary amines are generally used as catalysts.

Preferred alkali metals are lithium, sodium or potassium, potassium is particularly preferred.

Preferred alkali or alkaline earth metal hydroxides are lithium, sodium, potassium, calcium or barium hydroxides, lithium, sodium and potassium hydroxides are particularly preferred.

Preferred alkali or alkaline earth metal alcoholates are sodium methoxide, potassium methoxide, sodium ethoxide, potassium ethoxide or potassium tert-butoxide, sodium methoxide or potassium methoxide are particularly preferred.

Preferred alkali or alkaline earth metal acetates are sodium acetate (NaOAc) or potassium acetate (KOAc), sodium acetate (NaOAc) is particularly preferred.

Preferred alkali or alkaline earth metal hydrides are lithium hydride, sodium hydride or potassium hydride, sodium hydride is particularly preferred.

The preferred phosphine is triphenylphosphine.

Preferred Lewis acids are B(CH ₃ ) ₃ , B(OH) ₃ , BF ₃ , B(Cl) ₃ , AlCl ₃ , Al(OEt) ₃ , Ti(OiPr) ₄ , BF3 is particularly preferred.

Preferred tertiary amines are trimethylamine, triethylamine, tris(ethylhexylamine), tripropylamine, tributylamine, trihexylamine, trioctylamine or pyridine.

Preferred double metal cyanides are Mn ₃ [Co(CN) ₆ ] ₂ and Zn ₃ [Co(CN) ₆ ] ₂ .

The catalyst is preferably used in an amount of 0.01 to 5 mol %, based on the salt of the hydroxycarboxylic acid (III).

Preferably, the alkylation reaction is carried out in the absence of a catalyst.

The reaction in step a) can be carried out in the presence of a solvent which is inert under the reaction conditions. Examples of such solvents are, for example, tetrahydrofuran, methyl tert-butyl ether, dioxane, toluene or xylene. It is also possible to carry out the reaction in bulk, i. e. without external (added) solvents.

The reaction according to the invention can be carried out in batch or continuous mode, preferably it is carried out in batch mode.

The reaction according to the invention can be carried out in a stirred tank, a pumped reactor, a series of stirred tanks or a tubular reactor, preferably it is carried out in a stirred tank or a pumped reactor.

Step b)

Step b) is carried out if necessary. It may be advantageous, if necessary, to acidify the reaction product from step a) to obtain an alkoxylated hydroxycarboxylic acid.

As a rule, carboxylic acids, sulfonic acids, CO ₂ , mineral acids are used for this. It is also possible to use ion exchangers. Preferred are carboxylic acids and mineral acids, particularly preferred carboxylic acids.

The preferred carboxylic acid is acetic acid. Especially preferred is glacial acetic acid.

Another object of the invention is alkoxylated hydroxycarboxylic acids or their salts of formula (I) or (I') and mixtures thereof, obtained by the method described above.

The compounds of general formula (I) and general formula (I') are advantageously suitable for use as surfactants. In general, it can be, for example, cosmetic compositions, pharmaceutical compositions, hygiene products, detergents and cleaners, coating agents, compositions for the paper industry, compositions for the textile industry, etc.

In this case, the surfactants according to the invention can be used as the sole surfactant. In a preferred embodiment, the compounds of general formula (I) and general formula (I') are distinguished by their good compatibility with other surfactants.

Compositions containing surfactants

The compounds of general formula (I) or, respectively, of general formula (I') according to the invention are particularly preferably suitable for formulating compositions containing surfactants. In particular, we are talking about aqueous compositions containing surfactants. Compounds (I) or (I') in compositions of this type are distinguished by their good water solubility, good compatibility with many active ingredients and auxiliaries used in cosmetics, good foaming properties and good rheological properties.

Compositions containing surfactants according to the invention preferably have a total content of surfactants from 0.1 to 75% by weight, particularly preferably from 0.5 to 60% by weight, in particular from 1 to 50% by weight. , in terms of the total weight of the composition containing surfactants.

Suitable surfactants are anionic surfactants other than compounds (I) and (I'), nonionic surfactants, cationic surfactants, amphoteric surfactants and mixtures thereof.

Typical examples of anionic surface o-active substances are soaps, alkyl sulfonates, alkyl benzene sulfonates, olefin sulfonates, alkyl ether sulfonates, glycerol ether sulfonates, methyl ester sulfonates, fatty sulfonic acids, alkyl sulphates, fatty alcohol ether sulphates, glycerol ether sulphates, ether sulphates. fatty acid esters, mixed hydroxyether sulfates, monoglyceride (ether) sulfates, fatty acid simple (ether) amide sulfates, mono- and dialkyl sulfosuccinates, mono- and dialkyl sulfosuccinamates, sulfotriglycerides, amide soaps, carboxylic acid ethers and their salts, fatty isethionates fatty acids, fatty acid sarcosinates, fatty acid taurides, N-acylamino acids such as, for example, acylglutamates and acylaspartates, as well as acyl lactylates, acyl tartrates, alkyl oligoglucoside sulfates, alkyl glucose carboxylates, protein-fatty acid condensates and alkyl ether phosphates.

Suitable soaps are, for example, alkali, alkaline earth and ammonium salts of fatty acids, such as potassium stearate.

Suitable olefinsulfonates are obtained, for example, by adding SO ₃ to olefins of the formula R ⁵ -CH=CH-R ⁴ and subsequent hydrolysis and neutralization, and R ⁵ and R ⁴ independently of each other represent H or alkyl residues containing from 1 to 20 carbon atoms, provided that R ⁵ and R ⁴ together have at least 6, and preferably 8 to 20, in particular 10 to 16, carbon atoms. For preparation and use, reference should be made to the review article in J.Am. oil. Chem. Soc, 55, 70 (1978). The olefinsulfonates may be present as alkaline, alkaline earth, ammonium, alkyl ammonium, alkanolammonium or glucammonium salts. Preferably, the olefinsulfonates are present as sodium salts. Hydrolyzed product sulfonated alpha-olefin, that is, alpha-olefinsulfonate, consists of about 60% of the mass. alkanesulfonates and about 40% of the mass. hydroxyalkane sulfonates; of which about 80 to 85% of the mass. are monosulfonates, and from 15 to 20% of the mass. disulfonates.

Preferred methyl ether sulfonates (MES) are derived from the sulfonation of fatty acid methyl esters of vegetable or animal fats or oils. Preferred are methyl ethersulfonates from vegetable fats and oils, such as rapeseed oil, sunflower oil, soybean oil, palm oil, coconut oil, etc.

Preferred alkyl sulfates are fatty alcohol sulfates of the general formula R ⁶ -O-SO ₃ Y, in which R ⁶ is a linear or branched, saturated or unsaturated hydrocarbon residue having from 6 to 22 carbon atoms, and Y is an alkali metal, the monovalent equivalent of the alkaline earth charge metal, ammonium, mono-, di-, tri- or tetraalkylammonium, alkanolammonium or glucammonium. Suitable fatty alcohol sulfates are preferably obtained by sulfation of natural fatty alcohols or synthetic oxo alcohols and subsequent neutralization. Typical examples of fatty alcohol sulfates are the sulfation products of capro alcohol, capryl alcohol, 2-ethylhexyl alcohol, capric alcohol, lauryl alcohol, isotridecyl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, elaidyl alcohol, petroselinyl alcohol. alcohol, linoleic alcohol, linolenic alcohol, behenyl alcohol and eleostearyl alcohol, as well as their salts and mixtures. Preferred fatty alcohol sulfate salts are the sodium and potassium salts, especially the sodium salts. Preferred fatty alcohol sulphate mixtures are based on industrial alcohol mixtures, which are obtained, for example, by high-pressure hydrogenation of industrial methyl esters based on fats and oils, or by the hydrogenation of aldehydes from oxosynthesis, or by the dimerization of unsaturated fatty alcohols. Preferably, fatty alcohols and mixtures of fatty alcohols having from 12 to 18 carbon atoms and in particular from 12 to 14 carbon atoms are used for the preparation of alkyl sulfates. Typical examples of this are industrial alcohol sulfates based on vegetable raw materials.

Preferred sarcosinates are sodium lauroyl sarcosinate or sodium stearoyl sarcosinate.

Preferred protein and fatty acid condensates are wheat-based vegetable products.

Preferred alkyl phosphates are alkyl esters of mono- and diphosphoric acids.

Suitable acylglutamates are compounds of formula (V)

in which COR ⁷ is a linear or branched acyl residue having from 6 to 22 carbon atoms and 0, 1, 2 or 3 double bonds, and Y is a hydrogen atom, an alkali metal, a univalent charge equivalent of an alkaline earth metal, ammonium, alkylammonium, alkanolammonium, or glucammonium. Acylglutamates are obtained, for example, by Schotten-Baumann acylation of glutamic acid with fatty acids, fatty acid esters or fatty acid halides. Acylglutamates are commercially available from, for example, BASF SE, Clariant AG, Frankfurt/Germany, or Ajinomoto Co. Inc., Tokyo/Japan. A review regarding the preparation and properties of acylglutamates is found in M. Takehara et al. in J. Am. oil chem. soc. 49 (1972) 143. Exemplary acylglutamates are preferably derived from fatty acids having 6 to 22 carbon atoms and particularly preferably 12 to 18 carbon atoms. In particular, mono- or di-alkaline metal salts of acylglutamate are used. These include, for example, (trade names of Ajinomoto, USA in brackets): sodium cocoylglutamate (Amisoft CS-11), disodium cocoylglutamate (Amisoft ECS-22SB), triethanolammonium cocoylglutamate (Amisoft CT-12), triethanolammonium lauroylglutamate (Amisoft LT- 12), sodium myristoylglutamate (Amisoft MS-11), sodium stearoylglutamate (Amisoft HS-11 P) and mixtures thereof.

Nonionic surfactants include, for example:

- polyoxyalkylene esters of fatty alcohols, for example polyoxyethylene acetate of lauryl alcohol,

- simple alkyl polyoxyalkylene ethers, which are derivatives of low molecular weight alcohols with 1-6 carbon atoms or fatty alcohols with 7-30 carbon atoms. In this case, the ether component may be derived from ethylene oxide structural units, propylene oxide structural units, 1,2-butylene oxide structural units, 1,4-butylene oxide structural units and their random copolymers and block copolymers.

In particular, they include alkoxylates of fatty alcohols and alkoxylates of oxoalcohols, in particular, of the type RO-(R ⁸ O) _r (R ⁹ O) _s R ¹⁰ , where R ⁸ and R ⁹ independently of each other = C ₄ H ₄ , C ₆ H ₆ , C ₈ H ₈ , a R ¹⁰ = H or alkyl with 1-12 carbon atoms, R = alkyl with 3-30 carbon atoms or alkenyl with 6-30 carbon atoms, r and s independently of each other are from 0 to 50, both cannot be equal to 0, such as polyoxyethylene ethers of isotridecyl alcohol and oleyl alcohol,

- polyoxyethylene ethers of alkylaryl alcohol, for example polyoxyethylene ethers of octylphenol,

- alkoxylated animal and/or vegetable fats and/or oils, for example corn oil ethoxylates, castor oil ethoxylates, animal fat ethoxylates,

- esters of glycerol, such as, for example, glycerol monostearate,

- alkylphenol alkoxylates, such as, for example, ethoxylated isooctyl-, octyl- or nonylphenol, polyoxyethylene ether of tributylphenol,

- alkoxylates of fatty amines, alkoxylates of fatty acid amides and diethanolamides of fatty acids, in particular their ethoxylates,

- surfactant sugars, esters of sorbitol, such as, for example, esters of sorbitol and fatty acids (sorbitan monooleate, sorbitan tristearate), polyoxyethylene esters of sorbitol and fatty acids, alkyl polyglycosides, N-alkyl gluconamides,

- alkyl methyl sulfoxides,

- alkyldimethylphosphine oxides, such as, for example, tetradecyldimethylphosphine oxide.

Suitable amphoteric surfactants are, for example, alkyl betaines, alkyl amidopropyl betaines, alkyl sulfo betaines, alkyl glycinates, alkyl carboxyglycinates, alkyl amphoacetates or α-propionates, alkylamphodiacetes or α-dipropionates. For example, cocodimethylsulfopropyl betaine, lauryl betaine, cocamidopropyl betaine, sodium cocamphopropionate, or tetradecyldimethylamine oxide can be used.

Cationic surfactants include, for example, quaternized ammonium compounds, in particular alkyltrimethylammonium and dialkyldimethylammonium halides and alkyl sulfates, as well as pyridine and imidazoline derivatives, in particular alkylpyridinium halides. By way of example, behenyl or cetyltrimethylammonium chlorides can be used. Also suitable are the so-called esterquats, which are based on quaternary triethanolmethylammonium or quaternary diethanoldimethylammonium compounds with long hydrocarbon chains in the form of fatty acid esters. These include, for example, bis(acyloxyethyl)hydroxyethylammonium methosulfate. Also suitable is Dehyquart L 80 (INCI name: Dicocoylethyl Hydroxyethylmonium Methosulfate (and) Propylene Glycol).

Cosmetic and pharmaceutical

The compounds of general formula (I) and general formula (I') are preferably suitable for formulating cosmetic and pharmaceutical products, especially aqueous cosmetic and pharmaceutical products.

Another object of the invention is a cosmetic or pharmaceutical composition containing

a) at least one compound of general formula (I) or (I') as defined above,

b) at least one cosmetic or pharmaceutical active, and

c) optionally at least one cosmetic or pharmaceutical excipient different from components a) and b).

Preferably, at least one compound of general formula (I') is used as component a).

Preferably component c) comprises at least one cosmetic or pharmaceutical carrier.

Preferably the carrier component c) is selected from

i) water,

ii) water-miscible organic solvents, preferably C2-C4 alkane alcohols, in particular ethanol,

iii) oils, fats, waxes,

iv) other than iii) esters of monocarboxylic acids with 6-30 carbon atoms and mono-, di- or trihydric alcohols,

v) saturated acyclic and cyclic hydrocarbons,

vi) fatty acids,

vii) fatty alcohols,

viii) carrier gases, and mixtures thereof.

Particularly suitable cosmetically compatible oil or fatty components c) are described in Karl-Heinz Schrader, Grundlagen und Rezepturen der Kosmetika, 2. Auflage, Verlag Huthig, Heidelberg, pp. 319-355, to which reference is hereby incorporated.

The cosmetics according to the invention can be skin cosmetics, hair cosmetics, dermatological, hygiene or pharmaceutical products. Due to their surface-active properties, the compounds of formula (I) and formula (I') described above are suitable, in particular in compositions, for skin and/or hair cleansing.

Preferably, the agents of the invention are present in the form of an aqueous solution, a solid composition (eg a bar of soap or a cleaning stick), a foam, an emulsion, a suspension, a lotion, a gel, a paste or a spray. If desired, liposomes or microspheres can also be used.

The cosmetic preparations according to the invention may additionally contain cosmetically and/or dermatologically active and active substances, as well as excipients. Preferably, the cosmetics according to the invention contain at least one compound of formula (I) or formula (I') as defined above, at least one carrier C) as defined above, and at least one component different from them, which preferably selected from cosmetic actives, emulsifiers, surfactants, preservatives, perfume oils, co-thickening agents, hair polymers, hair and skin conditioners, graft polymers, water-soluble or dispersible silicone-containing polymers, light-blocking agents, whitening agents , gelling agents, conditioning agents, tinting agents, self-tanning agents, dyes, pigments, bodying agents, moisture retention agents, fat re-introducing agents, collagen, protein hydrolysates, lipids, antioxidants, defoamers, antistatic agents, emollients and plasticizers.

In addition to the compounds of formula (I) and formula (I'), cosmetics may contain at least one thickening agent. These include, for example, polysaccharides and organic layered minerals such as Xanthan Gum® (Kelzan® from Kelco), Rhodopol® 23 (Rhone Poulenc) or Veegum® (from R.T. Vanderbilt) or Attaclay® (from Engelhardt). Suitable thickening agents are also organic natural thickening agents (agar-agar, carrageenan, tragacanth, gum arabic, alginates, pectins, polyoses, guar gum, locust bean gum, starches, dextrins, gelatin, casein) and inorganic thickening agents (polysilicic acids, clay minerals such as montmorillonites, zeolites, silicic acids). Other thickening agents are polysaccharide gums such as gum arabic, agar, alginates, carrageenan and their salts, guar gum, guarana, tragacanth, gellan gum, ramsan gum, dextran or xanthan and their derivatives, such as propoxylated guar gum, and mixtures thereof. . Other polysaccharide thickeners are, for example, starches of various origins and starch derivatives, for example hydroxyethyl starches, starch phosphate esters or starch acetates or carboxymethylcellulose or its sodium salt, methyl-, ethyl-, hydroxyethyl-, hydroxy-propyl-, hydroxypropylmethyl- or hydroxyethylmethylcellulose or cellulose acetate. In addition, layered silicates can be used as a thickening agent. These include, for example, the magnesium or sodium-magnesium layered silicates available under the trade name Laponite® from Solvay Alkali and the magnesium silicates from Sud-Chemie.

Suitable cosmetic and/or dermatological actives are, for example, skin and hair coloring agents, self-tanning agents, whitening agents, keratin strengthening agents, antimicrobial actives, actives with light filters, repellant actives, hyperemic actives, with keratolytic and keratoplastic effect, anti-dandruff active substances, anti-inflammatory substances, substances with a keratinizing effect, active substances effective as antioxidants or radical scavengers, moisturizing or moisture-retaining substances in the skin, nourishing active substances, deodorizing active substances, sebostatic active substances, plant extracts, anti-erythematous or anti-allergic active substances and mixtures thereof.

Tanning actives which are suitable for browning the skin without natural or artificial exposure to UV radiation are, for example, dihydroxyacetone, alloxan or walnut shell extract. Suitable keratin strengthening agents are generally active agents such as those used in antiperspirants, such as potassium aluminum sulfate, aluminum hydroxychloride, aluminum lactate, etc. Antimicrobial actives are used to destroy or inhibit the growth of microorganisms, and thus serve both as a preservative and as a deodorant that reduces the formation or intensity of body odor. These include, for example, conventional preservatives known to those skilled in the art, such as p-hydroxybenzoic acid esters, imidazolidinyl urea, formaldehyde, sorbic acid, benzoic acid, salicylic acid, and the like. Substances with this type of deodorizing effect are, for example, zinc ricinoleate, triclosan, undecylenic acid alkylolamides, triethyl citric acid ester, chlorhexidine, and the like. Suitable active substances with light filters are those which absorb UV radiation in the UV-B and/or UV-A range. Suitable UV filters are those mentioned above. Also suitable are p-aminobenzoic acid esters, cinnamic acid esters, benzophenones, camphor derivatives, as well as UV-retarding pigments such as titanium dioxide, talc and zinc oxide. Suitable repellent actives are compounds which are able to keep or repel certain animals, especially insects, from people. These include, for example, 2-ethyl-1,3-hexanediol, N,N-diethyl-m-toluamide, etc. Suitable substances with a hyperemic action that activate the blood circulation in the skin are, for example, essential oils such as mountain pine, lavender, rosemary, juniper berries, horse chestnut extract, birch leaf extract, hay blossom extract, ethyl acetate, camphor, menthol, oil peppermint, rosemary extract, eucalyptus oil, etc. Suitable substances with a keratolytic and keratoplastic effect are, for example, salicylic acid, calcium thioglycolate, thioglycolic acid and its salts, sulfur, etc. Suitable anti-dandruff actives are, for example, sulfur, polyethylene glycol sorbitan sulfur monooleate, sulfur ricinol polyethoxylate, pyrithione-zinc, pyrithione-aluminum, etc. Suitable anti-inflammatory substances that prevent skin irritation are, for example, allantoin, bisabolol, dragosanthol, chamomile extract, panthenol, etc.

The cosmetic compositions according to the invention may contain at least one cosmetic or pharmaceutical polymer as a cosmetic active substance (as well as optionally as an excipient). These include, in general, anionic, cationic, amphoteric and neutral polymers.

Examples of anionic polymers are copolymers of acrylic acid and acrylamide and their salts; sodium salts of polyhydroxycarboxylic acids, water-soluble or water-dispersible polyesters, polyurethanes, such as Luviset PUR® from BASF, and polyureas. Particularly suitable polymers are copolymers of tert-butyl acrylate, ethyl acrylate, methacrylic acid (e.g. Luvimer® 100P), copolymers of ethyl acrylate and methacrylic acid (e.g. Luvimer® MAE), copolymers of N-tert-butyl acrylamide, ethyl acrylate, acrylic acid (Ultrahold® 8, strong ), copolymers of vinyl acetate, crotonic acid and optionally other vinyl esters (e.g. Luviset® brand), copolymers of maleic anhydride, optionally alcohol-reacted, anionic polysiloxanes, e.g. e.g. Luviskol® VBM), copolymers of acrylic acid and methacrylic acid with hydrophobic monomers, such as, for example, alkyl esters of (meth)acrylic acid with 4-30 carbon atoms in alkyl, alkyl vinyl esters with 4-30 carbon atoms in alkyl , simple alkylvinyl ethers with 4-30 carbon atoms in the alkyl and hyaluronic acid. A further example of an anionic polymer is the methyl methacrylate/methacrylic acid/acrylic acid/urethane acrylate copolymer commercially available under the designation Luviset® Shape (INCI name: Polyacrylate-22). In addition, examples of anionic polymers are copolymers of vinyl acetate and crotonic acid, such as, for example, are available under the names Resyn® (National Starch) and Gafset® (GAF) and vinylpyrrolidone/vinyl acrylate copolymers, available, for example, under the trade name Luviflex® (BASF). Other suitable polymers are terpolymers of vinylpyrrolidone/acrylate and sodium sulfonate-containing polyamides or sodium sulfonate-containing polyesters available under the name Luviflex® VBM-35 (BASF). Also suitable are vinyl pyrrolidone/ethyl methacrylate/methacrylic acid copolymers, such as those sold by Stepan under the trademarks Stepanhold-Extra and -R1, and the Carboset® brand by BF Goodrich.

Suitable cationic polymers are, for example, cationic polymers with the designation Polyquaternium according to the INCI nomenclature, e.g. ), copolymers of N-vinylpyrrolidone and dimethylaminoethyl methacrylate quaternized with diethyl sulfate (Luviquat® PQ 11), copolymers of N-vinylcaprolactam, N-vinylpyrrolidone and N-vinylimidazolium salts (Luviquat® Hold); cationic cellulose derivatives (Polyquaternium-4 and -10), acrylamide copolymers (Polyquaternium-7) and chitosan. Also suitable cationic (quaternized) polymers are Merquat® (polymer based on dimethyldiallylammonium chloride), Gafquat® (quaternary polymers that are formed by the reaction of polyvinylpyrrolidone with quaternized ammonium compounds), JR polymer (hydroxyethyl cellulose with cationic groups) and plant-based cationic polymers, for example, guar polymers such as Rhodia's Jaguar® brands.

The most suitable polymers are neutral polymers such as polyvinylpyrrolidones, copolymers of N-vinylpyrrolidone and vinyl acetate and/or vinyl propionate, polysiloxanes, polyvinylcaprolactam and other copolymers with N-vinylpyrrolidone, polyethyleneimines and their salts, polyvinylamines and their salts, cellulose derivatives, salts and derivatives polyaspartic acid. These include, for example, Luviflex® Swing (partially saponified copolymer of polyvinyl acetate and polyethylene glycol, BASF).

Suitable polymers are also non-ionic, water-soluble or water-dispersible polymers or oligomers, such as polyvinyl caprolactam, for example Luviskol® Plus (BASF SE), or polyvinylpyrrolidone and its copolymers, in particular with vinyl esters, such as vinyl acetate, for example , Luviskol® VA 37, VA 55, VA 64, VA 73 (BASF SE); polyamides, for example based on itaconic acid and aliphatic diamines, such as are described, for example, in DE-A-43 33 238.

Suitable polymers are also amphoteric or zwitterionic polymers, such as the copolymers of octylacrylamide, methyl methacrylate, tert-butylaminoethyl methacrylate, 2-hydroxypropyl methacrylate, available under the designation Amphomer® (National Starch), as well as zwitterionic polymers, such as are disclosed, for example, in German patent applications DE 3929973 , DE 2150557, DE 2817369 and DE 3708451. Copolymers of acrylamidopropyltrimethylammonium chloride and acrylic or methacrylic acid and their alkali metal or ammonium salts are preferred zwitterionic polymers. Further suitable zwitterionic polymers are copolymers of methacrylethyl betaine and methacrylate, which are commercially available under the designation Amersette® (AMERCHOL), and copolymers of hydroxyethyl methacrylate, N,N-dimethylaminoethyl methacrylate methyl methacrylate and acrylic acid (Jordapon®).

Suitable polymers are also non-ionic, siloxane-containing, water-soluble or water-dispersible polymers, for example polyethersiloxanes such as Tegopren® (Goldschmidt) or Belsil® (Wacker).

In one particular embodiment, the compositions according to the invention contain at least one polymer which acts as a thickener.

Suitable polymeric thickeners are, for example, optionally modified polymeric natural substances (carboxymethylcellulose and other cellulose ethers, hydroxyethyl- and -propylcellulose and the like), as well as synthetic polymeric thickeners (polyacrylic and polymethacrylic compounds, vinyl polymers, polycarboxylic acids, polyethers). , polyimines, polyamides). These include, in part, the previously mentioned polyacrylic and polymethacrylic compounds, for example, high molecular weight, cross-linked with a polyalkenylpolyether, in particular allyl ether, sucrose, pentaerythritol or propylene, acrylic acid homopolymers (INCI designation: Carbomer). Such polyacrylic acids are available, inter alia, from BF Goodrich under the trade name Carbopol®, for example Carbopol 940 (molecular weight about 4,000,000), Carbopol 941 (molecular weight about 1,250,000) or Carbopol 934 (molecular weight about 3,000,000). Also included are acrylic acid copolymers, which are available, for example, from Rohm & Haas under the trade names Aculyn® and Acusol®, for example, anionic, non-associative polymers Aculyn 22, Aculyne 28, Aculyn 33 (crosslinked), Acusol 810 , Acusol 823 and Acusol 830 (CAS number 25852-37-3). Particularly suitable are also associative thickeners, for example based on modified polyurethanes (HEUR) or hydrophobically modified copolymers of acrylic or methacrylic acid (thickeners of the HASE type - short for High Alkali Swellable Emulsion).

According to one preferred embodiment, the compositions according to the invention are skin cleansers.

Preferred skin cleansers are soaps with liquid to gel consistency such as clear soaps, luxury soaps, deodorant soaps, cream soaps, baby soaps, skin protecting soaps, abrasive soaps and synthetic detergents, paste soaps, mild soaps and detergents. pastes, liquid washes, showers and baths such as washing lotions, showers and gels, bath foams, bath oils and scrubs, shaving foams, lotions and creams.

Skin cleansers preferably contain at least compounds of formula (I) and formula (I') in a concentration of from about 0.001 to 70% by weight, preferably from 0.01 to 50% by weight, most preferably from 0.1 to 30 % wt., in terms of the total weight of the product.

According to another preferred embodiment, the compositions according to the invention are shower gels, shampoo compositions or bath products.

Such compositions contain at least one compound of general formula (I) or general formula (I') as a base surfactant and optionally at least one amphoteric and/or nonionic surfactant as an additional surfactant. . Other suitable actives and/or adjuvants are generally selected from lipids, perfume oils, colorants, organic acids, preservatives, antioxidants, thickeners/gelling agents, skin conditioning agents, and moisture retaining agents.

These compositions preferably contain from 2 to 50% by weight, preferably from 5 to 40% by weight, particularly preferably from 8 to 30% by weight. surfactant, based on the total weight of the composition.

All anionic, neutral, amphoteric or cationic surfactants commonly used in body cleansers can additionally be used in wash, shower and bath products.

Suitable surfactants are those mentioned above.

In addition, shower gel/shampoo compositions may contain additional thickeners such as, for example, common salt, PEG-55, propylene glycol oleate, PEG-120-methylglucosadioleate, and others. Suitable commercially available additional thickeners are, for example, Arlypon TT (INCI name: PEG/PPG-120/10 Trimethylolpropane Trioleate (and) Laureth-2) and Arlypon F (INCI name: Laureth-2). In addition, shower gel/shampoo compositions may contain other actives and excipients and water.

The compounds of formula (I) and formula (I') according to the invention are also preferably suitable as surfactants for shampoo compositions which may additionally contain other conventional surfactants.

Shampoo compositions can use conventional conditioning agents to achieve certain effects. These include, for example, the above cationic polymers with the designation Polyquaternium according to the INCI nomenclature, in particular, copolymers of vinylpyrrolidone and N-vinylimidazolium salts (Luviquat® FC, Luviquat® HM, Luviquat® MS, Luviquat® Care), copolymers of N- vinylpyrrolidone and dimethylaminoethyl methacrylate quaternized with diethyl sulfate (Luviquat®PQ 11), copolymers of N-vinylcaprolactam, N-vinylpyrrolidone and N-vinylimidazolium salts (Luviquat® Hold); cationic cellulose derivatives (Polyquaternium-4 and -10), acrylamide copolymers (Polyquaternium-7). In addition, protein hydrolysates can be used, as well as conditioning agents based on silicone compounds, such as polyalkylsiloxanes, polyarylsiloxanes, polyarylalkylsiloxanes, polyethersiloxanes or silicone resins. Other suitable silicone compounds are dimethicone copolyols (CTFA) and amino-functional silicone compounds such as amodimethicones. In addition, cationic guar gum derivatives such as guarhydroxypropyltrimonium chloride (INCI) may be used.

According to another preferred embodiment, the compositions according to the invention are skin care and protection cosmetics, nail care products or color cosmetic compositions.

In addition, the compounds of formula (I) and formula (I') can be used in nasal strips for cleansing pores, in acne products, repellents, shaving products, hair removers, intimate hygiene products, foot care products. as well as in child care products.

The skin cosmetic compositions, in addition to the compounds of formula (I) and formula (I') and suitable carriers, may also contain other active ingredients and excipients conventional in skin cosmetics, such as those described above.

Preferred oil and fat components of skin cosmetics and dermatological products are mineral and synthetic oils, such as, for example, paraffins, silicone oils or aliphatic hydrocarbons with more than 8 carbon atoms, animal and vegetable oils, such as, for example, sunflower oil, coconut oil, avocado oil, olive oil, lanolin or waxes, fatty acids, fatty acid esters, such as, for example, triglycerides of fatty acids with 6-30 carbon atoms, wax esters, such as, for example, jojoba oil, fatty alcohols, petroleum jelly, hydrogenated lanolin and acetylated lanolin, as well as mixtures thereof.

In order to regulate certain properties, such as, for example, improved tactile qualities, spreading characteristics, water resistance and/or binding of active and auxiliary substances, such as pigments with a cosmetic effect on the skin and dermatological compositions, conditioning agents based on silicone compounds can additionally also be contained. Suitable silicone compounds are, for example, polyalkylsiloxanes, polyarylsiloxanes, polyarylalkylsiloxanes, polyethersiloxanes or silicone resins.

The preparation of cosmetic or dermatological compositions which contain at least one compound of formula (I) or formula (I') is carried out in the usual manner known to the skilled person.

Preferably, the cosmetic and dermatological preparations are in the form of an emulsion, in particular water-in-oil (W/O) or oil-in-water (O/W) emulsions. However, it is also possible to choose other types of formulations, for example hydrodispersions, gels, oils, oily gels, multiple emulsions, for example in the form of a W/O/W or M/W/M emulsion, anhydrous ointments or ointment bases, etc. .

Obtaining emulsions is carried out by known methods. In addition to at least one compound of formula (I) or formula (I'), emulsions generally contain the usual components such as fatty alcohols, fatty acid esters and in particular fatty acid triglycerides, fatty acids, lanolin and its derivatives, natural or synthetic oils or waxes and emulsifiers in the presence of water. The selection of emulsion-specific additives and the preparation of suitable emulsions is described, for example, in Schrader, Grundlagen und Rezepturen der Kosmetika, Huthig Buch Verlag, Heidelberg, 2nd Edition, 1989, third part, to which direct reference is hereby made.

Preferred fat components that may be present in the fat phase of emulsions are: hydrocarbon oils such as paraffin oil, purcellin oil, perhydrosqualene, and solutions of microcrystalline waxes in these oils; animal or vegetable oils such as sweet almond oil, avocado oil, panthenium oil, lanolin and its derivatives, castor oil, sesame oil, olive oil, jojoba oil, shea butter, hoplostet oil; mineral oils whose atmospheric distillation starts at a temperature of about 250°C and whose distillation end temperature lies at 410°C, such as, for example, liquid paraffin; esters of saturated or unsaturated fatty acids such as alkyl myristates, for example isopropyl, butyl or cetyl myristate, hexadecyl stearate, ethyl or isopropyl palmitate, triglycerides of octanoic or decanoic acid and cetyl ricinoleate.

The fatty phase may also contain other oil soluble silicone oils such as dimethylpolysiloxane, methylphenylpolysiloxane and silicone glycol copolymer, fatty acids and fatty alcohols.

Waxes can also be used, such as, for example, carnauba wax, candle wax, beeswax, microcrystalline wax, ozocerite wax and oleates, myristates, linoleates and calcium (Ca), magnesium (Mg) and aluminum (Al) stearates.

In addition, the emulsion according to the invention may be an O/W type emulsion. Typically, this type of emulsion contains an oil phase, emulsifiers which stabilize the oil phase in an aqueous phase, and an aqueous phase which is usually present in thickened form. Suitable emulsifiers are preferably M/B type emulsifiers such as polyglycerol esters, sorbitan esters or partially esterified glycerides.

According to another preferred embodiment, the compositions according to the invention are hair care products.

Hair care products according to the invention preferably contain at least one compound of general formula (I) or (I') in an amount of from about 0.1 to 30 wt%, preferably from 0.5 to 20 wt%, in terms of to the total weight of the funds.

The compounds of formula (I) and formula (I') according to the invention are also suitable for modeling gels. As gelling agents, all gelling agents common in cosmetics can be used. To this end, reference is made to the previously mentioned conventional thickeners.

The compounds of formula (I) and formula (I') according to the invention are also suitable for the preparation of pharmaceutical compositions.

Suitable pharmaceutical excipients are those listed in the relevant drug registers (eg DAB, Ph. Eur., BP, NF) as well as other excipients whose properties do not preclude their use in physiology. Substances of this type are also described, for example, in Fiedler, H.P. Lexikon der Hilfsstoffe fur Pharmazie, Kosmetik und angrenzende Gebiete, 4. Aufl., Aulendorf: ECV-Editio-Kantor-Verlag, 1996.

Detergent and cleanser

The compounds of formula (I) and formula (I') according to the invention are also suitable for the manufacture of detergents or cleansers, for example for cleaning textile fabric flat surfaces and/or hard surfaces. Cleaners of this type may take the form of a hand or machine dishwashing detergent, an all-purpose cleaner for non-textile surfaces such as metal, lacquered wood or synthetic material, or a cleaner for ceramics such as porcelain, ceramic tiles, tiles. Preferably, the detergents or cleaning agents according to the invention are in the form of a liquid textile detergent. These agents may also, if desired, be formulated as paste compositions.

Examples of other compositions in which at least one compound of general formula (I) or formula (I') as defined above can preferably be used are, for example:

- plant protection products,

- wetting agents,

- thickeners,

- varnishes, coatings, adhesives, leather or fabric treatments or paper treatments, and/or

- chemicals for tertiary oil production.

Examples of other compositions in which at least one compound of general formula (I) or formula (I') as defined above can preferably be used are, for example:

- all-purpose cleaners, spray cleaners, hand dishwashing detergents for cleaning in the private, industrial and corporate sectors;

- means for deduction of moisture;

- cleaners for printing shafts and printed circuit boards in the printing industry;

compositions for use by spraying, for example in ink jet inks;

- means for treating metals, such as compositions for protection against corrosion;

- cutting, grinding or drilling aids and lubricants;

- compositions in the textile industry, such as leveling agents or yarn cleaning compositions;

- flotation aids and foaming aids.

Such compositions typically contain other ingredients such as surfactants, fillers, flavors and colorants, complexing agents, polymers, and other ingredients.

In general, the compounds of general formula (I) according to the invention can be used in all areas in which a thickening surfactant action is required. In addition, the compounds of general formula (I) are suitable to improve the solubility of other components, for example other surfactant components such as anionic surfactants. Thus, they also make a positive contribution to the formation of clear solutions containing surfactants.

EXAMPLES

The method is further explained in detail by means of the following examples.

Surface tension is measured as described in DIN EN 14370.

Example 1:

84.5 g of sodium lactate, 0.5 g of KOtBu and 200 ml of xylene are placed in an autoclave at 80°C. The autoclave is inerted with nitrogen. The vacuum is then released with nitrogen and the temperature is raised to 90°C. At this temperature, 166 g of ethylene oxide are added within 4 hours. Then stirred at this temperature for another 10 hours. All volatile components are removed in vacuo. 229.0 g of a brown viscous substance are obtained.

Saponification number: 0 mg KOH/g

IR spectroscopy: 1599 cm ^-1

Example 2:

76.1 g of sodium lactate, 0.6 g of KOtBu and 250 ml of xylene are placed in an autoclave at 80°C. The autoclave is inerted with nitrogen. The vacuum is then released with nitrogen and the temperature is raised to 120°C. At this temperature, 74.7 g of ethylene oxide are added over 1 hour. Then stirred at this temperature for another 6 hours. After 2 hours add 166 g of dodecene epoxide. Then stirred at this temperature for another 12 hours. All volatile components are removed in vacuo. After separation of the solvent, 270.0 g of a brown viscous substance are obtained.

Saponification number: 0.7 mg KOH/g

IR spectroscopy: 1599 cm ^-1

Surface tension: 27.4 mN/m (1 g/l, 25°C)

Example 3:

0.1 g of KOtBu is added to 87.4 g of the product from example 1. Under nitrogen and at a temperature of 50° C., 48.4 g of dodecene epoxide are added dropwise over 10 minutes. The temperature is then raised to 90°C and stirred at this temperature for another 6 hours. 134.0 g of a brown solid are obtained.

Surface tension: 30.5 mN/m (1 g/l, 25°C)

Example 4:

Under a nitrogen atmosphere and at a temperature of 90° C., 15.6 g of hexadecene epoxide are added dropwise over 10 minutes to 22.1 g of the product from example 1. Then the mixture is stirred at this temperature for another 14 hours. 134.0 g of a brown solid are obtained.

IR spectroscopy: 1600 cm ^-1

Example 5:

129.0 g of sodium salt of 12-hydroxystearic acid, 0.4 g of KOtBu and 800 ml of xylene are placed in an autoclave at 80°C. The autoclave is inerted with nitrogen. The vacuum is then released with nitrogen and the temperature is raised to 120°C. At this temperature, 86.9 g of ethylene oxide are added over 1.5 hours. Then stirred at this temperature for another 10 hours. All volatile components are removed in vacuo. 201.0 g of a beige solid are obtained.

Saponification number: 0 mg KOH/g

IR spectroscopy: 1561 cm ^-1

Example 6:

373.5 g of sodium ricinoleate, 1.2 g of KOtBu and 1000 ml of xylene are placed in an autoclave at 80°C. The autoclave is inerted with nitrogen. The vacuum is then released with nitrogen and the temperature is raised to 120°C. At this temperature, 220.0 g of ethylene oxide are added within 5 hours. Then stirred at this temperature for another 10 hours. All volatile components are removed in vacuo. 580.0 g of a beige solid are obtained.

Saponification number: 2.6 mg KOH/g

IR spectroscopy: 1557 cm ^-1

Example for comparison:

90.7 g of lactic acid (99.3%) and 0.54 g of KOH (50% solution in H ₂ O) are placed in an autoclave at 80°C. The autoclave is inerted with nitrogen. The mixture is then stirred for 2 hours at 80° C. under vacuum (<10 mbar). The vacuum is released with nitrogen and the temperature is raised to 90°C. At this temperature, 44.0 g of ethylene oxide are added within 10 minutes and stirred at this temperature for another 5 hours. All volatile components are then removed in vacuo. 134 g of a clear, clear liquid are obtained.

Acid number: 6.4 mg KOH/g

Saponification number: 433.9 mg KOH/g

IR spectroscopy: 1734 cm ^-1

Claims (66)

1. Mixture with surface-active properties of the compounds of formula (I'):

wherein R ¹ is selected from alkyl with 1-10 carbon atoms, a branched saturated or unsaturated aliphatic hydrocarbon residue with 1-30 carbon atoms, a linear unsaturated aliphatic hydrocarbon residue with 1-30 carbon atoms, saturated or unsaturated cycloaliphatic hydrocarbon radicals with 3-10 carbon atoms and arila; R ² means -CR ^a R ^b -CR ^c R ^d -, in which each R ^a , R ^b , R ^c and R ^d is independently selected from hydrogen, unsubstituted alkyl with 1-30 carbon atoms, unsubstituted cycloalkyl with 5 -7 carbon atoms and cycloalkyl with 5-7 carbon atoms, which contains 1, 2 or 3 substituents, which are independently selected from alkyl with 1-6 carbon atoms and alkenyl with 2-6 carbon atoms, wherein the two residues R ^a and R ^c , also together with the group-CR ^b -CR ^d - to which they are attached, can mean a cycloalkyl with 5-7 carbon atoms, which is unsubstituted or contains 1, 2 or 3 substituents, which are independently selected from each other from alkyl with 1-6 carbon atoms and alkenyl with 2-6 carbon atoms; R ³ is selected from hydrogen and methyl; X in each case means a bond, or a divalent linear or branched saturated or unsaturated aliphatic hydrocarbon residue with 1-30 carbon atoms, or a divalent saturated or unsaturated cycloaliphatic hydrocarbon residue with 3-10 carbon atoms; k means a number from 2 to 100; n means a number from 1 to 10; and And means hydrogen or cationic equivalent; with the exception of 2-[2-(2-hydroxyethoxy)ethoxy]propanoic acid, obtained in a way that a) at least one salt of hydroxycarboxylic acid of general formula (III')

, wherein R ^1' is selected from alkyl with 1-10 carbon atoms, branched saturated or unsaturated aliphatic hydrocarbon residue with 1-30 carbon atoms, linear unsaturated aliphatic hydrocarbon residue with 1-30 carbon atoms, saturated or unsaturated cycloaliphatic hydrocarbon radicals with 3-10 atoms carbon and aryl; R ^3' is selected from hydrogen and methyl; X' in each case means a bond, or a divalent linear or branched saturated or unsaturated aliphatic hydrocarbon residue with 1-30 carbon atoms, or a divalent saturated or unsaturated cycloaliphatic hydrocarbon residue with 3-10 carbon atoms; n has one of the values given in paragraph 1 or 8; and A' is the cationic equivalent; subjected to interaction with at least one epoxide of general formula (IV)

, wherein each R ^a , R ^b , R ^c and R ^d is independently selected from hydrogen, unsubstituted alkyl with 1-30 carbon atoms, unsubstituted cycloalkyl with 5-7 carbon atoms and cycloalkyl with 5-7 carbon atoms, which contains 1, 2 or 3 substituents which are independently selected from alkyl with 1-6 carbon atoms and alkenyl with 2-6 carbon atoms, wherein the two radicals R ^a and R ^c , also together with the -CR ^b -CR ^d - group to which they are attached, may be a C5-C7 cycloalkyl which is unsubstituted or has 1, 2 or 3 substituents, chosen independently from each other of alkyl with 1-6 carbon atoms and alkenyl with 2-6 carbon atoms; and b) if necessary, the reaction product from step a) is treated with acid. 2. The mixture according to claim 1, where R ² means -CHR ^a -CHR ^c -, in which each R ^a is independently selected from hydrogen, unsubstituted alkyl with 1-20 carbon atoms, unsubstituted cycloalkyl with 5-7 carbon atoms, cycloalkyl with 5-7 carbon atoms and with 1, 2 or 3 alkyl substituents with 1-6 carbon atoms and each R ^c is independently selected from hydrogen and methyl. 3. A mixture according to claim 1, wherein A is hydrogen, an alkali metal cation, or the equivalent of an alkaline earth metal cation. 4. Mixture according to claim 1, where k is a number from 2 to 50, in particular from 2 to 20, especially from 2 to 10. 5. A mixture according to claim 1, wherein R ¹ is selected from C 2 -C 25 alkenyl and phenyl. 6. A mixture according to claim 1, wherein R ¹ means methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isoamyl, n-hexyl, 2-ethylhexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, 2-propylheptyl, isotridecyl, isostearyl, oleyl, linoleyl or linolenyl. 7. A mixture according to claim 1, wherein X is selected from a bond, a C 1 -C 20 alkylene, and a C 2 -C 20 alkenylene. 8. A mixture according to claim 1, wherein R ³ is hydrogen. 9. A mixture according to one of paragraphs. 1-8, with n being 1 or 2, in particular 1. 10. Mixture according to claim 1, wherein the salt of hydroxycarboxylic acid is selected from salts of lactic acid, 12-hydroxystearic acid, ricinoleic acid, 3-hydroxybutyric acid, mandelic acid and mixtures thereof and especially from salts of lactic acid, 12-hydroxystearic acid and ricinoleic acid . 11. A mixture according to claim 1, wherein the alkylene oxide is selected from ethylene oxide, propylene oxide, 1,2-butylene oxide, 2,3-butylene oxide, C 10 -C 30 alkylene oxides, and mixtures thereof. 12. A mixture according to claim 11, wherein at least two different alkylene oxides are used for the reaction in step a), preferably one is selected from ethylene oxide, propylene oxide, 1,2-butylene oxide, 2,3-butylene oxide, and preferably the second is selected from alkylene oxides with 10-20 carbon atoms. 13. The method of obtaining a mixture of compounds of General formula (I') as defined in one of paragraphs. 1-9, in which a) at least one salt of hydroxycarboxylic acid of general formula (III')

, wherein R ^1' is selected from alkyl with 1-10 carbon atoms, branched saturated or unsaturated aliphatic hydrocarbon residue with 1-30 carbon atoms, linear unsaturated aliphatic hydrocarbon residue with 1-30 carbon atoms, saturated or unsaturated cycloaliphatic hydrocarbon radicals with 3-10 atoms carbon and aryl; R ^3' is selected from hydrogen and methyl; X' in each case means a bond, or a divalent linear or branched saturated or unsaturated aliphatic hydrocarbon residue with 1-30 carbon atoms, or a divalent saturated or unsaturated cycloaliphatic hydrocarbon residue with 3-10 carbon atoms; n has one of the values given in paragraph 1 or 8; and A' is the cationic equivalent; subjected to interaction with at least one epoxide of general formula (IV)

, wherein each R ^a , R ^b , R ^c and R ^d is independently selected from hydrogen, unsubstituted alkyl with 1-30 carbon atoms, unsubstituted cycloalkyl with 5-7 carbon atoms and cycloalkyl with 5-7 carbon atoms, which contains 1, 2 or 3 substituents which are independently selected from alkyl with 1-6 carbon atoms and alkenyl with 2-6 carbon atoms, wherein the two radicals R ^a and R ^c , also together with the -CR ^b -CR ^d - group to which they are attached, may be a C5-C7 cycloalkyl which is unsubstituted or has 1, 2 or 3 substituents, chosen independently from each other of alkyl with 1-6 carbon atoms and alkenyl with 2-6 carbon atoms; and b) if necessary, the reaction product from step a) is treated with acid. 14. Process according to claim 13, wherein the hydroxycarboxylic acid salt is selected from lactic acid, 12-hydroxystearic acid, ricinoleic acid, 3-hydroxybutyric acid, mandelic acid and mixtures thereof, and especially from lactic acid, 12-hydroxystearic acid and ricinoleic acid salts . 15. Process according to claim 13 or 14, wherein the alkylene oxide is selected from ethylene oxide, propylene oxide, 1,2-butylene oxide, 2,3-butylene oxide, C10-C30 alkylene oxides and mixtures thereof. 16. The method according to claim 15, wherein at least two different alkylene oxides are used for the reaction in step a), preferably one is selected from ethylene oxide, propylene oxide, 1,2-butylene oxide, 2,3-butylene oxide and preferably the second is selected from alkylene oxides with 10-20 carbon atoms. 17. A mixture of compounds of formula (I'), obtained by the method as defined in one of paragraphs. 13-16 for use as a surfactant. 18. The use of a mixture of compounds of formula (I'), as defined in one of paragraphs. 1-12, or obtained by the method as defined in one of paragraphs. 13-16, to form the composition: - cosmetics, - pharmaceuticals, - detergents and cleaners, - plant protection products, - wetting agents, - thickeners, - varnishes, coatings, adhesives, leather or fabric treatments and/or - chemicals for tertiary oil production.