DE10259847A1 - Alkylmonoglycerinether derivatives - Google Patents

Abstract

The present invention relates to alk (en) yl ether ester carboxylic acids based on a polyol skeleton. Furthermore, the present invention relates to processes for the preparation of such compounds and compositions which contain such compounds according to the invention. The present invention further relates to the use of compounds or compositions according to the invention.

Description

The present invention relates to Alk (en) yletherestercarbonsäuren based on a polyol framework. Farther The present invention relates to methods for producing such Compounds, as well as compositions containing such compounds according to the invention contain. The present invention further relates to the use of compounds according to the invention or compositions.

Anionic surfactants are one of the most important Component in surfactant Preparations such as dishwashing. washing or other cleaning agents as well as in cosmetic preparations Anionic surfactants are generally characterized by good cleaning power and good water solubility out. However, anionic surfactants have nonionic surfactants the disadvantage that they have poorer skin tolerance, in particular poorer tolerance to the mucous membrane, poor foaming power, and generally have poorer sensory properties.

There have been in the past Many attempts have been made to achieve the advantageous properties mentioned above anionic surfactants with the advantageous properties of nonionic To combine surfactants. To date, however, the problem has been that an improvement of anionic surfactants with regard to their skin and mucous membrane compatibility and their sensory properties usually with a loss in relation on cleaning power and water solubility.

There was therefore a need for anionic surfactants, which have the mild surfactant properties, the good ones sensory properties and the improved foaming power of have non-ionic surfactants, their excellent water solubility and cleaning power is not adversely affected. Farther there was a need by processes for the preparation of such anionic surfactants.

The present invention was therefore based on the task of providing anionic surfactants, the above have mild surfactant properties. The present invention was also based on the object of anionic Surfactants available to put that over excellent skin tolerance and especially about excellent mucosal tolerance and better sensory Properties. The present invention was also based on the object of anionic Surfactants available too put that over have one or more of the above characteristics and their cleaning power and / or their water solubility compared to anionic surfactants known from the prior art are not or only marginally is adversely affected. Furthermore, the present invention the task is to provide compositions that are special contain mild anionic surfactants with good foaming power and for example in washing or cleaning active compositions or in cosmetic Products can be used. The present invention was also based on the object Procedures available to provide with the anionic surfactants with one or more have the above properties manufactured.

The basis of the invention Problems are solved by alk (en) yl ether ester carboxylic acids which have a polyol structure, which is an ether bond, an optionally alkoxylated alk (en) yl ether radical and one or more carboxylic acid groups or one or more carboxylic acid groups and one or more sulfonic acid groups has, and by processes for the preparation of such compounds, and by compositions as described in the following Text are described.

worin R für ein gesättigtes oder olefinisch ungesättigtes lineares oder verzweigtes, cycloaliphatisches oder heterocycloaliphatisches Polyolgerüst oder ein aromatisches oder heteroaromatisches Polyolgerüst mit 2-16 C-Atomen, A für gesättigten oder olefinisch ungesättigten, linearen oder verzweigten Alkylrest oder einen aromatischen Alkylrest mit jeweils 2-20 C-Atomen, A' für H oder einen linearen oder verzweigten oder cyclischen Alkylrest mit 1 bis 10 C-Atomen steht und worin m und p jeweils unabhängig voneinander für eine ganze Zahl von 0 bis 20 und worin die Reste R' unabhängig voneinander für einen linearen oder verzweigten gesättigten oder olefinisch ungesättigten Alkyl- oder Cycloalkylrest oder einen Aryl- oder Heteroarylrest mit 2 bis 20 C-Atomen und mit jeweils mindestens einer Carboxylgruppe stehen und n für eine ganze Zahl von 1 bis 8 steht.The present invention therefore relates to a compound of the general formula I,

in which R represents a saturated or olefinically unsaturated linear or branched, cycloaliphatic or heterocycloaliphatic polyol structure or an aromatic or heteroaromatic polyol structure having 2-16 C atoms, A represents saturated or olefinically unsaturated, linear or branched alkyl radical or an aromatic alkyl radical each having 2-20 C atoms, A 'is H or a linear or branched or cyclic alkyl radical having 1 to 10 C atoms and in which m and p each independently represent an integer from 0 to 20 and in which the radicals R' independently of one another are linear or branched saturated or olefinically unsaturated alkyl or cycloalkyl radical or an aryl or heteroaryl radical having 2 to 20 carbon atoms and each having at least one carboxyl group and n being an integer from 1 to 8.

A compound of the general formula I according to the invention thus has three building blocks, namely a polyol skeleton (R), an alk (en) yl ether radical (A) and an at least one carboxylic acid group and optionally also one or more further substituents (R '). The polyol backbone is the central building block to which the alk (en) yl ether residue is bonded via an ether bond and one or more residues with carboxylic acid groups are bonded via one or more ester bonds. An inventive Ver Binding according to the general formula I thus has a radical R which stands for a polyol structure, that is to say can be derived from any polyol.

According to the invention, everyone under a "polyol structure" Radical R understood, which is a polyol with at least two OH groups derived. in principle Both monomeric polyols and polymeric polyols, such as those obtained by the polymerization corresponding OH groups carrying compounds or by polymer analogs Functionalization of corresponding polymers with OH groups are available.

Within the scope of the present invention can the polyol backbone R, for example, a linear, branched or cyclic structure exhibit. R can about it addition both saturated as well as olefinically unsaturated his. Within the scope of a preferred embodiment of the invention R however saturated. in principle the radical R can be an essentially arbitrary number of carbon atoms if the number of carbon atoms is the intended use still allowed. In the context of a preferred embodiment of the present Invention R, however, has about 2 to about 44, in particular about 3 to about 18 carbon atoms. Suitable radicals R have in particular about 2 to 12 or about 2 to 8 or about 3 to 6 carbon atoms. The C atoms have to do not necessarily form a continuous C-framework. It is also possible that between two carbon atoms one or more heteroatoms, in particular O, S or N atoms are. However, a radical R preferably has at least one sequence of carbon atoms in which at least 2 carbon atoms directly on top of each other follow and are connected by a covalent bond.

Since the rest of R are within the scope of In the present invention, it is derived from a polyol, for example, according to the invention then possible that he has no OH groups wearing, if one starts from a polyol carrying 2 OH groups. In this Fall one of the OH groups of the diol through the ether linkage to the rest A, the remaining OH group through an ester bond to the radical R 'in the course of production of the compounds of the invention of the general formula I "consumed". However, it is also according to the invention provided that a radical R has one or more OH groups. This is particularly the case if the compounds of the invention the general formula I of polyols with 3 or more OH groups is assumed and in addition to the ether and Ester bonds no further reaction involving an OH group took place ..

A polyol backbone can therefore be used as part of the present invention one or more OH groups, for example Have 1, 2, 3 or 4 OH groups. However, it is also possible that all OH groups of the polyol backbone are substituted with radicals, so that in the compound of the general Formula (I) no longer has a free OH group on the polyol skeleton is, whereby "free" in the sense of "not bound by a reaction within a covalent bond ".

It is further provided in the context of the present invention that the radical R bears one or more other functional groups. For example, the radical R can carry one or more SH, NH ₂ , NHA or NA ₂ groups, where A has the meaning already mentioned above.

The rest R stands out in the frame the compound of the invention of the general formula I in that it has at least one ether bond with the rest of A and over at least one ester bond is connected to at least one radical R '. polyols of which a polyol backbone is derived, therefore have at least two OH groups.

Examples of suitable polyols, of which a corresponding polyol backbone R can be derived are alkylene glycols such as ethylene glycol, diethylene glycol, Triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, three or more valued Polyols such as glycerin, technical oligoglycerine mixtures with one Degree of self-condensation from about 1.1 to about 10, for example technical diglycerine mixtures with a diglycerine content of approx 40 to about 50% by weight or pure diglycerin; triethylolpropane, trimethylolpropane; Sugar alcohols with 4 to 6 carbon atoms, for example Tetrite, Pentite, for example Threit, Erythrit, Ribit, Arabit, Xylitol, sorbitol, especially erythritol or mannitol.

In addition to the above polyols in their pure form also the reaction products of these polyols with alkylene oxides, in particular with ethylene oxide or propylene oxide or mixtures thereof, as a basis for the R serve.

According to a preferred embodiment In the present invention, R has at least one more OH group on.

This is particularly preferred Polyolgerüst R of glycerin, technical oligoglycerine mixtures, trimethylolpropane or triethylolpropane or glucose and their addition products with ethylene oxide. Glycerin and trimethylolpropane are particularly suitable or triethylol propane.

In addition to the central residue R. a compound of the invention at least one, optionally via one or more oxyalkylene groups, with the rest R over an ether bond linked residue A.

Basically, A stands in this case for one linear or branched, saturated or unsaturated aliphatic or cycloaliphatic alkyl radical or an aromatic Alkyl radical with 2-20 C atoms.

The remainder A is particularly direct of primary linear or branched alcohols with 2 to 24, for example 4 to 18 or 6 to 16 carbon atoms.

Typical examples of the suitable one Alcohols from which the radical A can be derived are butanol, capro alcohol, Caprylic alcohol, capric alcohol and undecyl alcohol and their technical Mixtures, such as those used in the hydrogenation of technical fatty acid methyl ester or in the course of the hydrogenation of aldehydes from Roelen's oxosynthesis be preserved. Other suitable examples are lauryl alcohol, Myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, Isostearyl alcohol, oleyl alcohol, elaidyl alcohol, petroselinyl alcohol, Arachyl alcohol, gadoleyl alcohol, behenyl alcohol, erucyl alcohol, Brassidyl alcohol and their technical mixtures, as described above can be obtained.

According to a preferred embodiment In the present invention, A represents a linear alkyl group with 2 to about 24, for example with 8 to about 18 C atoms.

If a compound according to the invention general formula I is derived, for example, from a polyol, which has been reacted with one or more alkylene oxides, or if the rest of A is already over had a corresponding alkoxylated OH group, it can be between the radical A and the radical R are one or more oxyalkylene groups are located. The number of consecutive oxyalkylene groups is described in the general formula I by the parameter m. there can the individual element m for are the same oxyalkylene group. However, it is possible according to the invention and provided that the individual elements m blockwise or statistically are different, for example block by block or statistical for follow of oxyethylene and oxypropylene.

Corresponding oxyalkylene radicals are derived from the alkylene oxides used in each case, the basic addition of alkylene oxides to alcohols being a reaction which is well known to the person skilled in the art. The radical A 'is therefore, depending on the alkylene oxide used, preferably hydrogen or CH ₃ or C ₂ H ₅ .

The corresponding in general Formula I sections marked with the parameter m can Residues A 'for example in a regular manner each on the C atom equipped with the rest A ' exhibit. However, it is in the nature of the corresponding polymerization reactions that that with non-symmetrical alkylene oxides (for example with propylene oxide) also cases occur in which successive oxyalkylene units corresponding residues A 'in each case on adjacent C atoms. Such cases are of general Formula I includes.

The parameter m can be in a connection of the general formula I, for example, for an integer from 0 to 20 or 2 to 10 are available. Within the scope of the present invention m but preferably for 2, 3, 4, 5 or 6.

A compound of the general formula I points in addition to that already explained Radical A and optionally the oxyalkylene units with a radical A 'at the central Polyolgerüst R has at least one further radical R '.

The radical R 'is within the general formula I for one optionally substituted saturated or olefinically unsaturated linear or branched alkyl or cycloalkyl radical or one Aryl or heteroaryl radical having 2 to 20 carbon atoms and has at least one carboxyl group as substituents.

In the context of the present invention, the radical R 'is at least an ester bond is connected to the polyol skeleton R, where optionally between the ester bond and the polyol backbone n Oxyalkylene units can be located.

In principle, all are suitable for introducing the remainder R ' Compounds that have at least two carboxylic acid groups or derivatives those compounds which, in the case of hydrolysis, give compounds with at least two carboxyl groups react. In this way, one of the in of such a compound containing carboxyl groups for binding of the rest R ' the polyol structure over a Ester bond can be used while another carboxyl group remains available as a substituent. Are suitable accordingly also compounds or their derivatives, the 3 or more carboxyl groups have, for example 4, 5 or 6 carboxyl groups.

The rest R 'must be at least one, but can be up to to 12 carboxyl groups, in particular 1, 2 or 3, preferably 1 or Have 2 carboxyl groups.

The rest R 'is therefore basically derived from monomeric or polymeric polycarboxylic acids and therefore preferably has about 2 to 20 carbon atoms, for example 3, 4, 5, 6, 7, 8, 9, 10, 12, 14, 16, 18 or 20 carbon atoms, the carbon atoms of the carboxyl groups not being included are. In the context of the present invention, R 'has in particular 2 to 10 or 2 to 6 carbon atoms, the carbon atoms of the carboxyl groups not being included are. In a preferred embodiment In the present invention, R 'has, for example, 2, 3, 4, 5 or 6 carbon atoms, where the carbon atoms of the carboxyl groups are not included.

Suitable polycarboxylic acids from from which the rest R 'is derived can be, for example, oxalic acid, malonic acid, phthalic acid, maleic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, azelaic acid, sebacic acid, fumaric acid, terephthalic acid, tartaric acid and citric acid, especially of maleic acid and citric acid.

According to a further embodiment The present invention has a compound according to the general Formula I therefore has a radical R ' 1, 2 or 3 carboxyl groups.

The basic structure of the radical R '(without the substituents bound carboxyl groups) can be saturated or olefinically unsaturated according to the invention. In another embodiment of the present invention has a compound, a radical R ', which is at least is simply olefinically unsaturated.

The rest comes particularly preferably R 'therefore, for example of maleic acid from.

In addition to a carboxyl group or two or more carboxyl groups may be a radical R 'of a compound according to the general Formula I have one or more further acid groups in which it is not carboxyl groups. Suitable other acid groups are, for example, sulfonic acid groups. According to one another embodiment The present invention has a connection of the general Formula I therefore, for example, a radical R 'with one or more sulfonic acid groups on.

In the context of the present invention, a radical R 'according to the invention can also have one or more further substituents in addition to one or more acid groups. In addition to one or more acid groups, it can also have one or more OH groups, for example 1, 2, 3 or 4 OH groups. It is also possible in the context of the present invention for the radical R to carry, for example, one or more SH, NH ₂ , NHA or NA ₂ groups, where A has the meaning already mentioned above.

Depending on the number of OH groups on originally on the formation of the polyol backbone R involved polyol and depending on the number of polycarboxylic acids, which are used to form the residues R ' be, a compound of general formula I one or have several radicals R '. Has been for example, a polyol with 2 OH groups is chosen as the starting point, so the number of residues R 'cannot be more than 1. However, for example, was used as a starting point selected a polyol with 2 OH groups, for example the number of radicals R ' 1 or 2, depending on the implementation of the connection to the United general formula I leading Reaction. Generally lets say that the number n of possible residues R ', starting from one Polyol with k OH groups is a maximum of k-1.

In principle, n in a compound of the general formula I can have any value, but preferably n stands for a number from 1 to about 8th , A compound of the general formula I stands for example for a monoester if n = 1, it stands for a diester if n = 2 and for a trieste if n = 3. According to a preferred embodiment of the present invention, however, n stands for 1 or 2.

The connections according to the general Formula I can in principle can be made in any way. For example, it is possible, that first an etherification reaction between a polyol and a suitable monoalcohol is made, which leads to a connection of residue A leads. Subsequently can the compound thus obtained by means of an esterification reaction between the ether resulting from the first process step and a polycarboxylic acid be converted into a compound of general formula I.

Another subject of the present The invention is therefore a process for the preparation of compounds of the general formula I, at least one monofunctional Alcohol is etherified with a polyol to an alk (en) yl ether, wherein a monoether forms, and the reaction product with at least one polycarboxylic or at least one polycarboxylic acid derivative capable of initial formation to a connection according to the general Formula I is implemented.

The production of these if necessary alkoxylated alk (en) yl ether from a polyol and a monofunctional Alcohol can basically done in any way. Suitable methods are known to the person skilled in the art known.

However, alk (en) yl ethers can be particularly advantageous by reacting polyol anions prepared with alk (en) yl (ether) sulfates or alkyl sulfuric acid become. This will be done first submitted the polyol and at a temperature of about 110 to about 130 ° C, for example at about 120 ° C, slowly added dropwise. Suitable as a base for the preparation of the polyol anions especially alkali metal, alkaline earth metal oxides, carbonates or hydroxides and preferably alkali metal or alkaline earth metal hydroxides and in particular Sodium hydroxide, preferably 25 to 50% by weight, or alkali metal or alkaline earth metal alkoxylates or alkali metal or alkaline earth metal hydrides or borohydrides. When the polyols are deprotonated, the resulting Water during of dropping or after dropping the base continuously 110 to 130 ° C and preferably 120 ° C away. For example, the result of the implementation Water at temperatures of 110 to 130 ° C, if necessary by applying a vacuum of about 150 to about 10mbar away. Here will for example at the start of water separation at the temperature listed above Vacuum from about 150 to about 80 mbar and this only on End of water separation increased to about 50 to about 10 mbar.

Then an alk (en) yl (ether) sulfate or a mixture of two or more alk (en) yl (ether) sulfates is added to the polyol (sum of polyol and deprotonated polyol). The implementation The alk (en) yl (ether) sulfates are used, for example, at a temperature of about 150 to about 220 ° C. The mixture is stirred at this temperature for about 7 to about 10 h.

The reaction is controlled via the Determination of the anionic surfactant content, which is clearly below 5, preferably 3 and in particular 1% by weight, based on the active substance content should. The alk (en) yl (ether) sulfates or alkyl sulfuric acid are preferably used and the polyol in a molar ratio of from about 1: 1 to about 1:10 used. The base and the alk (en) nyl (ether) sulfates or Schwefelsäurealkylestern are in a molar ratio of about 0.9: 1 to about 1.5: 1 used.

After the reaction is complete wait for the phase separation and separate the resulting phases. To do this, either first the sulfate salt is filtered off and then the polyol alkyl ether obtained from the watery Phase separated or it the polyol alkyl ether obtained from the aqueous Phase separated and then the sulfate salt from the aqueous Filtered phase. The aqueous phase obtained after working up, which contains unreacted polyols can be known per se Filtered (separation of the precipitated sulfate) and dried and subsequently be added to the process according to the invention as the starting polyol. The organic phase (polyol ether phase) with 100 to 500 ml Water per mole of alk (en) yl (ether) sulfate or alkyl sulfuric acid washed at a temperature of 70 to 95 ° C and again the Phases separated.

The organic phase is by means of Vacuum distillation freed from water and the polyol alkyl ether remains as a distillation residue back. A preferred reaction product contains - based on the total concentration - about 80 to 95 and preferably 90 wt .-% polyol mono- and 20 to 5 and preferably 10% by weight polyol dialkyl ether. The sulfate levels of the polyol alkyl ethers are preferably in the range from 0 to 5 and in particular at the most up to 2% by weight on the active substance content.

The manufactured in this way Monoethers then become with a polycarboxylic acid to a connection according to the general Formula I implemented.

To make the connections of the general formula I from the monoethers and polycarboxylic acids Within the scope of the present invention, two types of processes have a one-step process and a two-step process, as advantageous proved.

The one-step process draws is characterized in that a monoether with a polycarboxylic acid or a suitable polycarboxylic acid derivative, for example an active ester or a polycarboxylic anhydride, to a connection according to the general Formula I is implemented and the resulting from this reaction Ester the desired one Represents reaction product.

For this process step is carried out in addition to the optionally alkoxylated Monoether and a polycarboxylic acid another base needed.

In principle, inorganic bases are used or organic bases can be used. Within the scope of the present invention has the use of alkali metal, alkaline earth metal oxides, carbonates or hydroxides as cheap proved. According to one embodiment becomes an alkali metal or alkaline earth metal carbonate and in particular Sodium carbonate is preferably used as the base. The base can be in one Range of about 0.01-10 wt .-% based on the monoether used be added. A proportion of approximately is suitable, for example 0.1 to 1 or about 0.2 to 0.7, a proportion of about is preferred 0.5% by weight based on the monoether used.

• – Vorlegen des gegebenenfalls alkoxylierten Monoethers und einer Base (bevorzugt Natriumcarbonat),
• – erhitzen auf 70-100 °C (vorzugsweise unter Schutzgasatmosphäre),
• – nach Erreichen der Temperatur portionsweise Zugeben des Polycarbonsäureanhydrids oder der Polycarbonsäure,
• – insgesamt etwa 5 h rühren.

The sequence of a one-step method according to the invention can for example proceed according to the following steps:

• Presentation of the optionally alkoxylated monoether and a base (preferably sodium carbonate),
• - heat to 70-100 ° C (preferably under a protective gas atmosphere),
• - after reaching the temperature, adding the polycarboxylic anhydride or the polycarboxylic acid in portions,
• - stir for a total of about 5 hours.

When implementing the Parameters such as molar ratio the reactant, reaction temperature, reaction time varies become.

In the esterification of polyols with polycarboxylic acids is dependent the molar ratios of OH groups to carboxyl groups the risk of polymerization of the Links. It must therefore be taken into account in the present case whether the carboxyl groups in the polycarboxylic acid in the context of the implementation identical reactivity exhibit. In such a case, the number of OH groups should be exceed the number of carboxyl groups, to prevent polymerization. It is therefore often from Advantage of using polycarboxylic acids in such a reaction, the before or after implementation over Have carboxyl groups of different reactivity, for example compounds with activated carboxyl groups or in particular anhydrides. The Reaction conditions can for example, when using carboxylic anhydrides, that while opening of the anhydride one of the carboxyl groups involved in the anhydride is esterified will, the responsiveness the second carboxyl group formed, however, is not sufficient to to undergo further esterification under the reaction conditions.

Basically, the molar ratio of OH groups in the monoether to carboxylic acid groups which are reactive in the course of the esterification in the polycarboxylic acid or in the polycarboxylic acid derivative not less than about 1: 1 to compounds according to the general To produce Formula I.

Implementations are also conceivable where polycarboxylic acid derivatives with partially protected carboxylic acid groups are used, the carboxyl groups finally located on the radical R ', for example released by "deprotecting" these groups become. In such a case, to determine the above ratio only the unprotected carboxyl groups that are actually reactive during the esterification included.

In addition, the number of desired Ester bonds in the compound to be produced according to the general Formula I considered become. For example, the polyol monoether has 2 OH groups and if only one of these OH groups is to be esterified, it should The relationship from OH groups to carboxyl groups reacting in the course of the esterification be about 1: 1.

The temperature for the death reaction can depends on the specialist can basically be freely determined from the raw materials used. the reaction temperature is, for example, in the range of about 60 ° C to 240 ° C, preferably in the range of 70 ° C up to 200 ° C, for example in the range of 80 ° C up to 120 ° C or 120 ° C up to 160 ° C or in the range of 70 ° C up to 90 ° C.

Within the scope of the present invention a reaction time of about 2 to about 5 h has proven to be favorable. The reaction mixture should be during the response if possible be kept in constant motion, for example by stir.

• 1. Umsetzung eines Alk(en)ylmonopolyolethers mit mindestens einem Polycarbonsäureanhydrid oder mindestens einer Polycarbonsäure zu einer Verbindung der allgemeinen Formel I mit mindestens einer olefinisch ungesättigten Doppelbindung
• 2. Umsetzung des entstandenen ungesättigten Polycarbonsäureesters mit mindestens einem Alkali(hydrogen)sulfit unter Ausbildung einer Sulfonsäure.

A further embodiment of the invention comprises a two-stage process, the first stage being a compound of the general formula I with at least one olefinically unsaturated double bond being prepared by a process as described above, and then the resulting ester from the first process stage in a second process stage is reacted with at least one alkali hydrogen sulfate. The two process stages are therefore:

• 1. Reaction of an alk (en) yl monopolyol ether with at least one polycarboxylic anhydride or at least one polycarboxylic acid to a compound of general formula I with at least one olefinically unsaturated double bond
• 2. Reaction of the resulting unsaturated polycarboxylic acid ester with at least one alkali (hydrogen) sulfite to form a sulfonic acid.

Basically suitable for implementation with an alkali (hydrogen) sulfite is any compound according to the general Formula I, in which the radical R 'at least has a C = C double bond. For example, there is a connection of the general formula I using maleic anhydride was particularly good for the reaction with an alkali (hydrogen) sulfite is suitable.

The first procedural step takes place as already described in connection with the one-step process has been.

As part of the second stage of the process the resulting reaction is then carried out at least once olefinically unsaturated Polycarboxylic acid (half) ester with at least one alkali (hydrogen) sulfite.

Basically, as alkali (hydrogen) sulfite an alkali sulfite or an alkali hydrogen sulfite of any one Alkali metal can be used. It has been within the scope of the present However, the invention is particularly favorable proven when sodium sulfite or sodium bisulfite for the reaction is used.

When performing the second step can again the parameters like molar ratio of Reaction partner, reaction temperature and reaction time like it has already been described in the preceding text, can be varied.

Implementation of the method according to the invention can be solvent free or using a solvent respectively. in principle are suitable as solvents all compounds which are liquid under reaction conditions and which Reactants are inert.

Are suitable as solvents, each after process step, for example water, linear, branched or cyclic, saturated or unsaturated Alcohols with 2 to about 10 carbon atoms as well as ketones, esters, carboxylic acids and Mixtures of two or more of the solvent types mentioned.

Within the scope of the present invention can for example dialkyl ketones or alcohols and mixtures thereof as a solvent be used. Alcoholic solvents that can be used are methanol, ethanol, Isopropanol and propa nol. Other suitable organic solvents are glycerin, dimethyl sulfoxide, tetrahydrofuran, acetone, methyl ethyl ketone, Cyclohexanol, toluene, methylene chloride, chloroform, alkanes and alkyl acetate, especially ethyl acetate.

Basically, it is possible to above solvent each alone or as a mixture of two or more solvents use, provided the solvent mixtures do not interfere with ester formation or sulfitation.

In the context of a preferred embodiment of the present invention, solvent mixtures which contain water as a component are used in the second process step in the sulfitation special aqueous-alcoholic solvent mixtures, most preferred is water as solvent.

In the preparation of the compounds according to the invention the resulting solvent content can be adapted to the respective purpose. During the manufacturing process the amount of solvent in the context of the present invention preferably chosen such that the reaction mixture during the Implementing prevailing temperatures is easy to stir. Preferably points the reaction mixture contains an appropriate solvent in such a Amount on that viscosity at the reaction temperature about 50 to about 1000 mPas, for example is about 100 to about 500 mPas (measured according to Brookfield).

The removal of the solvent used can be carried out according to methods known to the person skilled in the art.

Following the removal of the solvent or even before the removal of the solvent, the reaction product undergo further treatment steps.

As another suitable treatment step is, for example, the bleaching of the reaction product obtained to call. Here you can those in the reaction products in a manner known to those skilled in the art by addition bleaching agents, for example by adding hydrogen peroxide or sodium hypochlorite.

Basically are for bleaching suitable for all processes which cause the reaction products to be decolorized, for example by treatment with activated carbon or by treatment with peroxo compounds, for example hydrogen peroxide or performic acid. It can several bleaching processes can also be used in combination.

When making connections of general formula I arise according to the methods described above in the vast majority Number of cases Mixtures of different compounds of the general formula I. If a mixture of substances is obtained as a reaction product, can a certain compound from the mixture of substances by known methods be cleaned up.

Within the scope of the present invention it is also possible the mixture of substances containing various compounds of the general Formula I for use other purposes.

Another subject of the present The invention is therefore a mixture of substances containing at least two various connections according to the general Formula I.

In principle, the mixtures of substances according to the invention can in one or more residues or parameters according to the general Differentiate formula I.

According to one embodiment of the present invention a mixture of substances, for example, both compounds of general Formula I where the value for n = 1 (corresponds to a monoester), as well as compounds of general formula I in which the value for n = 2 (corresponds to a diester) is. If necessary, you can additionally compounds of the general formula I may also be present, in which the value for n = 3 (corresponds to a triester).

The connections of the general Formula I or the mixtures of substances described above are suitable for Manufacture of compositions for washing and cleaning agents also for cosmetic preparations.

• a) Lösemittel
• b) waschaktive Substanzen
• c) Zusatzstoffe

The present invention therefore furthermore relates to compositions comprising at least one compound of the general formula I or a mixture of substances according to the invention and at least one further component from at least one of the following groups:

• a) Solvent
• b) wash-active substances
• c) additives

A1 additives are suitable, for example Filling or Fillers, fragrances, builders, builders, bleach, Bleach activators, detergent boosters, enzymes, enzyme stabilizers, Graying inhibitors, optical brighteners, soil repellants, foam inhibitors, inorganic salts and all other additives known to the person skilled in the art, as in cleaning compositions or cosmetic preparations be used.

Coming as wash-active substances in principle all surfactants into consideration. Suitable in the context of the present invention in particular nonionic surfactants or additional anionic surfactants.

Typical examples of suitable additional anionic surfactants are soaps, alkylbenzene sulfonates, secondary alkane sulfonates, olefin sulfonates, alkyl ether sulfonates, glycerin ether sulfonates, α-methyl ester sulfonates, sulfo fatty acids, alkyl and / or alkenyl sulfates, alkyl ether sulfates, glyceryl ether sulfates, hydroxymate ether sulfates sulfates, fatty acid amide (ether) sulfates, mono- and dialkyl sulfosuccinates, mono- and dialkyl sulfosuccinamates, sulfotriglycerides, amide soaps, ether carboxylic acids and their salts, fatty acid isethionates, fatty acid sarcosinates, fatty acid taurides, N-acyl amino acids, such as acyl lactate acrylate, acyl acyl lactate trate especially vegetable products based on wheat) and alkyl (ether) phosphates. If the anionic surfactants contain polyglycol ether chains, they can be conventional, but preferably have a narrow homolog distribution.

Anionic surfactants are preferred selected from the group formed by alkyl and / or alkenyl sulfates, Alkyl ether sulfates, alkyl benzene sulfonates, soaps, monoglyceride (ether) sulfates and alkane sulfonates, in particular fatty alcohol sulfates, fatty alcohol ether sulfates, secondary Alkanesulfonates and linear alkylbenzenesulfonates.

As washing-active substances can also contain nonionic surfactants in a composition according to the invention his.

Typical examples of non-ionic Surfactants are fatty alcohol polyglycol ethers, alkylphenol polyglycol ethers, fatty acid, Fettsäureamidpolyglykolether, Fatty amine polyglycol ethers, alkoxylated triglycerides, mixed ethers or Mixed formal, optionally partially oxidized alk (en) yl oligoglycosides or glucoronic acid derivatives, Fatty acid N-alkylglucamides “Protein hydrolyzates (especially vegetable products based on wheat), polyol fatty acid esters, Sugar esters, sorbitan esters, polysorbates and amine oxides.

As washing-active substances can also Amphoteric or zwitterionic surfactants in a composition according to the invention be included. Typical examples of amphoteric or zwitterionic Surfactants are alkyl betaines, alkyl amido betaines, aminopropionates, aminoglycinates, Imidazolinium betaines and sulfobetaines.

The surfactants mentioned it exclusively about known connections. In terms of structure and manufacture these substances are on relevant reviews for example J. Falbe (ed.), "Surfactants in consumer Products", Springer Verlag Berlin, 1987, pp.54-124 or J. Falbe (ed.), “Catalysts, Surfactants and Mineral oil additives ", Thieme Verlag Stuttgart, 1978, pp. 123-217.

The compositions according to the invention can comprise surfactants contained in amounts of 0.5 to 50 wt .-%.

Also suitable as additives are builders.

In particular, finely crystalline, synthetic and bound water-containing zeolite such as zeolite NaA in detergent quality is used as a solid builder. However, zeolite NaX and mixtures of NaA and NaX are also suitable. The zeolite can be used as a spray-dried powder or as an undried stabilized suspension that is still moist from its production. In the event that the zeolite is used as a suspension, it can contain minor additions of nonionic surfactants as stabilizers, for example 1 to 3% by weight, based on zeolite, of ethoxylated C12-cis fatty alcohols with 2 to 5 ethylene oxide groups or ethoxylated isotridecanols. Suitable zeolites have an average particle size of less than 10 μm (volume distribution; measurement method: counter counter) and preferably contain 18 to 22, in particular 20 to 22% by weight of bound water. Suitable substitutes or partial substitutes for zeolites are crystalline, layered sodium silicates of the general formula NaMSixO2x + 1-yH2O, where M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 to 20 and preferred values for x is 2, 3 or 4. Such crystalline layered silicates are described, for example, in the European patent application EP 0164514 A described. Preferred crystalline phyllosilicates are those in which M in the general formula represents sodium and x assumes the values 2 or 3. In particular, both β- and γ-atrium disilicate Na2Si2O5-yH2O are preferred, wherein β-sodium disilicate can be obtained, for example, by the method described in international patent application WO 91/08171. The powder detergents according to the invention preferably contain 10 to 60% by weight of zeolite and / or crystalline layered silicates as solid builders, mixtures of zeolite and crystalline layered silicates in any ratio being particularly advantageous. In particular, it is preferred that the agents contain 20 to 50% by weight of zeolite and / or crystalline layered silicates. Particularly preferred agents contain up to 40% by weight of zeolite and in particular up to 35% by weight of zeolite, in each case based on anhydrous active substance. Other suitable ingredients of the agents are water-soluble amorphous silicates; they are preferably used in combination with zeolite and / or crystalline layered silicates.

Agents which contain sodium silicate with a molar ratio (module) Na20: SiO2 of 1: 1 to 1: 4.5, preferably 1: 2 to 1: 3.5, are particularly preferred. The content of amorphous sodium silicates in the agents is preferably up to 15% by weight and preferably between 2 and 8% by weight. Phosphates such as tripolyphosphates, pyrophosphates and orthophosphates can also be present in small amounts in the compositions. The content of the phosphates in the compositions is preferably up to 15% by weight, but in particular 0 to 10% by weight. In addition, the compositions can additionally contain layered silicates of natural and synthetic origin. Layered silicates of this type are, for example, from the patent applications DE 2334899 B . EP 0026529 A and DE 3526405 A known. Their usability is not limited to a special composition or structural formula. However, smectites, in particular bentonites, are preferred here. Suitable layered silicates, which belong to the group of water-swellable smectites, are, for example, montmorrilonite, hectorite or saponite. In addition, small amounts of iron can be incorporated into the crystal lattice of the layered silicates of the above compounds. Furthermore, due to their ion-exchanging properties, the layered silicates can contain hydrogen, alkali, alkaline earth ions, in particular Na ″ and Ca 2 ′. The amount of water of hydration is usually in the range from 8 to 20% by weight and is of the swelling state or depending on the type of processing. Suitable layer silicates are, for example, from US 3,966,629 . US 4,062,647 . EP 0026529 A and EP 0028432 A known. Layered silicates are preferably used which are largely free of calcium ions and strongly coloring iron ions due to an alkali treatment.

Usable organic builders are, for example, the polycarboxylic acids preferably used in the form of their sodium salts, such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), as long as such use is not objectionable for ecological reasons, and mixtures of these , Preferred salts are the salts of polycarboxylic acids such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids and mixtures of these. Suitable polymeric polycarboxylates are, for example, the sodium salts of polyacrylic acid or polymethacrylic acid, for example those with a relative molecular weight of 800 to 150,000 (based on acid). Suitable copolymeric polycarboxylates are, in particular, those of acrylic acid with methacrylic acid and of acrylic acid or methacrylic acid with maleic acid. Copolymers of acrylic acid with maleic acid which contain 50 to 90% by weight of acrylic acid and 50 to 10% by weight of maleic acid have proven to be particularly suitable. Their relative molecular weight, based on free acids, is generally 5,000 to 200,000, preferably 10,000 to 120,000 and in particular 50,000 to 100,000. The use of polymeric polycarboxylates is not absolutely necessary. However, if polymeric polycarboxylates are used, agents are preferred which are biodegradable polymers, for example terpolymers, the monomers acrylic acid and maleic acid or salts thereof, and vinyl alcohol or vinyl alcohol derivatives, or the monomers acrylic acid and 2-alkylallylsulfonic acid or salts thereof as well as sugar derivatives. Terpolymers which are based on the teaching of German patent applications are particularly suitable DE 4221381 A and DE 4300772 A be preserved.

Other suitable builder substances are polyacetals which, by reacting dialdehydes with polyolcarboxylic acids, have soft 5 to 7 carbon atoms and at least 3 OH groups, for example as in the European patent application EP 0280223 A described, can be obtained. Preferred polyacetals are obtained from dialdehydes such as glyoxal, glutaraldehyde, terephthalaldehyde and mixtures thereof and from polyol carboxylic acids such as gluconic acid and / or glucoheptonic acid.

Among the bleaching agents Compounds providing hydrogen peroxide in water have sodium perborate tetrahydrate and the sodium perborate monohydrate a special meaning.

Other bleaching agents are, for example Peroxycarbonate, citrate perhydrates and salts of peracids, such as Perbenzoates, peroxyphthalates or diperoxydodecanedioic acid. she are common used in amounts of 8 to 25 wt .-%. Use is preferred of sodium perborate monohydrate in amounts of 10 to 20% by weight and in particular from 10 to 15% by weight. Through its ability to train the Being able to bind tetrahydrate-free water contributes to increasing it stability of the agent at.

In addition, the composition by adding suitable preservatives, for example by Addition of formaldehyde, p-hydroxybenzoate, sorbic acid or other known preservatives can be preserved.

If the composition is in the form of a liquid or a paste, it can be dried in the process according to the invention by processes known from the prior art and known to the person skilled in the art. Suitable drying processes are, for example, spray drying, fluidized bed drying or granulation. Particularly suitable processes for drying anionic surfactants are, for example DE 198 53 893 . DE 42 09 339 or the DE 44 46 444 refer to.

Individual as perfume oils or fragrances Fragrance compounds, e.g. B. the synthetic products of the type the esters, ethers, aldehydes, ketones, alcohols and hydrocarbons be used. Fragrance compounds are of the ester type z. B. benzyl acetate, phenoxyethyl isobutyrate, p-tert-butylcyclohexyl acetate, Linalyl acetate, dimethylbenzylcarbinylacetate, phenylethyl acetate, Linalyl benzoate, benzyl formate, ethyl methylphenyl glycinate, allyl cyclohexyl propionate, Styrallyl propionate and benzyl salicylate. The ethers include, for example Benzyl ethyl ether, to the aldehydes z. B. the linear alkanals 8-18 C atoms, citral, Citronellal, citronellyloxyacetaldehyde, cyclamenaldehyde, hydroxycitronellal, Lilial and bourgeonal, to the ketones z. B. the Jonone, α-isomethyl ionone and Methyl cedryl ketone, to the alcohols anethole, citronellol, eugenol, Geraniol, linalool, phenylethyl alcohol and terpineol, to the hydrocarbons belong mainly the terpenes like limes and pinene. However, mixtures are preferred different fragrances, which together make an appealing Generate fragrance. Such perfume oils can also natural fragrance mixtures contain as they are accessible from plant sources, e.g. B. Pine, Citrus, Jasmine, patchouly, rose or ylang-ylang oil. Are also suitable Muscatel, sage oil, Chamomile oil, Clove oil, lemon balm oil, mint oil, cinnamon leaf oil, linden blossom oil, juniper berry oil, vetiver oil, olibanum oil, galbanum oil and labdanum oil as well Orange blossom oil, neroliol, Orange peel oil and sandalwood oil.

The fragrances can be incorporated directly into the agents according to the invention, but it can also be advantageous to apply the fragrances to carriers which increase the adhesion of the perfume to the laundry and ensure a long-lasting fragrance of the textiles due to a slower fragrance release. Cyclodextrins, for example, have proven successful as such carrier materials, the cyclodextrin-perfume complexes can also be coated with other auxiliaries.

If desired, the compositions of the invention still inorganic salts as fillers or adjusting agents, such as sodium sulfate, which preferably in amounts of 0 to 10, in particular 1 to 5% by weight on medium - included is.

Another subject of the present Invention is the use of compounds according to the general Formula I and mixtures of substances containing such a compound or mixtures of two or more such compounds in washing and Detergents or in cosmetic preparations.

The present invention is as follows through examples explained.

1. Production of C ₁₂ glycerol ether by using Na alkyl sulfate powder

552 g (6 mol) of glycerol were heated to 120 ° C. in a 2-liter four-necked flask, 100 g (1.25 mol) of 50% sodium hydroxide solution were slowly added dropwise, and the water formed was continuously added at 120 ° C. and a vacuum of 100 mbar condensed. At the end of the water separation, the vacuum was reduced to 10 mbar. The thus-formed sodium Glycerinat was added with 300 g (1 mol) Texapon K12P ^® (Natrimlaurylsulfat powder) suspended, heated to 180 ° C and stirred at this temperature. 8 The reaction was checked by determining the anionic surfactant content. After 8 hours this was clearly below 1%. For working up, the reaction mixture was mixed with 225 ml of water and 5 ml of 50% sodium hydroxide solution at a temperature of 90 ° C. and the phase separation was then waited for. The resulting phases were then separated. For this purpose, the lower phase was filtered to remove the precipitated sodium sulfate and the upper organic phase (glycerol ether phase) was washed with 250 ml of water at a temperature of 90 ° C. and the phases were separated again. The organic phase was freed from water by distillation by means of vacuum distillation. The C ₁₂ glycerol ether remains as a distillation residue. The product contained approximately 90% monolaurylglycerol ether and 10% dilaurylglycerol ether.

2. Preparation of C _16/18 glycerol ether by using Na alkyl sulfate powder

In a 2-liter four-necked flask, 552 g (6 mol) of glycerol were heated to 120 ° C, 100 g (1.25 mol) of 50% sodium hydroxide solution were slowly added dropwise, and the water formed was continuously added at 120 ° C and a vacuum of 100 mbar condensed. At the end of the water separation, the vacuum was reduced to 10 mbar. The Na glycerinate thus formed was mixed with 380 g (1 mol) of Lanette E powder (sodium cetylstearyl sulfate powder), suspended and stirred at 180 ° C. for 8 h. The reaction was checked by determining the anionic surfactant content, which was clearly below 1% after a reaction time of 8 hours. For working up, the reaction mixture was mixed with 225 ml of water and 5 ml of 50% sodium hydroxide solution at a temperature of 90 ° C. and the phase separation was then waited for. The resulting phases were then separated. For this purpose, the lower phase was filtered to remove the precipitated sodium sulfate and the upper organic phase (glycerol ether phase) was also filtered and the upper organic phase (glycerol ether phase) was washed with 250 ml of water at a temperature of 90 ° C. and the phases were separated again. The organic phase was freed from water by distillation by means of vacuum distillation. The C _16/18 glycerol ether remains in the distillation residue. The product contained approximately 70% mono-C _16/18 glycerol ether and approximately 10% di-C _16/18 glycerol ether.

3. Production of C ₁₂ glycerol ether by using Na alkyl sulfate granules

In a 2-liter four-necked flask, 552 g (6 mol) of glycerol were heated to 120 ° C, 100 g (1.25 mol) of 50% sodium hydroxide solution were slowly added dropwise, and the water formed was continuously added at 120 ° C and a vacuum of 100 mbar condensed. At the end of the water separation, the vacuum was reduced to 10 mbar. The thus-formed sodium Glycerinat was added with 300 g (1 mol) Texapon ^® K12G (Natrimlaurylsulfat granules) suspended, heated to 180 ° C and stirred at this temperature. 8 The reaction was checked by determining the anionic surfactant content. After 8 hours this was clearly below 1%. For working up, the reaction mixture was mixed with 225 ml of water and 5 ml of 50% sodium hydroxide solution at a temperature of 90 ° C. and the phases were then waited for. The resulting phases were then separated. For this purpose, the lower phase was filtered to remove the precipitated sodium sulfate and the upper organic phase (glycerol ether phase) was washed with 250 ml of water at a temperature of 90 ° C. and the phases were separated again. Vacuum distillation removes the organic phase from the water by distillation. The C12 glycerol ether remains as a distillation residue. The product contained approximately 90% monolaurylglycerol ether and 10% dilaurylglycerol ether.

4. Preparation of C ₁₂ glycerol ether by neutralization with acidic Na alkyl sulfuric acid esters

In a 2-liter four-necked flask 213 g (0.8 mol) of C were ₁₂ -Schwefelsäureester (made of C ₁₂ fatty alcohol by sulfating with SO ₃₎ in a mixture of 400 g (4.37 mol) of Na-Glycerinat ( from 4.37 mol glycerol and 0.87 mol 50% sodium hydroxide solution and 64 g (0.8 mol) 50% sodium hydroxide solution. The water contained was removed at 100 ° C. under vacuum. The reaction mixture was then stirred at 180 ° C. for 8 h. The reaction was checked by determining the anionic surfactant content. After 8 hours this was below 3%. For working up, the reaction mixture was mixed with 225 ml of water and 5 ml of 50% sodium hydroxide solution at a temperature of 90 ° C. and the phases were then waited for. The resulting phases were then separated. For this purpose, the lower phase was filtered to remove the precipitated sodium sulfate and the upper organic phase (glycerol ether phase) was washed with 250 ml of water at a temperature of 90 ° C. and the phases were separated again. The organic phase was freed from water by distillation by means of vacuum distillation. The C ₁₂ glycerol ether remains as a distillation residue. The product contained approximately 80% monolaurylglycerol ether and 8% dilaurylglycerol ether.

5. Esters of Alkyl monoglycerin ether with dicarboxylic acids

First stage:

390.0 g (1.50 mol) of C ₁₂ monoglycerol ether and 2.0 g (0.5% by weight, based on the alcohol used) of anhydrous sodium carbonate were placed in a stirred container and heated to 80 ° C. under a nitrogen atmosphere. After the temperature had been reached, 161.8 g (1.65 mol) of maleic anhydride were added in portions and the mixture was stirred for a further 2.5 hours, during which the temperature rose slightly to 100.degree. A light brown, clear liquid was present as the stage 1 product.
Yield: 551.8 g

Second step:

824.3 g of distilled water (corresponds to an active substance (AS) content in the end product of 40%) and 149.5 (1.19 mol) of anhydrous sodium sulfite were placed in another stirred vessel and heated to 75 ° C. under a nitrogen atmosphere. After the temperature had been reached, 400.0 g of the 1st stage (C12 monoglycerol ether maleate) were added and the mixture was stirred for 2 hours. The unreacted sodium sulfite was then destroyed with hydrogen peroxide. A yellow, clear liquid was present as a stage 2 product.
Yield: 1373.8 g

6. Sulfosuccinate Basis of alkyl monoglycerol ether maleinates

First stage:

436.0 g (1.0 mol) of C12 monoglycerol ether with 4 EO (ethylene oxide) and 2.2 g (0.5% by weight based on alcohol used), anhydrous sodium carbonate, were placed in a stirred vessel and heated to 80 ° C. under a nitrogen atmosphere. After the temperature had been reached, 107.9 g (1.1 mol) of maleic anhydride were added in portions and the mixture was stirred for 5 hours, with a slight rise in temperature to 90 ° C. A light brown, clear liquid was present as the stage 1 product.
Yield: 543.9 g

Second step:

751.7 g of distilled water (corresponds to an AS content in the end product of 40%) and 101.1 (0.80 mol) of anhydrous sodium sulfate were placed in a further stirred vessel and heated to 75 ° C. under a nitrogen atmosphere. After the temperature had been reached, 400.0 g of the 1st stage (C 12-monoglycerol ether maleate) were added and the mixture was stirred for 2 hours. The unreacted sodium sulfite was then destroyed with hydrogen peroxide. There was a beige, solid product.
Yield: 1252.8 g

7. Mixtures of monoesters and diesters based on alkyl monoglycerol ethers with dicarboxylic acids and corresponding sulfosuccinates

First stage:

348.8 g (0.8 mol) of C12 monoglycerol ether with 4 EO (ethylene oxide) and 1.7 g (0.5% by weight, based on the alcohol used) of anhydrous sodium carbonate were placed in a stirred vessel and brought to 80 under a nitrogen atmosphere ° C heated. After the temperature had been reached, 156.9 g (1.6 mol) of maleic anhydride were added in portions and the mixture was stirred for a further 5 hours, with a slight rise in temperature to 94 ° C. A light brown, clear liquid was present as the product.
Yield: 505.7 g

Second step:

740.2 g of distilled water (corresponds to an active substance content in the end product of 40%) and 138.4 g (1.1 mol) of anhydrous sodium sulfite were placed in another stirred vessel and heated to 75 ° C. under a nitrogen atmosphere. After the temperature had been reached, 350.0 g of the 1st stage (C12 monoglycerol ether maleate) were added and the mixture was stirred for 2 hours. The unreacted sodium sulfite was then destroyed with hydrogen peroxide. There was a beige, solid product.
Yield: 1228.6 g

8. Preparation of C12 monoglycerol ether citrate

312.0 g (1.2 mol) of C12 monoglycerol ether and 230.5 g (1.2 mol) of citric acid (anhydrous) were added to placed in a stirred tank and heated to 160 ° C under a nitrogen atmosphere. After the theoretical acid number had been reached, the mixture was cooled to 100 ° C. and converted to the distillation apparatus. The mixture was stirred at 105 ° C. for one hour under vacuum (187 mbar). There was a brown, solid ester as a product.
Distillate: 24.0 g
Yield: 518.5 g

9. Preparation of C12 monoglycerol ether 4EO citrate

741.2 g (1.7 mol) of C12 monoglycerol ether and 4 EO (ethylene oxide) and 326.6 g (1.7 mol) of citric acid (anhydrous) were placed in a stirred vessel with a water separator and heated to 160 ° C. under a nitrogen atmosphere. After the theoretical acid number had been reached, the mixture was cooled to 100 ° C. and converted to the distillation apparatus. The mixture was stirred at 100 ° C. for one hour under vacuum (37 mbar). A brown, viscous, slightly cloudy ester was present as the product.
Distillate: 32.3 g
Yield: 1035.5 g

Claims (11)

Compound according to general formula I,

in which R represents a saturated or olefinically unsaturated linear or branched, cycloaliphatic or heterocycloaliphatic polyol structure or an aromatic or heteroaromatic polyol structure having 2-16 C atoms, A represents saturated or unsaturated, linear or branched alkyl radical or an aromatic alkyl radical each having 2-20 C -Atoms, A 'is H or a linear or branched or cyclic alkyl radical having 1 to 10 carbon atoms and in which m and p are each independently an integer from 0 to 20 and in which the radicals R' are each independently a linear one or branched saturated or olefinically unsaturated alkyl or cycloalkyl radical or an Ary1 or heteroaryl radical having 2 to 20 carbon atoms and each having at least one carboxyl group and n being an integer from 1 to 8. A compound according to claim 1, wherein R 'is one or more further carboxyl groups or one or more sulfonic acid groups or one or more carboxyl groups and one or more sulfonic acid groups having. A compound according to claim 1 or 2, wherein R 'is one, two or has three carboxyl groups. A compound according to any one of claims 1 to 3, wherein R 'is saturated or is at least simply olefinically unsaturated. A compound according to any one of claims 1 to 4, wherein R 'is at least one sulfonic acid having. Process for the preparation of compounds according to a of claims 1 to 5, in which at least one monofunctional alcohol with a Polyol is etherified and the reaction product with at least one polycarboxylic or at least one polycarboxylic acid derivative capable of initial formation is converted into a reaction product. A method according to claim 6, characterized in that the reaction product, provided it is at least one olefinic unsaturated Has double bond, with at least one alkali (hydrogen) sulfite is implemented. Mixture of substances containing at least two different ones Compounds of the general formula I. A mixture of substances according to claim 8, containing at least a compound of general formula I, with n = 1 and at least a compound of general formula I, with n = 2. Composition containing at least one compound according to one of claims 1 to 5 and at least one further connection selected from at least one of the groups consisting of: a) Solvent b) wash-active substances c) additives Use of compounds according to one of claims 1 to 5 or mixtures of substances according to claim 8 or 9 or of compositions according to claim 10 in washing or Detergents or cosmetic preparations.