EP0874802A1 - Fettsäurederivate und ihre verwendung als tenside in wasch- und reinigungsmitteln - Google Patents
Fettsäurederivate und ihre verwendung als tenside in wasch- und reinigungsmittelnInfo
- Publication number
- EP0874802A1 EP0874802A1 EP96937203A EP96937203A EP0874802A1 EP 0874802 A1 EP0874802 A1 EP 0874802A1 EP 96937203 A EP96937203 A EP 96937203A EP 96937203 A EP96937203 A EP 96937203A EP 0874802 A1 EP0874802 A1 EP 0874802A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- fatty acid
- radical
- groups
- surfactants
- alkyl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C229/00—Compounds containing amino and carboxyl groups bound to the same carbon skeleton
- C07C229/02—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton
- C07C229/04—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated
- C07C229/26—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated having more than one amino group bound to the carbon skeleton, e.g. lysine
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C229/00—Compounds containing amino and carboxyl groups bound to the same carbon skeleton
- C07C229/02—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton
- C07C229/04—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated
- C07C229/06—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated having only one amino and one carboxyl group bound to the carbon skeleton
- C07C229/10—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated having only one amino and one carboxyl group bound to the carbon skeleton the nitrogen atom of the amino group being further bound to acyclic carbon atoms or to carbon atoms of rings other than six-membered aromatic rings
- C07C229/16—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated having only one amino and one carboxyl group bound to the carbon skeleton the nitrogen atom of the amino group being further bound to acyclic carbon atoms or to carbon atoms of rings other than six-membered aromatic rings to carbon atoms of hydrocarbon radicals substituted by amino or carboxyl groups, e.g. ethylenediamine-tetra-acetic acid, iminodiacetic acids
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C229/00—Compounds containing amino and carboxyl groups bound to the same carbon skeleton
- C07C229/02—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton
- C07C229/04—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated
- C07C229/22—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated the carbon skeleton being further substituted by oxygen atoms
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C237/00—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by amino groups
- C07C237/02—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by amino groups having the carbon atoms of the carboxamide groups bound to acyclic carbon atoms of the carbon skeleton
- C07C237/04—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by amino groups having the carbon atoms of the carboxamide groups bound to acyclic carbon atoms of the carbon skeleton the carbon skeleton being acyclic and saturated
- C07C237/06—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by amino groups having the carbon atoms of the carboxamide groups bound to acyclic carbon atoms of the carbon skeleton the carbon skeleton being acyclic and saturated having the nitrogen atoms of the carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C237/00—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by amino groups
- C07C237/02—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by amino groups having the carbon atoms of the carboxamide groups bound to acyclic carbon atoms of the carbon skeleton
- C07C237/04—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by amino groups having the carbon atoms of the carboxamide groups bound to acyclic carbon atoms of the carbon skeleton the carbon skeleton being acyclic and saturated
- C07C237/08—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by amino groups having the carbon atoms of the carboxamide groups bound to acyclic carbon atoms of the carbon skeleton the carbon skeleton being acyclic and saturated having the nitrogen atom of at least one of the carboxamide groups bound to an acyclic carbon atom of a hydrocarbon radical substituted by singly-bound oxygen atoms
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C237/00—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by amino groups
- C07C237/02—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by amino groups having the carbon atoms of the carboxamide groups bound to acyclic carbon atoms of the carbon skeleton
- C07C237/04—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by amino groups having the carbon atoms of the carboxamide groups bound to acyclic carbon atoms of the carbon skeleton the carbon skeleton being acyclic and saturated
- C07C237/10—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by amino groups having the carbon atoms of the carboxamide groups bound to acyclic carbon atoms of the carbon skeleton the carbon skeleton being acyclic and saturated having the nitrogen atom of at least one of the carboxamide groups bound to an acyclic carbon atom of a hydrocarbon radical substituted by nitrogen atoms not being part of nitro or nitroso groups
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C237/00—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by amino groups
- C07C237/02—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by amino groups having the carbon atoms of the carboxamide groups bound to acyclic carbon atoms of the carbon skeleton
- C07C237/22—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by amino groups having the carbon atoms of the carboxamide groups bound to acyclic carbon atoms of the carbon skeleton having nitrogen atoms of amino groups bound to the carbon skeleton of the acid part, further acylated
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/02—Anionic compounds
- C11D1/04—Carboxylic acids or salts thereof
- C11D1/10—Amino carboxylic acids; Imino carboxylic acids; Fatty acid condensates thereof
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/38—Cationic compounds
- C11D1/46—Esters of carboxylic acids with amino alcohols; Esters of amino carboxylic acids with alcohols
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/38—Cationic compounds
- C11D1/52—Carboxylic amides, alkylolamides or imides or their condensation products with alkylene oxides
- C11D1/523—Carboxylic alkylolamides, or dialkylolamides, or hydroxycarboxylic amides (R1-CO-NR2R3), where R1, R2 or R3 contain one hydroxy group per alkyl group
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/38—Cationic compounds
- C11D1/52—Carboxylic amides, alkylolamides or imides or their condensation products with alkylene oxides
- C11D1/525—Carboxylic amides (R1-CO-NR2R3), where R1, R2 or R3 contain two or more hydroxy groups per alkyl group, e.g. R3 being a reducing sugar rest
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/38—Cationic compounds
- C11D1/52—Carboxylic amides, alkylolamides or imides or their condensation products with alkylene oxides
- C11D1/528—Carboxylic amides (R1-CO-NR2R3), where at least one of the chains R1, R2 or R3 is interrupted by a functional group, e.g. a -NH-, -NR-, -CO-, or -CON- group
Definitions
- Fatty acid derivatives and their use as surfactants in washing and cleaning agents are Fatty acid derivatives and their use as surfactants in washing and cleaning agents
- the present invention relates to the use of fatty acid derivatives of the general formula I
- a 1 is an aliphatic C ⁇ -C 24 radical with an unbranched carbon chain, which contains one or more groups of the formula II in the chain
- R 1 is a radical -N (R 2 ) R 3 , a hydroxyl radical and its alkali or ammonium salts, a C 1 -C 4 alkoxy radical or a radical of a mono-, di- or triglyceride, the latter two radicals being more natural saturated or unsaturated fatty acids or the same or different radicals A 1 ;
- R 2 is a hydrophilic radical with 2-40 C atoms
- R3 is hydrogen, a C 1 -C 4 -alkyl radical or one of the radicals R 2 .
- the invention also relates to the new fatty acids of the formula I a
- R 4 is hydrogen or an alkali metal or ammonium cation of the corresponding fatty acid salt and A 1 has the meaning given above and its use as surfactants.
- the invention also relates to surfactant formulations which contain the compounds I and Ia.
- DE-A 27 34 596 discloses fatty acid derivatives of type I as active washing substances for washing textiles.
- surfactants In order to clean non-textile surfaces, surfactants must have additional properties such as good fat-removing properties.
- Such cleaning processes are mainly found in the metal industry, in the food industry, in GabtsLütter. commercial and household.
- metal objects often have to be freed of drawing and rolling greases after they have been processed.
- the primary task is to free equipment and containers from greases of different origins, since greases prevent the wetting of other dirt particles.
- the invention was based on the use of surfactants for aqueous cleaning agent systems for cleaning non-textile material with a better fat-removing ability as an object.
- the compounds I are known per se by epoxidation of fatty acid esters III
- a 2 here stands for an unsaturated residue which corresponds to the saturated or partially saturated residue A 1 in I
- B 1 means the residue of a 1- to 3-valent aliphatic Ci-C ß alcohol. If it is a polyhydric alcohol, its remaining hydroxyl groups can also be esterified, preferably with fatty acids.
- the epoxy groups mainly react with the amine V.
- B 1 is replaced by the radical -N (R 2 ) R 3 .
- the new fatty acids or their alkali metal salts can be prepared, for example, from known reactions such as alkaline hydrolysis and, if desired, acidification, from the reaction obtained from the reaction.
- the likewise new ammonium salts are preferably obtainable directly from the epoxidized fatty acids by reaction with V.
- the preferred ammonium salts are obtained with ®NH 2 R2 R 3 as the cation, in which R 2 and R 3 have the same meanings as in the amino group of the fatty acid ester.
- Any ammonium salts can be prepared by subsequent reaction of a fatty acid Ia 'with an amine.
- ricinoleic acid can be considered as unsaturated hydroxy fatty acid, but preferably:
- C 9 -C 25 fatty acids such as Petroselin acid, undecenoic acid, ⁇ 9 -Decylen Textre, ⁇ 9 -Dodecylen Textre, vaccenic, palmitoleic acid, erucic acid and especially oleic acid
- triple unsaturated fatty acids such as elaeostearic and preferably linolenic acid.
- Ci ⁇ fatty acids are particularly suitable because of their good availability.
- the acids obtainable by isomerization of the double bond are also suitable. 4
- Fatty acid or fatty acid ester mixtures such as are obtainable, for example, by transesterification or saponification of natural fats with C 1 -C 4 alcohols, can also be used.
- the preparation of the compounds I is preferably based on natural fats, that is to say the glycerol esters which contain at least one unsaturated radical A 2 .
- natural fats are, for example, olive oil, cottonseed oil, linseed oil, tallow, fish oils, tall oils, castor oil, coconut oil, camelina oil, sunflower oil, peanut oil, palm oil, euphorbia oil and above all soybean oil and turnip oil.
- the epoxidation is carried out in a manner known per se by reacting compound III with peracids such as performic acid and peracetic acid.
- peracids such as performic acid and peracetic acid.
- some epoxidized fatty acid esters IV are also commercially available.
- the amines V are primary or secondary amines with at least one hydrophilic aliphatic C 2 -C 4 n radical.
- the amines can be branched and carry several hydroxyl or amino groups, such as (trishydroxymethylene) methylamine, but preferably have at least one unbranched ⁇ -hydroxyalkyl radical or an ⁇ -aminoalkyl radical with 2 to 6 carbon atoms, the alkyl radical being formed by non-adjacent oxygen atoms, -NH groups, NC 1 -C 4 alkyl groups or NC 1 -C 4 hydroxyalkyl groups can be interrupted.
- the N -CC 4 -alkyl-substituted derivatives are suitable if they still contain at least one reactive amino or imino group. The following are preferred:
- Hydroxyalkylamines such as mono- and diethanoiamine, mono- and diisopropanolamine, 2- (2-aminoethoxy) ethanol, 2- [(2-aminoethyl) amino] ethanol, 3-aminopropanol and N-alkyl-substituted hydroxyalkylamines such as methylethanolamine, n-propylethanolamine , Butylethanolamine, 2-aminobutanol-1 and particularly preferably aminopropyldiethanolamine.
- Aminoalkylamines such as ethylenediamine, trimethylenediamine, 1,2-propylenediamine, 3-amino-1-methylaminopropane, diethylenetriamine, dipropylenetriamine, N, N'-bis (3-aminopropyl) ethylenediamine, 3- (2-aminoethoxy) propylamine , 2- (2-aminoethoxy) ethylamine, 3- (3-aminopropoxy) propylamine and their symmetrical and unsymmetrical N-substituted mono- and dialkyl derivatives such as N, N-dimethylaminopropylamine, diethylaminoethylamine, diethylaminopropylamine, 1-diethylamino 4-aminopentane, neopentane diamine, hexamethylene diamine 4,9-dioxadodecane-1,12-diamine, 4,7,10-trioxatridecane
- R 4 is hydrogen or a C1-C4 alkyl radical
- Suitable amines are, for example, methylglycolamine and methyltetraglycolamine.
- the reaction of the epoxidized fatty acid esters, acids or their salts with the amines is generally carried out at 30 to 170 ° C., preferably in the presence of an alkaline catalyst such as alkali metal hydroxides, carbonates or alcoholates, for example sodium methylate.
- an alkaline catalyst such as alkali metal hydroxides, carbonates or alcoholates, for example sodium methylate.
- the reaction is complete when no more epoxy groups can be detected. At 100 ° C the reaction is complete after about 2 to 4 hours.
- the reaction can be carried out in the presence of a solvent, but this is usually not necessary, so that one preferably works without a solvent.
- the amine is generally used in a stoichiometric to 10 molar amount, preferably a stoichiometric to 2.5 molar amount per epoxy unit. If epoxidized fatty acids are reacted, the reaction with at least 2 equivalents of amine is recommended, since part of the amine reacts to form the ammonium salt. 6
- isomer mixtures are generally obtained since the oxirane rings can open at both C — O bonds.
- reaction mixture which, in addition to the compounds I, may also contain glycerol and possibly the amides of saturated fatty acids.
- the aminohydroxyfatty acid derivatives I show good fat-dissolving properties, such as are necessary for surfactants in aqueous cleaning systems on non-textile surfaces.
- the surfactants I also show good foam damping behavior.
- the cleaning processes described at the outset are predominantly mechanical processes in which the use of foam-suppressing surfactants is important. Since there is a strong circulation of water during machine cleaning, a lot of foam is otherwise generated, which weakens the mechanical cleaning power. Because of this extremely good foam damping behavior, the surfactants I are also suitable for use in
- Agents such as rinse aids for the dishwasher, in which the fat-removing ability is of little importance.
- the surfactants are also suitable for cleaning all non-textile surfaces such as metal, lacquered wood, plastic or ceramic products, for example porcelain, tiles, tiles, which occur in the household and in trade.
- the agents can be applied manually, for example, with a damp cloth or sponge, or by spray cleaning. 7
- the agents are usually marketed in the form of aqueous concentrates and can be used diluted or undiluted.
- Common cleaners for non-textile surfaces are, for example, car window cleaners, car shampoos, oven cleaners, window / synthetic leather cleaners, plastic cleaners, sanitary cleaners, abrasives and tub cleaners.
- the fatty acid derivatives I according to the invention are therefore particularly suitable for aqueous cleaning systems for grease-soiled non-textile surfaces, since, in addition to their good ability to remove grease, they also have good foam damping properties.
- the nonionic surfactants in particular from the group of fatty acid amines, are particularly preferred for the use according to the invention. Since ..-- Lei, they are easily accessible and readily biodegradable.
- the aqueous-based cleaning agent systems for cleaning non-textile materials contain Tenide I, their mixtures and, if appropriate, builders, solvents or solubilizers and other additives customary for such agents in the amounts customary for the agents. It is possible to use surfactants I in combination with anionic or non-ionic surfactants such as mentioned in DE-A 27 34 597 to use.
- Well-suited rinse aids for dishwashers contain e.g.
- a hand dishwashing detergent consists, for example, of 5 to 50, preferably 5 to 30,% by weight of I
- a solubilizer such as cumene sulfonate or alcohol
- a composition according to the invention of a dip degreasing agent for metal objects consists, for example, of 1 to 10, preferably 1 to 5% by weight of I and 10 to 70% by weight of alkaline builders.
- the fat-removing ability, the cloud point, the foaming power, the surface tension and the foam attenuation in the dishwasher of aqueous preparations were investigated as the application properties of the aminohydroxyfatty acid derivatives I.
- the cloud point was determined in accordance with DIN 53917. The temperature above which the solution becomes cloudy and is therefore a mixture of two liquid phases was determined. The lower the cloud temperature, the lower the foaming power.
- the foaming power was determined in accordance with DIN 53902 by measuring the foam volume in ml one minute after the end of foam generation.
- the surface tension was determined according to DIN 53924 by measuring the force in mN / m which is necessary to pull a plate or a horizontally suspended ring out of the liquid surface.
- Foam was produced in a commercial household dishwasher by adding an egg and the average number of revolutions of the spray arm per minute was reached during a twelve-minute heating-up phase. averages. The formation of foam reduces the number of revolutions due to the reduced recoil force and thus represents a measure of the suitability of surfactants in cleaning machines.
- the present invention further relates to alkoxylated fatty acid derivatives VII, obtainable by reacting the compounds VIII
- a 2 is an aliphatic C ⁇ -C 24 radical with unbranched carbon chain, which contains one or more groupings of the formula IX in the chain
- R 5 is a radical -N (R 6 ) R 7 , a hydroxyl radical and its alkali metal or ammonium salts, a C 1 -C 4 alkoxy radical or a radical of a mono-, di- or triglyceride, the di- or triglyceride radicals Residues of natural saturated or unsaturated fatty acids or identical or different radicals A 2 are and
- R 6 and R 7 independently of one another are hydrogen, an unsubstituted C 1 -C 6 -alkyl radical or a C 1 -C 14 -alkyl radical which is hydroxyl-, amino-substituted and / or aminocarbonyl-substituted and / or by non-adjacent oxygen atoms, -NH groups and / or NC 1 -C 4 alkyl groups can be interrupted and / or the radicals -COOH or -SO 3 H and their alkali metal salts or ammonium salts,
- the invention relates to novel fatty acid derivatives villa, the production of these fatty acid derivatives VII and villa, their use as surfactants in detergents and cleaning agents and formulations with these surfactants. 13
- DE-A 16 19 081 discloses alkoxylation products of quaternary ammonium hydroxy fatty acid derivatives in softening agents for textiles.
- DE-A 27 34 596 and DE-A 27 34 597 describe the uses of aminohydroxystearic acid amides or esters as detergent active substances in detergents or cold detergents.
- EP-A-0 633 243 describes a production process for ⁇ -hydroxylated secondary and tertiary amines.
- the products obtained by reacting epoxidized olefins such as epoxydodecane with amino acids are surface-active substances and are therefore suitable for numerous uses.
- the aim of the present invention was to provide surfactants with advantageous properties.
- alkoxylated fatty acid derivatives VII defined at the outset, the fatty acid derivatives serving as starting compounds, a process for the preparation of VII and Villa, their use as surfactants in detergents and cleaning agents and formulations comprising VII or Villa were found.
- the alkoxylated fatty acid derivatives VII are obtained by reacting VIII with 3 to 15 equivalents of ethylene oxide, propylene oxide and / or butylene oxide per equivalent IX.
- the compounds VIII generally contain several reactive groups, but at least one hydroxyl group, which can be alkoxylated.
- the optionally present hydroxyl, -NH-, -NH 2 and carboxylic acid residues of R 5 , R 6 and R 7 are also alkoxylated. Insertion by alkylene oxide can also be observed in the case of ester groups. Since the compounds VIII are reacted with at least the three-molar amount of alkylene oxide per mole VIII, product mixtures are obtained.
- the compounds are preferably reacted with ethylene oxide and / or propylene oxide, particularly preferably with ethylene oxide, since these products are particularly readily biodegradable.
- the reaction with several alkylene oxides can be carried out in succession or directly with a mixture. 14
- the reaction takes place under known alkoxylation conditions, preferably in the presence of an alkaline catalyst such as potassium hydroxide, sodium hydroxide, sodium methoxide or potassium tert-butoxide. It is possible to carry out the reaction both under pressure and under pressure, preferably at a pressure of 1-20 bar, particularly preferably at 1.5-10 bar.
- an alkaline catalyst such as potassium hydroxide, sodium hydroxide, sodium methoxide or potassium tert-butoxide. It is possible to carry out the reaction both under pressure and under pressure, preferably at a pressure of 1-20 bar, particularly preferably at 1.5-10 bar.
- the alkylene oxide is added in portions.
- the reaction takes place at room temperature, but is preferably carried out in a temperature range of 80-120 ° C. and results in mixtures above 150 ° C. in which the proportion of alkoxylated amino groups is increased.
- the ReaKtions ⁇ auex beL -.--. YL Je-Lei depending on the selected temperatures between 0.5 and 10 hours, 5 whereby low temperatures require a longer reaction time and vice versa.
- inert solvents such as toluene or xylene are possible, but it is more advantageous not to use an additional solvent, since there is no need to separate off the solvent.
- the compounds VIII 0 are in a manner known per se by epoxidizing fatty acids or their salts or esters
- R 7 accessible by opening the epoxy ring.
- D stands for 5 an unsaturated radical which corresponds to the saturated or partially saturated radical A 2 in VIII, and R 11 denotes a hydroxyl radical and its alkali metal or ammonium salts or the 15
- Remainder of a 1- to 3-valent aliphatic C -C -C alcohol If it is a polyhydric alcohol, its remaining hydroxyl groups can also be esterified, preferably with fatty acids.
- R 11 can also be replaced by the radical -N (R 6 ) R 7 .
- the fatty acids or their alkali metal salts can be prepared from the esters or amides optionally obtained by the reaction, for example by known reactions, such as alkaline hydrolysis and, if desired, acidification.
- the ammonium salts are preferably ⁇ ire-ct from the epoxidite-rLer. Fatty acids obtainable by reaction with XII. In this case, the preferred ammonium salts are obtained with ®NHR 6 R 7 as the cation, in which R 6 and R 7 have the same meanings as in the amino group of the fatty acid ester. Any ammonium salts can be prepared by subsequent reaction of a fatty acid VIII with an amine.
- ricinoleic acid can be considered as unsaturated hydroxy fatty acid, but preferably
- C 9 -C 25 fatty acids such as petroselinic acid, undecenoic acid, ⁇ 9 -Decylenklare, ⁇ 9 -Dodecylklare, vaccenic acid, palmitoleic acid, erucic acid, and especially oleic acid
- di-unsaturated fatty acids such as stilingic acid, preferably linoleic acid
- triple unsaturated fatty acids such as elaeostearic and preferably linolenic acid.
- Unsaturated Ci ⁇ fatty acids are particularly suitable because of their good availability.
- Fatty acid or fatty acid ester mixtures such as those obtainable, for example, by transesterification or saponification of natural fats with C 1 -C 4 alcohols, preferably methanol, can also be used.
- the preparation of the compounds VII is preferably based on natural fats, that is to say the glycerol esters, which contain at least one unsaturated radical D.
- natural fats are, for example, olive oil, cottonseed oil, linseed oil, tallow, fish oils, tall oils, castor oil, coconut oil, hemp oil, sperm oil, lard, tallow, goose fat, beef tallow, claw oil, tallow fatty acid, camelot oil, sunflower oil, peanut oil, palm oil and Euphor all soybean oil and rapeseed oil.
- the epoxidation is carried out in a manner known per se by reacting the compound XI with peracids such as performic acid and peracetic acid.
- peracids such as performic acid and peracetic acid.
- some epoxidized fatty acid derivatives X are also commercially available.
- the amines XII are ammonia, primary or secondary amines with an unsubstituted Ci-C ⁇ -alkyl radical or a substituted C 1 -C 14 -alkyl radical.
- the amines can be branched and carry several hydroxyl or amino groups, such as (trishydroxymethylene) methylamine, but preferably have at least one unbranched ⁇ -hydroxyalkyl radical or an ⁇ -aminoalkyl radical with 2 to 6 C atoms, the alkyl radical being formed by non-adjacent oxygen atoms, NH groups or NC 3.
- -C 4 alkyl groups can be interrupted.
- the N-C 1 -C 4 -alkyl-substituted derivatives are suitable if they still contain at least one reactive amino or imino group.
- Suitable aliphatic amines are short-chain secondary amines, for example C 1 -C 6 -alkylamines such as dimethylamine, diethylamine, dipropylamine, dibutylamine, the corresponding mixed-substituted amines, for example methylethylamine, and primary amines, for example C 1 -C 6 -alkylamines such as methylamine, ethylamine, propylamine, Butylamine, pentylamine and hexylamine and branched amines, for example isopropylamine.
- the reaction products VIII of the primary amines are preferred since they contain an alkoxylatable imino group.
- Preferred substituted amines are the reaction products VIII of the following amines:
- Hydroxyalkylamines such as mono- and diethanoiamine, mono- and diisopropanolamine, 2- (2-aminoethoxy) ethanol, 2 - [(2-aminoethyl) amino] ethanol, 3-aminopropanol, aminopropyldiethanol- ⁇ utiine, aminosorbitol, glucamine and N-alkyl-substituted Hydroxyalkylamines such as methylethanolamine, n-propylethanolamine, butylethanolamine, N-methylglucamine and 2-aminobutanol-l, 17
- Aminoalkylamines such as ethylenediamine, trimethylenediamine, 1,2-propylenediamine, 3-amino-1-methylaminopropane, diethylenetriamine, dipropylenetriamine, N, N'-bis (3-aminopropyl) ethylenediamine, 3- (2-aminoethoxy) propylamine, 2- (2-aminoethoxy) ethylamine, 3- (3-aminopropoxy) propylamine and their symmetrically and asymmetrically substituted mono- and dialkyl derivatives such as N, N-dimethylaminopropylamine, diethylaminoethylamine, diethylaminopropylamine, 1-diethylamino-4-aminopentane, Neopentan ⁇ diamine, hexamethylene diamine, 4,9-dioxadodecane-l, 12-diamine, 4,7,10-trioxatridecane-l, 13-
- the nurses can be amino acids l-cu. ⁇ lei_. ⁇ .
- a 3 is an aliphatic C ⁇ -C 24 radical with an unbranched carbon chain which contains one or more groupings of the formula IXa in the chain
- R 8 is a radical -N (R 6 ) R 7 , a hydroxyl radical and its alkali metal or ammonium salts, a C 1 -C 4 alkoxy radical or a radical of a mono-, di- or triglyceride, the latter two radicals being more natural saturated or unsaturated fatty acids or the same or different radicals A 3 and
- R 9 is a C ⁇ -C 6 -alkyl radical which can be hydroxy-, amino-substituted and / or aminocarbonyl-substituted and / or can be interrupted by non-neighboring NH groups and a radical 18th
- R 10 is hydrogen or one of the radicals R 9 .
- Amino acids NHR 9 R 10 are to be understood as aliphatic carboxylic acids or sulfonic acids with amino and / or imino groups.
- the carboxylic or sulfonic acids are preferably unbranched. They can also carry further acid or acid amide groups and can optionally be substituted with hydroxyl radicals. It is irrelevant for the effect of VII and Villa whether D or L forms or mixtures are used.
- the known amino acids are generally readily accessible, for example, by means of the Strecker reaction. A large part is also still commercially available. Examples of suitable amino acids are:
- Monocarboxylic acids such as valine, leucine, isoleucine, ornithine, citrulline, serine, threonine, preferably alanine, arginine, lysine, particularly preferably glycine and sarcosine
- Dicarboxylic acids such as asparagine, aspartic acid, glutamine, glutamic acid, particularly preferably iminodiacetic acid and ethylenediaminediacetic acid
- Tricarboxylic acid such as aspartic acid monoacetic acid
- Sulfonic acids such as N-methyl taurine and taurine.
- the reaction of the epoxidized fatty acid esters, acids or their salts with the amines is generally carried out at 30 to 280 ° C., preferably 80 to 140 ° C., preferably in the presence of an alkaline catalyst such as alkali metal hydroxides, carbonates or alcoholates for example sodium methylate.
- the reaction is complete when no more epoxy groups can be detected. For example, the reaction at 120 ° C. is complete after 2 to 4 hours.
- the reaction can be carried out in the presence of a solvent, but this is usually not necessary, so that the process is preferably carried out without a solvent.
- amines are not liquids, but solids such as amino acids, their implementation as a suspension in water-soluble or partially water-soluble solvents is preferred.
- the amino acid partly as a solution and partly undissolved 19 is present, in a preferred embodiment the Na salt of the amino acid is introduced in, for example, propylene glycol with the alkali catalyst and the epoxidized compound XI is added. Reaction temperatures of 60 to 200 ° C., in particular 100 to 180 ° C., are advantageous here.
- temperatures are required at which the mixture is in the form of a melt, which may well be below the fixed point of the amino acid itself, generally above 200 ° C.
- the preferred upper temperature range is 220 to 2bU ° C.
- the amino acid is dissolved in a little water and heated together with the base and the epoxidized fatty acid or its ester. The high temperatures cause the water to evaporate directly, so that the reaction mixture is in the form of a melt.
- the amine is generally used in a stoichiometric to 5 molar amount, preferably 2.5 molar amount, per epoxy unit. If epoxidized fatty acids are reacted, then it is advisable to react with at least 2 equivalents of amine, since part of the amine reacts to form the ammonium salt.
- reaction of the fatty acid esters with the amines By reaction of the fatty acid esters with the amines, reaction with 1.4 to 5 equivalents of the amine, especially the fatty acid amides, are obtained as reaction products. A larger excess of amine is possible, but may require subsequent removal of the unreacted amine.
- reaction mixture which, in addition to the compounds VIII, can also contain glycerol and possibly the amides of saturated fatty acids. However, these substances do not need to be separated off for the subsequent alkoxylation since they do not interfere.
- reaction products villa of epoxidized fatty acid derivatives with amino acids lead to compounds with good surface-active properties, which are therefore outstandingly suitable for use as anionic surfactants in washing and cleaning agents.
- Low surface and interfacial tension are found in the test.
- Dar- In addition, they show good fat dissolving power and good primary washing power.
- the alkoxylated aminohydroxy fatty acid derivatives VII show good fat-dissolving properties in application tests. These grease-dissolving properties are a very important requirement in the field of cleaning agents for hard surfaces, since greases generally prevent the wetting of other dirt particles.
- the fat-dissolving power of a surfactant is just as important for washing textiles. Surfactants with such properties are often poorly water-soluble, which is evident in the low cloud points.
- the compounds VII according to the invention also have higher cloud points, so that they are suitable, for example, as a surfactant in a heavy-duty detergent.
- alkoxylated aminohydroxyfatty acid derivatives described above are used in detergents alone or in combination with at least one anionic and / or nonionic surfactant, usually in an amount of 2 to 50, preferably 8 to 30,% by weight, based on the total weight of the particular formulation.
- the detergents can be in powder form or can also be in liquid form.
- the composition of the detergents and cleaners can be very different.
- Detergent and cleaning agent formulations usually contain 2 to 50% by weight of surfactants and optionally builders. This information applies to both liquid and powder detergents. Detergent and cleaning agent formulations that are common in Europe, the USA and Japan can be found, for example, in Chemical and Engn. News, volume 67, 35 (1989). Further information about the composition of detergents and cleaning agents can be found in Ullmann's encyclopedia of industrial chemistry, 21
- Phosphate-reduced detergents are to be understood as meaning formulations which contain at most 25% by weight of phosphate, calculated as pentasodium triphosphate.
- the detergents can be full detergents or special detergents. Both anionic and nonionic or mixtures of anionic and nonionic surfactants are suitable as surfactants.
- the surfactant content of the detergents is preferably 8 to 30% by weight.
- Suitable anionic surfactants are, for example, FcLLalkühol sulfates of fatty alcohols having 8 to 22, preferably 10 to 15, 18 carbon atoms, for example Cg to Cn alcohol sulfates, C 2 to C 13 alcohol sulfates, cetyl sulfate, myristyl sulfate, palmityl sulfate, stearyl sulfate and tallow fatty alcohol.
- Suitable anionic surfactants are sulfated, ethoxylated C ⁇ to C 22 alcohols or their soluble salts.
- Compounds of this type are prepared, for example, by first alkoxylating a C ⁇ to C 22 "# preferably a C ⁇ o to Ci ⁇ alcohol and then sulfating the alkoxylation product.
- ethylene oxide are used for the alkoxylation, with one per mole of fatty alcohol 2 to 50, preferably 3 to 20, moles of ethylene oxide are used, but the alkoxylation of the alcohols can also be carried out using propylene oxide alone and, if appropriate, butylene oxide, and alkoxylated C 6 -C 22 -alcohols containing ethylene oxide and propylene 0 are also suitable
- the alkoxylated C 6 -C 22 alcohols can contain the ethylene oxide, propylene oxide and butylene oxide units in the form of blocks or in statistical distribution.
- Suitable anionic surfactants are alkyl sulfonates such as C ⁇ - to C 24 -, preferably Cio-Ci ⁇ -alkanesulfonates and soaps such as the salts of C ⁇ - to C 24 -carboxylic acids.
- Suitable anionic surfactants are C 9 to C 2 o-linear 0 alkylbenzenesulfonates (LAS).
- LAS o-linear 0 alkylbenzenesulfonates
- the fatty acid derivatives according to the invention are preferably used in LAS-poor detergent formulations with less than 4%, particularly preferably in LAS-free formulations.
- the anionic surfactants are preferably added to the detergent in the form of salts. Suitable cations in these salts are alkali metal salts such as sodium, potassium, lithium and 22
- Ammonium salts such as Hydroxyethylammonium, di (hydroxyethyl) ammonium and tri (hydroxyethyl) ammonium salts.
- Suitable nonionic surfactants are, for example, alkoxylated C ⁇ to C 22 alcohols.
- the alkoxylation can be carried out with ethylene oxide,
- Propylene oxide and / or butylene oxide can be carried out. All alkoxylated alcohols which contain at least two molecules of an alkylene oxide mentioned above can be used as the surfactant.
- block polymers of ethylene oxide, propylene oxide and / or butylene oxide come into consideration or addition products which contain the alkylene oxides mentioned in a statistical distribution. 2 to 50, preferably 3 to 20, moles of at least one alkyl .. oxide are used per mole of alcohol.
- Ethylene oxide is preferably used as the alkylene oxide.
- the alcohols preferably have 10 to 18 carbon atoms.
- alkyl polyglucosides with 8 to 22, preferably 10 to 18 carbon atoms in the alkyl chain. These compounds contain 1 to 20, preferably 1.1 to 5, glucoside units.
- N-alkylglucamides of the general structure XIII or XIV
- Y is a C ⁇ to C 22 alkyl
- X is an H or C 3 to C 4 alkyl
- Z is a polyhydroxyalkanyl radical having 5 to 12 C atoms and at least 3 hydroxyl groups.
- Y is preferably C 10 - to Ci ⁇ -alkyl
- X is CH 3 -
- Z is a C 5 or C 6 radical.
- such compounds are obtained by the acylation of reducing aminated sugars with acid chlorides of C 10 -C 3 . 8 carboxylic acids.
- the detergent formulations preferably contain C 10 -C 16 alcohols ethoxylated with 3-12 mol ethylene oxide, particularly preferably ethoxylated fatty alcohols as nonionic surfactants.
- surfactants are the end group-capped fatty acid amide alkoxylates of the general formula known from WO-A-95/11225
- L 1 denotes a C 5 to C 21 alkyl or alkenyl radical
- L 2 is a 0 ⁇ - to C 4 -alkyl group
- A is C 2 - to C 4 -alkylene
- n denotes the number 2 or 3
- x has a value from 1 to 6.
- Examples of such compounds are the reaction products of n-butyltriglycolamine of the formula H 2 N- (CH 2 -CH 2 -O) 3 -C 4 H 9 with methyl dodecanoate or the reaction products of ethyltetraglycolamine of the formula H 2 N- ( CH 2 -CH 2 -O) 4 -C 2 H 5 with a commercially available mixture of saturated C ⁇ - to Ci ⁇ -Fettauremec-.ylesLexj ...
- the powdered or granular detergents and, if appropriate, structured liquid detergents also contain one or more inorganic builders. All conventional inorganic builders such as aluminosilicates, silicates, carbonates and phosphates are suitable as inorganic builder substances.
- Suitable inorganic builders are e.g. Aluminum silicates with ion-exchanging properties such as Zeolites.
- zeolites are suitable, in particular zeolite A, X, B, P, MAP and HS in their Na form or in forms in which Na is partly replaced by other cations such as Li, K, Ca, Mg or ammonium.
- Suitable zeolites are described, for example, in EP-A-0 038 591, EP-A-0 021 491, EP-A-0 087 035, US-A-4 604 224, GB-A-2 013 259, EP-A- 0 522 726, EP-A-0 384 070A and WO-A-94/24251.
- Suitable inorganic builders are e.g. amorphous or crystalline silicates such as e.g. amorphous disilicates, crystalline disilicates such as the layered silicate SKS-6 (manufacturer Hoechst AG).
- the silicates can be used in the form of their alkali, alkaline earth or ammonium salts. Na, Li and Mg silicates are preferably used.
- Suitable inorganic builder substances are carbonates and hydrogen carbonates. These can be used in the form of their alkali, alkaline earth or ammonium salts. Na, Li and Mg carbonates or bicarbonates, in particular sodium carbonate and / or sodium bicarbonate, are preferably used.
- the inorganic builders can be present in the detergents in amounts of 0 to 60% by weight together with organic cobuilders which may be used.
- the inorganic builders can either be used alone or in any combination. 24 be worked into the detergent.
- powdered or granular detergents they are added in amounts of 10 to 60% by weight, preferably in amounts of 20 to 50% by weight.
- structured (multi-phase) liquid detergents inorganic builders are added in amounts of up to 40% by weight, preferably up to 20% by weight. They are suspended in the liquid formulation components.
- Organic cobuilders are present in powder or granular as well as in liquid detergent formulations in amounts of 0.1 to 20% by weight, preferably in amounts of 1 to 15% by weight, together with inorganic builders.
- the powdery or granular heavy-duty detergents can also contain, as other usual constituents, a bleaching system consisting of at least one bleaching agent, optionally in combination with a lead activator and / or a bleaching catalyst.
- Suitable bleaches are perborates and percarbonate in the form of their alkali metal salts, in particular their Na salts. They are present in quantities of 5 to 30% by weight, preferably 10 to 25% by weight
- bleaching agents are inorganic and organic peracids in the form of their alkali or magnesium salts or in some cases also in the form of the free acids.
- suitable organic percarboxylic acids or salts are e.g. Mg monoterephthalate, phthalimidopercaproic acid and
- Dodecane-1,10-diper acid An example of an inorganic peracid salt is potassium peroxomonosulfate (oxone).
- Suitable bleach activators are e.g.
- Acylamines such as tetraacetylethylene diamine, tetraacetyl glycol uril, N, N '-diacetyl-N, N' -dimethylurea and 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine
- acylated lactams such as acetylcaprolactam, octanoylcaprolactam and benzoylcaprolactam
- substituted phenol esters of carboxylic acids such as e.g. Na acetoxybenzenesulfonate, Na octanoyloxybenzenesulfonate and Na nonanoyloxybenzenesulfonate
- acylated sugars such as Pentaacetyl glucose
- Anthranil derivatives such as 2-methylanthranil or 2-phenylanthrani1 25th
- Enol esters such as Isopropenyl acetate
- Oxime esters such as O-acetylacetone oxime
- Carboxylic anhydrides e.g. Phthalic anhydride or acetic anhydride.
- Tetraacetylethylenediamine and Na nonanoyloxybenzenesulfonates are preferably used as bleach activators.
- the bleach activators are heavy-duty detergents in amounts of 0.1 to 15% by weight, preferably in amounts of 1.0 to 8.0% by weight, particularly preferably in amounts of 1.5 to 6.0% by weight. % added.
- Suitable bleaching catalysts are quaternized imines and sulfonimines as described in US-A-5 360 568, US-A-5 360 569 and EP-A-0 453 003 and Mn complexes, cf. e.g. WO-A-94/21777. If bleach catalysts are used in the detergent formulations, they are in amounts of up to 1.5% by weight, preferably up to 0.5% by weight, in the case of the very active manganese complexes in amounts of up to 0.1% by weight .% contain.
- the detergents preferably contain an enzyme system. These are proteases, lipases, amylases and cellulases commonly used in detergents.
- the enzyme system can be limited to a single one of the enzymes or contain a combination of different enzymes. Of the commercially available enzymes, amounts of 0.1 to 1.5% by weight, preferably 0.2 to 1.0% by weight, of the finished enzyme are generally added to the detergents.
- Suitable proteases are Savinase ® and Esperase (manufactured by Novo Nordisk).
- a suitable lipase is, for example, Lipolase ® (manufacturer Novo Nordisk).
- a suitable Cellu ⁇ lase is Celluzym ® (manufactured by Novo Nordisk).
- the detergents preferably contain soil release polymers and / or graying inhibitors as other common constituents. This is e.g. around
- Polyesters from polyethylene oxides with ethylene glycol and / or propylene glycol and aromatic dicarboxylic acids or aromatic and aliphatic dicarboxylic acids are known, cf. for example US-A-3 557 039, GB-A-1 154 730, EP-A-0 185 427, EP-A-0 241 984, EP-A-0 241 985, EP-A-0 272 033 and US -A-5 142 020.
- soil release polymers are amphiphilic graft or copolymers of vinyl and / or acrylic esters on polyalkylene oxides, cf. US-A-4 746 456, US-A-4 846 995, DE-A-3 711 299, US-A-4 904 408, US-A-4 846 994 and US-A-4 849 126 or modi Treated celluloses such as methyl cellulose, hydroxypropyl cellulose or carboxymethyl cellulose.
- Graying inhibitors and soil release polymers are present in the detergent formulations in an amount of 0 to 2.5% by weight, preferably 0.2 to 1.5% by weight, particularly preferably 0.3 to 1.2% by weight.
- Soil release polymers are preferably used are the A-4 746 456 US-known graft polymers of vinyl acetate on polyethylene oxide of molecular 2büü from the - ⁇ ö ⁇ Oü in weight ratio 1,2: / polyoxyethylene terephthalates terephthalate 1, as well as commercially available polyethylene: 1 to 3.0 the molecular weight 3000 to 25000 from polyethylene oxides of the molecular weight 750 to 5000 with terephthalic acid and ethylene oxide and a molar ratio of polyethylene terephthalate to polyoxyethylene terephthalate from 8: 1 to 1: 1 and the block polycondensates known from DE-A-4 403 866, the blocks from (a) contain ester units from polyalkylene glycols with a molecular weight of 500 to
- a typical powder or granular heavy-duty detergent can have the following composition, for example:
- a color transfer inhibitor based on water-soluble homopolymers of N-vinylpyrrolidone or N-vinylimidazole, water-soluble copolymers of N-vinylimidazole and N-vinylpyrrolidone Copolymers of N-vinyl imidazole and N-vinyl pyrrolidone with a particle size of 0.1 to 500, preferably up to 250 ⁇ m, these copolymers being 0.01 to 5, preferably 0.1 to 2% by weight of N, N ' -Divinylethyleneurea contain as crosslinker.
- Further color transfer inhibitors are water-soluble and also crosslinked polymers of 4-vinylpyridine-N-oxide, which can be obtained by polymerizing 4-vinylpyridine and subsequent oxidation of the polymers.
- a bleaching system is often completely or partially dispensed with in color-gentle special detergents (for example in so-called color detergents).
- color detergents for example in so-called color detergents.
- a typical powder or granular color detergent can have the following composition, for example:
- a soil release polymer e.g. a graft polymer of vinyl acetate on polyethylene glycol.
- the powdery or granular detergents can contain up to 60% by weight of inorganic adjusting agents as other common constituents. Sodium sulfate is usually used for this. However, the detergents according to the invention are preferably low in adjusting agents and contain up to 20% by weight, particularly preferably up to 8% by weight of adjusting agents.
- Wa.1ch ⁇ itte.1 l.önr.cr. have different densities in the range from 300 to 950 g / l.
- Modern compact detergents generally have high bulk densities, for example 550 to 950 g / l, and show a granular structure.
- liquid detergents according to the invention contain, for example
- glycols such as ethylene glycol, diethylene glycol or propylene glycol or glycerin.
- the detergents can optionally contain other customary additives.
- Other additives which may be used include, for example, complexing agents, phosphonates, optical brighteners, dyes, perfume oils, foam dampers and corrosion inhibitors.
- Cleaners for hard surfaces include, for example, cleaners for cleaning metal, plastics, glass and ceramics, floor cleaners, sanitary cleaners, all-purpose cleaners in the household and in commercial applications, technical cleaners (for use in car washes or high-pressure cleaners), cold cleaners, dishwashers , Hand dishwashing detergents, rinse aids, disinfectant cleaners, cleaners for the food and beverage industry, in particular as bottle cleaners, as CIP cleaners (cleaning-in-place) in dairies, breweries and other companies operated by food manufacturers.
- CIP cleaners cleaning-in-place
- Cleaners that contain the surfactants according to the invention are particularly suitable for cleaning hard surfaces such as glass, plastic and plastic.
- the cleaners can be alkaline, acidic or ⁇ > neutral. They usually contain surfactants in amounts of about 5 to 90, preferably 10 to 75,% by weight, based on the active substance content.
- surfactants can be anionic, nonionic or cationic surfactants and mixtures of surfactants which are compatible with one another, for example mixtures of anionic and nonionic or of cationic and nonionic surfactants.
- Alkaline cleaners may contain soda, potash, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium sesquicarbonate, potassium sesquicarbonate, sodium hydroxide, potassium hydroxide, amine bases such as monoethanolamine, diethanoiamine, triethanolamine, ammonia or silicate in amounts of up to 60% by weight, in some cases even up to 80% by weight. %.
- the cleaners can also contain citrates, gluconates or tatrates in amounts of up to 80% by weight. They can be in solid or liquid form.
- the surfactants VII and Villa mentioned are also suitable as dyeing aids in leather dyeing.
- the derivatives VIII obtained in accordance with the general instructions or special embodiment of Example 7 were mixed with m mol of ethylene oxide (this corresponds to k mol per epoxy unit originally present) in the presence of 1% by weight of potassium hydroxide (based on VIII) at 100-110 ° C. implemented in a pressure vessel at 1.4 to 5.9 bar. The addition time was 5 hours and stirring was continued for a further 4 hours.
- the compounds according to the invention were obtained in the form of yellow pastes. (The number of epoxy units was determined by titration.)
- the cloud point was determined in accordance with DIN 53917.
- the temperature is determined above which the solution becomes cloudy and thus exists as a mixture of two liquid phases. In general, the lower the cloud temperature, the lower the foaming power.
- the foam capacity was determined in accordance with DIN 53902 by measuring the foam volume in ml one minute after the end of foam generation.
- the surface tension was determined in accordance with DIN 53914 by measuring the force in mN / m which is necessary to pull a plate or a horizontally suspended ring out of the liquid surface.
- the surfactants Villa according to the invention were tested under standard conditions (60 ° C., 5 g / l, 19% addition Villa) in model detergent formulation A without other surfactants.
- surfactants according to the invention from Examples 8 and 9 were used in combination with a nonionic surfactant in a model detergent formulation A without further surfactants under standard conditions (60 ° C., 5 g / l, 19% additive, thereof 38.6% Villa and 61.4% Ci 3 / ⁇ s-oxo alcohol with 7 mol ethylene oxide) checked.
- the fabrics were spun and the fabrics hung up individually to dry.
- the fabric was measured with an Elrepho 2COO from Data Color. Heidenheim, namely 6 measuring points per piece of tissue.
- the reflectance value was determined at 480 nm.
- Table 6 summarizes the total remission value R and the mean values of the primary washing power.
- the surfactants according to the invention can be used in the following example detergent formulations. O 3 tons
- Cobuilder 1 AS / MS (acrylic acid / maleic acid) copolymer MW 70000
- the present invention further relates to fatty acid amide derivatives with nonionically hydrophilically substituted amide groups and anionically substituted amine groups in the fatty acid chain or with anionically substituted amide groups and nonionically hydrophilic substituted amine groups in the fatty acid chain.
- the invention further relates to a process for the preparation of these fatty acid amide derivatives via corresponding epoxidized fatty acid amides and such epoxidized fatty acid amides themselves as intermediates in the production of surfactants.
- the invention further relates to mixtures of fatty acid amide derivatives with amine groups in the fatty acid chain and those with alkoxy groups in the fatty acidececte. Contrary to the present invention are also detergents and cleaning agents which contain the fatty acid amide derivatives or the mixtures of fatty acid amide derivatives mentioned as surfactants.
- DE-A 27 34 596 and DE-A 27 34 597 disclose the uses of aminohydroxystearic acid amides or esters as detergent substances in detergents or cold detergents.
- EP-A-0 633 243 describes a production process for ⁇ -hydroxylated secondary and tertiary amines.
- the products obtained by reacting epoxidized olefins such as epoxydodecane with amino acids are surface-active substances and are therefore suitable for numerous uses.
- US Pat. No. 3,155,658 discloses the reaction of epoxycarboxylic acid amides with amines.
- the products obtained are suitable as corrosion inhibitors, mineral oil additives and ore flotation aids.
- the object of the present invention was to provide surfactants with an even more advantageous range of properties than with the surfactants known in the prior art.
- a 4 is an aliphatic C 8 -C 24 radical with an unbranched carbon chain, which contains one or more in the chain
- R 12 is a hydroxyl- and / or amino-substituted hydrophilic radical with 2 to 40 C atoms
- Ri3 is hydrogen, an unsubstituted Ci C b alkyl radical or a radical R 12 ,
- Ri 4 is a C 1 -C 4 -alkyl radical which carries carboxyl and / or sulfonic acid groups in the form of the free acids and / or their alkali metal or ammonium salts and which has non-adjacent oxygen atoms, -NH groups and / or NC 1 -C 4 alkyl groups can be interrupted,
- R 15 is hydrogen, an unsubstituted Ci-C ⁇ -alkyl radical or a radical R 14 ,
- ricinoleic acid can be considered as unsaturated hydroxy fatty acid, but preferably
- C 9 -C 25 fatty acids such as petroselinic acid, undecenoic acid, ⁇ 9-decylenic acid, ⁇ 9-dodecylic acid, vaccenic acid, palmitoleic acid, erucic acid, elaidic acid and especially oleic acid,
- C 9 -C 25 polyunsaturated fatty acids such as stilingic acid and in particular linoleic acid as well
- triple unsaturated C 9 -C 25 fatty acids such as elaeostearic and in particular linolenic acid.
- Ci ⁇ fatty acids are particularly suitable due to their good availability.
- the fatty acids obtainable by isomerization of the double bond are also suitable.
- the fatty acid amide derivatives XV according to the invention can also be based on mixtures, in particular naturally occurring mixtures of such fatty acids.
- the amines HN (R 12 ) R 13 on which the amide groups in XV are based, with one or two nonionic hydrophilic substituents, can be branched and carry several hydroxyl or amino groups, such as (trishydroxymethylene) methylamine, but preferably have at least one unbranched ⁇ -hydroxyalkyl group or one unbranched ⁇ -amino-alkyl group ⁇ il in each case 2 to 6 C- ⁇ .to ⁇ er, whereby the underlying alkyl group by non-adjacent oxygen atoms, NH groups, N-C ⁇ -C 4 alkyl groups, N-C ⁇ -C 4 -hydroxy - Alkyl groups or N -CC 4 aminoalkyl groups can be interrupted. Furthermore, the N-C 1 -C 4 -alkyl-substituted derivatives are suitable if they still contain at least one reactive amino or imino group.
- Hydroxyalkylamines such as mono- and diethanoiamine, mono- and diisopropanolamine, 2- (2-aminoethoxy) ethanol, 2- [(2-aminoethyl) amino] ethanol, 3-aminopropanol, aminopropyldiethanolamine, aminosorbitol, glucamine and N-alkyl-substituted Hydroxyalkylamines such as methylethanolamine, n-propylethanolamine, butylethanolamine, N-methylglucamine and 2-aminobutanol-1,
- Aminoalkylamines such as ethylenediamine, trimethylene diamine,
- amino acids amino or iminocarboxylic acids
- amino acids amino or iminosulfonic acids
- carboxylic or sulfonic acids are preferably unbranched. You can also further acid or acid wear amide groups and optionally substituted with hydroxyl radicals. It is irrelevant for the effect whether D or L forms or mixtures thereof, for example racemates, are used.
- the known amino acids are generally easily accessible, for example, by the Strecker reaction. A large part of the amino acids is commercially available. Examples of amino acids which can be considered are:
- Monocarboxylic acids such as valine, leucine, isoleucine, ornithine, citrulline, serine, threonine, in particular alanine, arginine, lysine, especially glycine and sarcosine,
- Dicarboxylic acids such as ATP, aspartic acid, glutamine, glutamic acid, especially iminodiacetic acid and ethylenediaminodiacetic acid,
- Tricarboxylic acid such as aspartic acid monoacetic acid
- Sulfonic acids such as N-methyl taurine and taurine.
- radicals R 13 and / or R 15 are C ⁇ -C 6 -alkyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, see. -Pentyl, tert. -Pentyl, neo-pentyl, hexyl or in particular methyl or ethyl.
- the reaction of the epoxidized fatty acid amides XVII with the amines HN (R 14 ) R 15 is usually carried out at 20 to 280 ° C, in particular 50 to 200 ° C, especially 80 to 180 ° C, usually at normal pressure and preferably in Presence of a basic catalyst, for example an alkali metal hydroxide, alkali metal carbonate or alkali metal alcoholate such as sodium methylate, sodium ethylate or potassium tert. -butylate.
- a basic catalyst for example an alkali metal hydroxide, alkali metal carbonate or alkali metal alcoholate such as sodium methylate, sodium ethylate or potassium tert. -butylate.
- the reaction is complete when no more epoxy groups can be detected.
- the epoxidized fatty acid amides XVII themselves can be obtained by reacting corresponding epoxidized fatty acid esters, fatty acids or their salts with the amines HN (R 12 ) R 13 . In principle, the same conditions with regard to temperature, pressure, catalysts used or other reaction parameters as Dei der UmseLzuny are epoxidized. Fatty acid amides XVII with the amines HN (R 14 ) R 15 applied.
- the epoxidized fatty acid esters, fatty acids or their salts used as starting materials can be prepared by epoxidation of corresponding unsaturated fatty acid esters, fatty acids or their salts by customary methods.
- the epoxidation is usually carried out in a manner known per se by reaction with peracids such as performic acid and peracetic acid.
- peracids such as performic acid and peracetic acid.
- some epoxidized fatty acid esters or fatty acids are also commercially available.
- the production of the epoxidized fatty acid esters or fatty acids is preferably based on natural fats, that is to say the glycerol esters, in particular triglycerides, which contain at least one unsaturated fatty acid residue.
- natural fats are, for example, olive oil, cottonseed oil, linseed oil, tallow, fish oils, tall oil, castor oil, coconut oil, hemp oil, sperm oil, lard, tallow, goose fat, beef tallow, claw oil, tallow fatty acid, camelina oil, sunflower oil, peanut oil, palm oil and Euphor all soybean oil, rapeseed oil and turnip oil.
- fatty acid or fatty acid ester mixtures can also be used, such as those obtainable, for example, by transesterification or saponification of natural fats with C 1 -C 4 alcohols, preferably methanol.
- reaction of the epoxidized fatty acid esters or fatty acids with the amines HN (R 12 ) R 13 and the reaction of the epoxidized fatty acid amides XVII with the amines HN (R 14 ) R 15 can be carried out in the presence of a solvent, but this is often not the case is necessary, so that one often gets by without a solvent.
- the amines HN (R 12 ) R 13 or HN (R 14 ) R 15 are not liquids, but solids such as, for example, the amino acids, their implementation as a suspension in water-soluble or partially water-soluble solvents possible.
- polyhydric alcohols and, in particular, glycerin, ethylene glycol and propylene glycol are suitable, since they can subsequently remain in the product.
- the Na salt of the amino acid is introduced in, for example, propylene glycol with the basic catalyst and the reactant is metered in; Reaction temperatures of 60 to 200 ° C., in particular 100 to 180 ° C., are advantageous here.
- the amines mentioned, in particular the amino acids are purely aqueous solutions in the reaction.
- the Na salt of the amino acid ars besx.a i.oLZ de-u reaction gich is added.
- the preferred upper temperature range is 220 to 260 ° C.
- the amino acid is dissolved in a little water and heated together with the base and the epoxidized fatty acid or its ester. The high temperatures cause the water to evaporate directly, so that the reaction mixture is in the form of a melt.
- the epoxidized fatty acid esters, epoxidized fatty acids or their salts are generally reacted with one or approximately one equivalent of amine HN (R 12 ) R 15 per carboxylic acid unit.
- amine HN R 12
- R 15 per carboxylic acid unit.
- Such a production process for the epoxidized fatty acid amides XVII is also the subject of the present invention.
- the amine reacts alone or to a large extent with the ester or. Carboxylic acid function with amide formation, the epoxy grouping remains 5 completely or almost completely. If epoxidized fatty acids are used in the acid form, the reaction with up to two equivalents of amine is recommended, since part of the amine reacts to form the ammonium salt.
- the epoxidized fatty acid amides XVII are reacted with at least one equivalent of amine HN (R 14 ) R 15 per epoxy unit, 1 to 2.5, in particular 1 to 1.3 equivalents of amine per epoxy unit being preferred.
- a mode of operation is very particularly preferred in which the reaction of the epoxidized fatty acid esters or fatty acids with the amines HN (R 12 ) R 13 and the subsequent reaction of the obtained ones epoxidized fatty acid amides XVII with the amines HN (R 14 ) R 15 in a two-stage "one-pot" synthesis, ie in the same reaction vessel without intermediate isolation.
- epoxidized fatty acid lower alkyl esters or epoxidized triglycerides with hydroxyalkylamines or aminoalkylamines can be reacted with alcohol to the corresponding epoxidized fatty acid amides XVII and then the fatty acid amide derivative with the solid Na salt of an amino acid or with the aqueous solution of such a salt Make XV.
- epoxidized fatty acid lower alkyl esters or epoxidized triglycerides with the Na salt of an amino acid in solution or suspension to the corresponding epoxidized fatty acid amides XVII uinaetüeij u.iJ then by further reaction with hy ⁇ -hydroxyal.kylamines or aminoalkylamines derived therefrom the fatty acid amide derivative make XV.
- the epoxidized fatty acid amides XVII described thus represent a central intermediate on the way to the fatty acid amide derivatives XV.
- N-nucleophiles amines (e.g. NH 3 , urotropin), amino acids,
- Aminoacetonitriles e.g. RNH-CHR '-CN
- amides ureas, thioureas, imides, hydroxylamines (e.g. H 2 N0H), hydrazines (e.g. H 2 NNH 2 )
- Hydrazides e.g. RC0NHNH 2
- cyanamides e.g. RNH-CN
- nitrocyanamides e.g. NaN (N0 2 ) CN
- nitrate nitrite
- N0 2 - azide
- Nitrones N-oxides, cyanates, isocyanates (NCO "), isothiocyanate,
- 0-nucleophiles alcohols (e.g. Ci-C ⁇ -alkanols, also polyhydric alcohols such as ethylene glycol, glycerin), sugar (e.g. glucose, sucrose),
- alcohols e.g. Ci-C ⁇ -alkanols, also polyhydric alcohols such as ethylene glycol, glycerin
- sugar e.g. glucose, sucrose
- Carboxylates eg acetates, formates, oxalates, lactates, salts of malic acid
- Carboxylates eg acetates, formates, oxalates, lactates, salts of malic acid
- free acids water, hydroxide (OH-), hydroperoxide (OOH-), phenolates
- S nucleophiles bisulfite (HSO 3 -), sulfite (S0 3 2 "), thiocyanate (SCN”), isothiocyanate, S 2 2 ', mercaptans (HS ", RS”), S 2 0 3 2 "
- S nucleophiles bisulfite (HSO 3 -), sulfite (S0 3 2 "), thiocyanate (SCN”), isothiocyanate, S 2 2 ', mercaptans (HS ", RS”), S 2 0 3 2 "
- H- hydroxide
- OOH- hydroperoxid
- nucleophiles phosphonates, borates and the corresponding free acids, LiAIH 4 and other H'-donors, halides.
- R and R ' are organic radicals.
- the present invention also relates to epoxidized fatty acid amides of the general formula XVII
- B 3 is an aliphatic C 8 -C 24 radical with an unbranched carbon chain which contains one or more epoxide groups in the chain,
- R " is a hydroxyl- and / or amino-substituted hydrophilic radical having 2 to 40 C atoms or a C 1 -C 14 alkyl radical which carries carboxyl and / or sulfonic acid groups in the form of the free acids and / or their alkali metal or ammonium salts and which can be interrupted by non-adjacent oxygen atoms, -NH groups and / or N-C 1 -C 4 -alkyl groups, and
- R 1 is hydrogen, an unsubstituted C 1 -C 6 -alkyl radical or a radical R 12 ,
- the fatty acid amide derivatives XV are compounds with excellent surface-active properties, which are therefore outstandingly suitable for use as anionic surfactants in detergents and cleaning agents. Low surface and interfacial tension are found in the test. In addition, they show good fat-dissolving power and good primary washing power.
- the extremely advantageous property profile of these surfactants is mainly explained by the balanced balance between non-ionically hydrophilic and anionic substituents in XV.
- the present invention therefore also relates to detergents and cleaning agents which contain the er-.iiidur.gsgemc-l.cr- fatty acid amide derivatives XV as surfactants in amounts customary for this purpose and other additives customary for such agents.
- synergistic effects can be observed in the primary washing power which exceed previously known effects with mixtures of anionic and nonionic surfactants.
- synergistic effects also occur with anionic surfactants, for example with fatty alcohol sulfonates or fatty alcohol ester sulfates.
- the fatty acid amide derivatives XV show good fat-dissolving properties in application tests. These grease-dissolving properties are a very important requirement in the field of cleaning agents for hard surfaces, since greases generally prevent the wetting of other dirt particles.
- the fat-dissolving power of a surfactant is just as important for washing textiles. Surfactants with such properties are often poorly water-soluble, which is reflected in low cloud points.
- the compounds XV according to the invention also have higher cloud points so that they are suitable, for example, as a surfactant in a heavy-duty detergent.
- the compounds XV are used in detergents alone or in combination with at least one anionic and / or nonionic surfactant, usually in an amount of 2 to 50, preferably
- the detergents can be in powder form or can also be in liquid form.
- the composition of the detergents and cleaners can be very different.
- Detergent and cleaning agent formulations usually contain 2 to 50% by weight Surfactants and optionally builders. This information applies to both liquid and powder detergents. Detergent and cleaning agent formulations that are common in Europe, the USA and Japan can be found, for example, in Chemical and Engn. News, volume 67, 35 (1989). Further information on the composition of detergents and cleaners can be found in Ulimann's Encyclopedia of Industrial Chemistry, Verlag Chemie, Weinheim 1983, 4th edition, pages 63 to 160.
- Phosphate-reduced detergents are understood to mean those formulations which contain at most 25% by weight of phosphate, calculated as pexite- ⁇ xiaLrit-i -triphosphet.
- Detergent can be a full detergent or a special detergent. Both anionic and nonionic or mixtures of anionic and nonionic surfactants are suitable as surfactants.
- the surfactant content of the detergents is preferably 8 to 30% by weight.
- Suitable anionic surfactants are, for example, fatty alcohol sulfates of fatty alcohols having 8 to 22, preferably 10 to 18 carbon atoms, for example C 9 to Cn alcohol sulfates, C ⁇ 2 to C 3 . 3- alcohol sulfates, cetyl sulfate, myristyl sulfate, palmityl sulfate, stearyl sulfate and tallow fatty alcohol sulfate.
- Suitable anionic surfactants are sulfated, ethoxylated C ⁇ to C 22 alcohols or their soluble salts.
- Compounds of this type are prepared, for example characterized in that firstly a C ⁇ - to C 22 -, preferably a C 10 - to Ci ⁇ alcohol alkoxylated and subsequently sulfating the alkoxylation.
- Ethylene oxide is preferably used for the alkoxylation, 2 to 50, preferably 3 to 20, moles of ethylene oxide being used per mole of fatty alcohol.
- the alkoxylation of the alcohols can also be carried out using propylene oxide alone and, if appropriate, butylene oxide.
- alkoxylated C ⁇ to C 22 alcohols which contain ethylene oxide and propylene oxide or ethylene oxide and butylene oxide.
- the alkoxylated Cs * to C 22 "alcohols can contain the ethylene oxide, propylene oxide and butylene oxide units in the form of blocks or in a statistical distribution.
- Suitable anionic surfactants are alkyl sulfonates such as C ⁇ - to C 24 -, preferably Cio-Ci ⁇ -alkanesulfonates and soaps such as the salts of C ⁇ - to C 24 -carboxylic acids.
- Other suitable anionic surfactants are Cg to C 20 linear alkylbenzenesulfonates (LAS).
- the fatty acid derivatives according to the invention are preferably used in low-LAS detergent formulations with less than 4% by weight, particularly preferably in LAS-free formulations.
- the anionic surfactants are preferably added to the detergent in the form of salts.
- Suitable cations in these salts are alkali metal salts such as sodium, potassium or lithium salts and ammonium salts such as e.g. Hydroxyethylammonium, di (hydroxyethyl) ammonium and tri (hydroxyethyl) ammonium salts.
- Suitable nonionic yensides are, for example, alkoxylated C ⁇ to C 22 "alcohols.
- the alkoxylation can be carried out using ethylene oxide, propylene oxide and / or butylene oxide. All alkoxylated alcohols which contain at least two molecules of an abovementioned alkylene oxide added can be used as surfactants.
- block polymers of ethylene oxide, propylene oxide and / or butylene oxide come into consideration or adducts which contain the alkylene oxides mentioned in a statistical distribution, 2 to 50, preferably 3 to 20, mol of at least one alkylene oxide being used per mole of alcohol ethylene oxide as the alkylene oxide
- the alcohols preferably have 10 to 18 carbon atoms.
- alkyl polyglucosides with 8 to 22, preferably 10 to 18 carbon atoms in the alkyl chain. These compounds contain 1 to 20, preferably 1.1 to 5, glucoside units.
- N-alkylglucamides of the general structure XIII or XIV
- Y is a C ⁇ to C 22 'alkyl
- X is an H or Cj to C 4 alkyl
- Z is a polyhydroxyalkanyl radical having 5 to 12 C atoms and at least 3 hydroxy groups.
- Y is preferably C 10 - bis
- Ci ⁇ -alkyl, X for CH 3 - and Z for a C 5 or C ⁇ radical are obtained by the acylation of reducing aminated sugars with acid chlorides of Cio-Ci ⁇ -carboxylic acids.
- the detergent formulations preferably contain C 10 -C 16 alcohols ethoxylated with 3-12 mol ethylene oxide, O 97/16408 PO7EP96 / 04560
- surfactants are the end group-capped fatty acid amide alkoxylates of the general formula known from WO-A-95/11225
- L 2 represents a C 1 to C 4 alkyl group
- m denotes the number 2, 3 or 4
- n denotes the number 2 or 3
- x has a value from 1 to 6.
- Examples of such compounds are the reaction products of n-butyltriglycolamine of the formula H 2 N- (CH 2 -CH 2 O) 3 -C 4 H 9 with methyl dodecanoate or the reaction products of ethyl tetraglycolamine of the formula H 2 N- (CH 2 -CH 2 -O) 4 -C 2 H 5 with a commercially available mixture of saturated C ⁇ - to Ci ⁇ -fatty acid methyl esters.
- the powdered or granular detergents and, if appropriate, structured liquid detergents also contain one or more inorganic builders. All conventional inorganic builders such as aluminosilicates, silicates, carbonates and phosphates are suitable as inorganic builder substances.
- Suitable inorganic builders are e.g. Aluminum silicates with ion-exchanging properties such as Zeolites.
- zeolites are suitable, in particular zeolite A, X, B, P, MAP and HS in their Na form or in forms in which Na is partly replaced by other cations such as Li, K, Ca, Mg or ammonium.
- Suitable zeolites are described, for example, in EP-A-0 038 591, EP-A-0 021 491, EP-A-0 087 035, US-A-4 604 224, GB-A-2 013 259, EP-A- 0 522 726, EP-A-0 384 070 and WO-A-94/24251.
- Suitable inorganic builders are, for example, amorphous or crystalline silicates such as, for example, amorphous disilicates, crystalline disilicates such as the layered silicate SKS-6 (manufacturer Hoechst AG).
- the silicates can be used in the form of their alkali, alkaline earth or ammonium salts.
- Na, Li and Mg silicates are preferably used.
- Other suitable inorganic builder substances are carbonates and hydrogen carbonates. These can be used in the form of their alkali, alkaline earth or ammonium salts.
- Na, Li and Mg carbonates or bicarbonates, in particular sodium carbonate and / or sodium bicarbonate, are preferably used.
- the inorganic builders can be present in the detergents in amounts of 0 to 60% by weight together with organic cobuilders which may be used.
- the inorganic builders can be incorporated into the detergent either alone or in any combination with one another.
- powdered or granular detergents they are added in amounts of 10 to 60% by weight, preferably in amounts before * 20 to 50% by weight.
- structured (multi-phase) liquid detergents inorganic builders are added in amounts of up to 40% by weight. %, preferably up to 20% by weight. They are suspended in the liquid formulation components.
- Organic cobuilders are present in powder or granule form and in liquid detergent formulations in amounts of 0.1 to 20% by weight, preferably in amounts of 1 to 15% by weight, together with inorganic builders.
- the powdery or granular heavy-duty detergents can also contain, as other usual constituents, a bleaching system consisting of at least one bleaching agent, optionally in combination with a bleaching activator and / or a bleaching catalyst.
- Suitable bleaches are perborates and percarbonate in the form of their alkali metal salts, in particular their Na salts. They are present in quantities of 5 to 30% by weight, preferably 10 to 25% by weight
- bleaching agents are inorganic and organic peracids in the form of their alkali or magnesium salts or in some cases also in the form of the free acids.
- suitable organic percarboxylic acids or salts are e.g. Mg monoterephthalate, phthalimidopercaproic acid and
- Dodecane-1,10-diper acid An example of an inorganic peracid salt is potassium peroxomonosulfate (oxone).
- Suitable bleach activators are e.g.
- Acylamines such as tetraacetylethylenediamine (TAED), tetraacetylglycoluril, N, N'-diacetyl-N, N'-dimethylurea and 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine,
- TAED tetraacetylethylenediamine
- N, N'-diacetyl-N, N'-dimethylurea 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine
- acylated lactams such as, for example, acetylcaprolactam, octanoylcaprolactam and benzoylcaprolactam, substituted phenol esters of carboxylic acids such as, for example, Na acetoxybenzenesulfonate, Na octanoyloxybenzenesulfonate and Na nonanoyloxybenzenesulfonate,
- Anthranil derivatives such as 2-methylanthranil or 2-phenylanthranil,
- Oxime esters such as O-acetylacetone oxime
- Carboxylic anhydrides e.g. Phthalic anhydride or 15 acetic anhydride.
- Tetraacetylethylene diamine and Na nonanoyloxybenzenesulfonates are preferably used as bleach activators.
- the bleach activators are heavy-duty detergents in amounts of 0.1 to 20 15% by weight, preferably in amounts of 1.0 to 8.0% by weight, particularly preferably in amounts of 1.5 to 6.0% by weight. -% added.
- Suitable bleaching catalysts are quaternized imines and sulfonimines as described in US Pat. Nos. 5,360,568, 5,360,569 and 5 EP-A-0 453 003 and Mn complexes, cf. e.g. WO-A-94/21777. If bleaching catalysts are used in the detergent formulations, they are up to 1.5% by weight, preferably up to 0.5% by weight, in the case of the very active manganese complexes up to 0.1% by weight .% contain. 0
- the detergents preferably contain an enzyme system. These are proteases, lipases, amylases and cellulases commonly used in detergents.
- the enzyme system can be limited to a single one of the enzymes or contain a combination of different enzymes. Of the commercially available enzymes, amounts of 0.1 to 1.5% by weight, preferably 0.2 to 1.0% by weight, of the finished enzyme are generally added to the detergents.
- Suitable proteases are Savinase ® and Esperase (manufactured by Novo Nordisk).
- a suitable lipase is 0 eg Lipolase ® (manufactured by Novo Nordisk).
- a suitable Cellu ⁇ loosely Celluzym ® (manufactured by Novo Nordisk).
- the detergents preferably contain soil release polymers and / or graying inhibitors as other common constituents.
- These are, for example, polyesters made of polyethylene oxides with ethylene glycol and / or propylene glycol and aromatic dicarboxylic acids or aromatic and aliphatic dicarboxylic acids or Polyesters from polyethylene oxides end-capped with di- and / or polyhydric alcohols and dicarboxylic acids.
- Such polyesters are known, cf. for example US-A-3 557 039, GB-A-1 154 730, EP-A-0 185 427, EP-A-0 241 984, EP-A-0 241 985, EP-A-0 272 033 and US -A-5 142 020.
- soil release polymers are amphiphilic graft or copolymers of vinyl and / or acrylic esters on polyalkylene oxides (cf. US Pat. No. 4,746,456, US Pat. No. 4,846,995, DE-A-3,711,299, US) -A-4 904 408, US-A-4 846 994 and US-A-4 849 126) or modified celluloses such as, for example Methyl cellulose, hydroxypropyl cellulose or carboxymethyl cellulose.
- Graying inhibitors and soil release polymers are contained in the detergent formulations in an amount of 0 to 2.5% by weight, preferably 0.2 to 1.5% by weight, particularly preferably 0.3 to 1.2% by weight.
- Soil release polymers used with preference are the graft polymers of vinyl acetate on polyethylene oxide of molecular weight 2500-8000 in a weight ratio of 1.2: 1 to 3.0: 1, known from US Pat. No.
- polyethylene terephthalate / polyoxyethylene terephthalates the molecular weight 3000 to 25000 from polyethylene oxides of the molecular weight 750 to 5000 with terephthalic acid and ethylene oxide and a molar ratio of polyethylene terephthalate to polyoxyethylene terephthalate from 8: 1 to 1: 1 and the block polycondensates known from DE-A-4 403 866, the blocks from (a) contain ester units from polyalkylene glycols with a molecular weight of 500 to 7500 and aliphatic dicarboxylic acids and / or monohydroxymonocarboxylic acids and (b) ester units from aromatic dicarboxylic acids and polyhydric alcohols.
- These amphiphilic block copolymers have molecular weights from 1500 to 25000.
- a typical powder or granular heavy-duty detergent can, for example, have the following composition:
- a color transfer inhibitor based on water-soluble homopolymers of N-vinylpyrrolidone or N-vinylimidazole, water-soluble copolymers of N-vinylimidazole and
- N-vinylpyrrolidone crosslinked copolymers of N-vinylimidazole and N-vinylpyrrolidone with a particle size of 0.1 to 5CC, preferably up to and including 250 ⁇ n>, the copolymers being 0.01 to 5, preferably 0.1 to Contain 2% by weight of NN'-divinylethylene urea as crosslinking agent;
- further color transfer inhibitors are water-soluble and also crosslinked polymers of 4-vinylpyridine-N-oxide, which can be obtained by polymerizing 4-vinylpyridine and subsequent oxidation of the polymers;
- a bleaching system is often completely or partially dispensed with in color-gentle special detergents (for example in so-called color detergents).
- color detergents for example in so-called color detergents.
- a typical powder or granular color detergent can have the following composition, for example:
- a soil release polymer e.g. a graft polymer of vinyl acetate on polyethylene glycol.
- the powdery or granular detergents can contain up to 60% by weight of inorganic stabilizers as other common constituents. Sodium sulfate is usually used for this. However, the detergents according to the invention are preferably low in adjusting agents and contain up to 20% by weight, particularly preferably up to 8% by weight of adjusting agents.
- the detergents according to the invention can have different bulk densities in the range from 300 to 950 g / l.
- Modern compact detergents generally have high bulk densities, e.g. 550 to 950 g / l, and show a granular structure.
- Typical liquid detergents contain, for example:
- glycols such as ethylene glycol, diethylene glycol or propylene glycol or glycerin.
- the detergents can optionally contain other customary additives.
- additives e.g. Complexing agents, phosphonates, optical brighteners, dyes, perfume oils, foam dampers and corrosion inhibitors can be included.
- cleaning agents in particular those for hard surfaces, for example cleaners for cleaning metal, plastics, glass and ceramics, floor cleaners, sanitary cleaners, all-purpose cleaners in the household and in commercial applications, are intended to be more technical (for use in car washes) or high-pressure cleaners), cold cleaners, dishwashers, hand dishwashing detergents, rinse aids, disinfectant cleaners, cleaners for the food and beverage industry, in particular as bottle cleaners, as CIP cleaners (cleaning-in-place) in dairies, breweries and other food businesses - manufacturers are understood.
- detergent boosters are products rich in surfactants, the focus of which is on easy-care textiles, in which certain washing temperatures should not be exceeded. Soaking agents are usually strongly alkaline washing aids based on mixtures of anionic and nonionic surfactants that loosen stubborn and firmly adhering dirt.
- Post-treatment agents such as softening agents, tumble aids, form washers, spray starches, ironing aids and other stiffeners.
- Carpet cleaning agents including detaching agents, which are offered as aerosols for removing water-soluble stains based on surfactant and alcohol, and foam cleaners (spray and liquid products with aqueous solutions of surfactants, to which water-soluble organic solvents can be added) and powder cleaners and spray extraction cleaner.
- the powdery cleaners suitable for intermediate cleaning consist of a combination of active cleaning solutions and carrier materials with a large surface area.
- the active substances contain mixtures of surfactants, solvents and water.
- Spray extraction cleaners are aqueous concentrated Löö-u-yer. or powders containing surfactants, water softeners and optionally defoamers.
- cleaning agents such as all-purpose cleaners, abrasives, special cleaners (e.g. for limestone and urine scale) can also be used.
- solvent-based cleaning agents and aqueous cleaning agents alkaline, neutral, acidic
- surfactants for washing cars, trucks, railroad cars automated washing lines, systems and engine washing as well as for manual car cleaning
- passivating cleaning agents passivating cleaning agents
- combined cleaning and disinfectants food processing industry
- oil-in-water emulsions mayonnaise, sauces, etc.
- water-in-oil emulsions margarine and the like
- (soft) ice cream Biscuits, chewing gum, liquorice, caramels, chocolate, baked goods, dry products (such as powdered beverages, milk powder, pudding powder, etc.), sausage and cheese.
- plant protection product formulations are also suitable for fertilizers, synthetic fertilizers and salts (powders, granules, prills) which tend to form agglomerates ("baking").
- surfactants show anti-caking properties if they have a hy Form a hydrophobic film on the surface of the crystals and displace the water.
- the active ingredient in a preparation can be specifically activated by surfactants, so that absorption and compatibility can be controlled.
- Pretreatment agents for fibers production of rayon fibers, spin finishes and textile lubricants, dyeing aids, finishing agents, water repellents, auxiliaries for printing, antistatic agents and flocking and coating agents are mentioned here.
- watering aids for the preparation of active ingredient emulsions, -disper't> i ⁇ .- ⁇ - i- and Lc-tice-. and to name additions to inheritance baths.
- cooling lubricants hardness oils, hydraulic oil emulsions, polishing pastes, mold release agents, drawing oils, pickling agents, metal cleaners and metal dryers.
- Surfactants as biocides, for fire fighting (foam extinguishers, quick wetting of parts of buildings); Treatment of glass devices and glass fibers in order to maintain their strength and the desired properties; for dust control (e.g. in grinding processes, tensides are added to the spray water used), - Teijsidt, to pump feir.gc-r.ah.lcne coal or non-flowing heavy oils through pipelines with the help of aqueous dispersions (slurries) (increase in price).
- Cleaners containing the surfactants XV according to the invention are particularly suitable for cleaning hard surfaces such as glass, ceramic, plastic and metal, e.g. of floors, tiles and tiles.
- the cleaners can be alkaline, acidic or neutral. They usually contain surfactants in amounts of about 5 to 90, preferably 10 to 75,% by weight, based on the active substance content. These can be anionic, non-ionic or cationic surfactants as well as mixtures of surfactants that are compatible with one another, e.g. Mixtures of anionic and non-ionic or of cationic and non-ionic surfactants.
- Alkaline cleaners can contain soda, potash, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium sesquicarbonate, potassium sesquicarbonate, sodium hydroxide, potassium hydroxide, amine bases such as monoethanolamine, diethanoiamine,
- Triethanolamine, ammonia or silicate in amounts up to 60% by weight, in some cases even up to 80% by weight.
- the cleaners can also contain citrates, gluconates or tartrates in amounts of up to 80% by weight. They can be in solid or liquid form.
- a 4 is an aliphatic C ⁇ -C 24 radical with an unbranched carbon chain which contains one or more groupings of the formula XVI in the chain
- R 14 and R 16 and, independently of one another, a hydroxy- and / or amino-substituted hydrophilic radical with 2 to 40 carbon atoms.
- R 15 and R 17 are hydrogen, an unsubstituted Ci-C ß- alkyl radical or a radical R 14 or R 16 , and
- E is an aliphatic C ⁇ -C 24 residue with unbranched
- Carbon chain means which one or more groupings of the formula XX in the chain
- R 18 represents C 1 -C 4 alkyl
- the components (i) and (ii) being in a weight ratio of 99: 1 to 1:99, in particular 90:10 to 30:70, especially 80:20 to 45:55,
- radical R 18 in particular ethyl, propyl, isopropyl, butyl, tert-butyl and especially methyl are possible.
- Mixtures of components (i) and (ii) according to the invention can be, for example: Mixtures of fatty acid amide derivatives XVIII in which the groupings -N (R 14 ) R 15 and -N (R 16 ) R 17 are each derived from hydroxyalkylamines or aminoalkylamines (preferably -N (R 14 ) R 15 and -N ( R 16 ) R 17 identical), and fatty acid amide derivatives XIX, which are also based on hydroxyalkylamines or aminoalkylamines in the amide group (preferably the identical amines to the amines in XVIII);
- fatty acid amide derivatives XVIII in which the groups -N (R 14 ) R 15 and -N (R 16 ) R 17 are each derived from amino acids (preferably -N (R 14 ) R 15 and -N (R 16 ) R 17 identical), and fatty acid amide derivatives XIX, which are also based on Mi.-io-.aurei. ixi the A-r ⁇ dgrupptechnik ⁇ delay * .. 'ise the identical amino acids to the amino acids in XVIII);
- fatty acid amide derivatives XVIII in which the groupings -N (R 14 ) R 15 are derived from amino acids and the grouping -N (R 16 ) R 17 is derived from hydroxyalkylamines or aminoalkylamines, and fatty acid amide derivatives XIX, which are likewise derived from hydroxyalkylamines or aminoalkylamines the amide group (preferably the identical amines to the amines in the amide group -N (R 16 ) R 17 of XVIII);
- fatty acid amide derivatives XVIII in which the groupings -N (R 14 ) R 15 are derived from hydroxyalkylamines or aminoalkylamines and the grouping -N (R 16 ) R 17 is derived from amino acids, and fatty acid amide derivatives XIX, which are also based on amino acids in the amide grouping (preferably the identical amino acids to the amino acids in the amide group -N (R 16 ) R 17 of XVIII).
- the mixtures according to the invention can be prepared by corresponding epoxidized fatty acid amides, in particular the above-mentioned epoxidized fatty acid amides XVII, or corresponding epoxidized fatty acid esters, fatty acids or their salts with corresponding amines in the presence of alkanols of the formula R 18 -0H or their Salting. Some of the epoxy groups then react with the amine, the other with the alkanol. With regard to the fatty acid amide derivatives XIX, as with the fatty acid amide derivatives XVIII, isomer mixtures are generally obtained, since the oxirane rings can open at both C-O bonds.
- alkali metal alcoholate catalysis for example, 1 to 60 mol%, in particular 5 to 30 mol%, based on the amount to be converted is preferably used.
- an alkali metal alcoholate such as sodium methoxide or sodium ethanolate - the built-in residue -OR 18 comes from this alcoholate.
- a fatty acid lower alkyl ester for example a fatty acid methyl ester, is used as the starting material, the built-in radical -OR 18 comes from this alcohol released by exchanging the alcohol residue for the amine residue.
- the mixtures according to the invention also have the advantage that no excess amine can be removed for their preparation if such free amine is not desired in the product, because without the reaction with alkanols ⁇ ⁇ - üH become noiiu ⁇ lerweiae ÜLci ⁇ chuß-.iei "iC,” he. to Arr.ir_ is required to fully open the oxirane ring, since amines are somewhat less reactive than alcohols or alcohol ions under the reaction conditions towards oxiranes. Furthermore, the mixtures according to the invention are readily biodegradable.
- the present invention furthermore relates to detergents and cleaning agents which contain the mixture according to the invention of components (i) and (ii) as surfactants in the amounts customary for this purpose and other additives customary for such agents.
- the surfactant mixture mentioned comprises (i ) and (ii) is also suitable as a dyeing aid for leather dyeing.
- the interfacial tension was determined as a function of the contact time between an aqueous surfactant solution and an oil phase.
- the contact angle was measured as the wetting ability of a hard surface by the surfactant solution. Complete wetting (spreading) corresponds to zero contact angle.
- the surface tension was determined in accordance with DIN 53914 by measuring the force in mN / m which is necessary to pull a plate or a horizontally suspended ring out of the liquid surface.
- the fatty acid amide derivatives XV according to the invention show a typical property profile of anionic surfactants. They stand out from conventional anionic surfactants such as LAS due to their lower surface tension and lower interfacial tension, especially with a longer oil contact time. In particular, they show a very good fat-removing ability of olive oil and neutral oil from glass, they are usually soluble in clear water or only slightly cloudy in hard water.
- reaction products of aminopropyldiethanolamine with sarcosine or glycine and epoxidized beet oil methyl ester show similarly good performance properties as the reaction products of diethanoiamine with sarcosine or glycine and epoxidized beet oil methyl ester (examples 15 and 16).
- Example 19 and Comparative Example 20 show similarly good performance properties as the reaction products of diethanoiamine with sarcosine or glycine and epoxidized beet oil methyl ester (examples 15 and 16).
- Example 15 The substances from Example 15 were further tested under standard conditions (60 ° C., 5 g / l) in a model detergent formulation together with a C 3 / Is oxo alcohol reacted with 7 mol of ethylene oxide as nonionic surfactant (19% surfactant additive , 47% of which the substance from Example 15 and 53% of the non-ionic surfactant mentioned) (Example 19).
- the comparison used was an analog model detergent formulation with 19% of surfactant, of which 47% of a C ⁇ 2 / ⁇ * alkyl sulfate as the anionic surfactant and 53% of the ge nonionic surfactant called (Example 20).
- Acrylic acid / maleic acid - 5% copolymer (MW 70000)
- Surfactant mixture 19% After rinsing, the fabrics were spun and the fabrics hung up individually to dry. The fabric was measured with an Elrepho 2000 from Data Color, Heidenheim, namely 6 measuring points per piece of fabric. The reflectance value was determined at 480 nm.
- a mixture of 1575 g (15 mol) of diethanoiamine and 369 g of sodium methylate solution (2.0 mol, 30% in methanol) was heated to 90 ° C. under a protective gas atmosphere and under reflux and slowly at this temperature with 2291 g ( 7.5 mol) of epoxidized rape oil methyl ester.
- the mixture was then heated to 130 ° C. and stirred at this temperature for a further 5 h.
- the conversion was checked by means of GC, amine-epoxy double titration and Preussmann test and the product mixture was released after the reaction was complete.
- the reaction product was obtained as a highly viscous yellowish liquid. It contained the corresponding components (i) and (ii) in a weight ratio of 80:20.
- Example 21 was repeated with the difference that instead of 15 mol of diethanoiamine only 7.5 mol of diethanoiamine was used.
- the resulting product mixture contained the corresponding components (i) and (ii) in a weight ratio of 45:55.
- the interfacial tension was determined as a function of the contact time between an aqueous surfactant solution and an oil phase.
- the wettability of a hard surface through the surfactant solution was measured via the rend angle. Complete wetting (spreading) corresponds to zero contact angle.
- the surface tension was determined in accordance with DIN 53914 by measuring the force in mN / m which is necessary to pull a plate or a horizontally suspended ring out of the liquid surface.
- the cloud point was determined in accordance with DIN 53917.
- the temperature is determined above which the solution becomes cloudy and thus exists as a mixture of two liquid phases. In general, the lower the cloud temperature, the lower the foaming power.
- the interfacial tension values of the mixtures according to the invention of components (i) and (ii) against the various oils are significantly lower than those of conventional nonionic surfactants such as corresponding sugar surfactants or corresponding fatty alcohol ethoxylates.
- the wetting capacity on cotton of the mixtures according to the invention is at least as good as that of most conventional nonionic surfactants.
- Your fat-removing ability from various Sen surfaces, especially in olive oil, is significantly better than many common nonionic surfactants, such as fatty alcohol ethoxylates.
- the mixture of components (i) and (ii) according to the invention show degradation values of 40 to 60% in the modified storm test in the order of 40 to 60% DOC degradation after 28 days and degradation values in the order of 50 to 70% in the tooth-wave test. after 28 days or 80 to 90% after 56 days (DOC elimination level in each case).
- component (ii) in the inventive mixtures show degradation values of 40 to 60% in the modified storm test in the order of 40 to 60% DOC degradation after 28 days and degradation values in the order of 50 to 70% in the tooth-wave test. after 28 days or 80 to 90% after 56 days (DOC elimination level in each case).
- the biodegradability also increases noticeably.
- K.L. Johnson describes in J. Am. Oil Chem. Soc, 1966, 43, pp. 497-500 as nonionic detergents based on epoxidized oils, the compounds obtainable by reaction of methylpolyglycols with methyl epoxystearic acid and subsequent reaction with alkanolamines.
- the reaction of the methyl polyglycols with the epoxy ester takes place in the presence of a "Friedel-Crafts catalyst" such as tin tetrachloride, boron trifluoride or antimony pentachloride.
- the fatty acid amides obtained are recommended as surface-active agents in low-foam cleaners, in dishwashing detergents, in floor cleaning agents and in other cleaning formulations.
- Cio-alkenoxy (or alkynoxy) -hydroxy-substituted fatty acid amides are known in the fatty acid chain. These are suitable as emulsifiers, textile auxiliaries or cosmetic additives.
- G is an aliphatic C ⁇ * C 24 radical with an unbranched carbon chain which has one or more groupings of the formula XXII in the chain
- R 19 represents C 1 -C 4 -alkyl or hydrogen
- R 16 is a hydroxyl- and / or amino-substituted hydrophilic radical having 2 to 40 C atoms or a C 1 -C 14 alkyl radical which carries carboxyl and / or sulfonic acid groups in the form of the free acids and / or their alkali metal or ammonium salts and which can be interrupted by non-adjacent oxygen atoms, -NH groups and / or NC 1 -C 4 alkyl groups means and
- j> - 7 'Messersteff denotes an unsubstituted Ci -Cr alkyl radical or an R 16 radical.
- the unsaturated unbranched aliphatic fatty acids are those mentioned above. Unsaturated Ci ⁇ fatty acids are preferred.
- Methyl is particularly suitable as the C 1 -C 4 -alkyl radical for R 19 .
- the amines HN (R 16 ) R 17 on which the amide groups in XXI are based, with one or two nonionic hydrophilic substituents, can be branched and carry several hydroxyl or amino groups such as (trishydroxymethylene) methylamine, but preferably have at least one unbranched ⁇ -hydroxyalkyl group or one unbranched ⁇ -aminoalkyl group, each having 2 to 6 carbon atoms, the underlying alkyl group being formed by non-adjacent oxygen atoms, NH groups, NC 1 -C 4 alkyl groups, NC 1 -C 4 hydroxyalkyl groups or N-C 1 -C 4 -Aminoalkyl groups can be interrupted. Furthermore, the N-Ci-C 4 -alkyl-substituted derivatives are suitable if they still contain at least one reactive amino or imino group.
- Such amines include, in particular, those mentioned above.
- the compounds containing the amide groupings -N (R 16 ) R 17 in XXI on which the carbon and / or sulfonic acid residues are based are, in particular, amino acids as mentioned above.
- the present invention also relates to a process for the preparation of the fatty acid derivatives XXI according to the invention, which is characterized in that an epoxidized fatty acid derivative of the general formula XXIII B 3 -CO-R 20 (XXIII)
- B 3 is an aliphatic C ⁇ -C24 radical with unbranched carbon chain, which contains one or more epoxy groups in the chain, and
- R 20 is a hydroxyl radical and its alkali metal or ammonium salts, a C 1 -C 4 alkoxy radical or a radical of a mono-, di- or triglyceride, the di- or triglyceride radicals being residues of natural saturated or unsaturated fatty acids,
- the reaction of the epoxidized fatty acid derivative with 2 equivalents of amine is base-catalyzed by the conventional method, as described above.
- One molar equivalent of the amine initially reacts with the ester to form amine, then the remaining amine reacts with the epoxide.
- the alkanol released from the alkyl ester like the alkanol from the alcoholate catalyst solution, usually remains in the reaction system according to this process, as a result of which the alcohol competes with the amine when attacking the epoxy group and it also forms in the fatty acid chain alkoxy-substituted structures comes.
- the epoxidized fatty acid derivative XXIII is first acid-catalyzed, preferably using Lewis acids such as BF 3 . OEt 2 , FeCl 3 or TiCl 4 or with protonic acids such as tetrafluoroboric acid, orthophosphoric acid or phosphorous acid or with acidic rem ion exchanger with which alcohol is reacted.
- Lewis acids such as BF 3 .
- protonic acids such as tetrafluoroboric acid, orthophosphoric acid or phosphorous acid or with acidic rem ion exchanger with which alcohol is reacted.
- the epoxide is opened very quickly to the vicinal alkoxy-hydroxy-fatty acid ester. There is no transesterification.
- This ester or triglyceride is then base-catalyzed with the hydrophilic amine or the amino acid to form the surface-active compound.
- the vicinal alkoxy-hydroxy fatty acid ester can be distilled for purification or can also be used directly in the subsequent amidation. These two reaction steps can also be easily combined to form a "one-pot reaction". In this case, slightly more basic catalyst must be used to neutralize the acidic catalyst.
- acid derivative usually an ester or triglyceride, acid-catalyzed, preferably with protic acids such as H 3 P0 4 , H 3 P0 3 or HBF 4 or with an acidic ion exchanger, with water
- protic acids such as H 3 P0 4 , H 3 P0 3 or HBF 4 or with an acidic ion exchanger
- water The epoxide is opened to the vicinal dihydroxy fatty acid ester, and under the chosen reaction conditions there is practically no saponification to give the carboxylic acid, and this ester is then reacted with the hydrophilic amine or the amino acid, the vicinal dihydroxy Fatty acid ester can be distilled for purification or can also be used directly in the subsequent amidation.
- the process according to the invention differs from the conventional base-catalyzed process in particular in that the total reaction time is significantly shortened, since the rate-determining epoxide opening is considerably faster in the present acid catalysis (generally ⁇ 30 min compared to> 300 min).
- the uniform products produced by the acid-catalyzed process are highly viscous, sufficiently pure and clearly water-soluble.
- the amidation can be carried out without a solvent.
- opening the epoxy with the alcohol usually requires a certain excess of alcohol (usually 5 to 10 equivalents of alcohol) as a solvent.
- the excess alcohol can then be removed from the product without problems, for example by distillation.
- the alcohol can be used again for the epoxy opening.
- toluene or cyclohexane is preferably added.
- the solvent can then simply be separated from the higher-boiling product of value in a vacuum.
- An added phase transfer catalyst shortens the reaction time.
- the fatty acid amide derivatives XXI according to the invention are compounds with excellent surface-active properties, which are therefore outstandingly suitable for use as nonionic or anionic surfactants in detergents and cleaning agents, as described above. Low surface and interfacial tension are found in the test. In addition, they show good fat dissolving power and good primary washing power. In addition, they also have good solubility in hard water and are generally insensitive to water hardness.
- the present invention therefore also relates to detergents and cleaning agents which contain the fatty acid amide derivatives XXI according to the invention as surfactants in amounts customary for this purpose and other additives customary for such agents.
- the surfactants XXI mentioned are also suitable as dyeing aids in leather dyeing.
- the fatty acid amide derivatives XXI according to the invention are simple and inexpensive to produce by means of the process described.
- a simple apparatus for example a conventional stirred kettle
- the reaction can be carried out in short yields in high yields.
- the course of the reaction can be tracked quickly and easily using infrared spectroscopy, gas chromatography (GC) or titrations.
- the fatty acid amide derivatives XXI according to the invention are based on renewable raw materials and are therefore particularly ecologically advantageous. As a rule, they are readily biodegradable.
- the present invention is illustrated by the following examples.
- the interfacial tension was determined as a function of the contact time between an aqueous surfactant solution and an oil phase.
- the contact angle was measured as the wettability of a hard surface by the surfactant solution. Complete wetting (spreading) corresponds to zero contact angle.
- the surface tension was determined in accordance with DIN 53914 by measuring the force in mN / m which is necessary to pull a plate or a horizontally suspended ring out of the liquid surface.
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- Engineering & Computer Science (AREA)
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Abstract
Description
Claims
Applications Claiming Priority (7)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE1995140091 DE19540091A1 (de) | 1995-10-27 | 1995-10-27 | Verwendung von Fettsäurederivaten als Tenside |
DE19540091 | 1995-10-27 | ||
DE19607642 | 1996-02-02 | ||
DE1996107642 DE19607642A1 (de) | 1996-02-29 | 1996-02-29 | Alkoxylierte Aminohydroxyfettsäurederivate |
DE19620613 | 1996-05-22 | ||
DE19620613A DE19620613A1 (de) | 1996-05-22 | 1996-05-22 | Fettsäureamidderivate und ihre Verwendung als Tenside |
PCT/EP1996/004560 WO1997016408A1 (de) | 1995-10-27 | 1996-10-21 | Fettsäurederivate und ihre verwendung als tenside in wasch- und reinigungsmitteln |
Publications (1)
Publication Number | Publication Date |
---|---|
EP0874802A1 true EP0874802A1 (de) | 1998-11-04 |
Family
ID=27215601
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP96937203A Withdrawn EP0874802A1 (de) | 1995-10-27 | 1996-10-21 | Fettsäurederivate und ihre verwendung als tenside in wasch- und reinigungsmitteln |
Country Status (3)
Country | Link |
---|---|
US (5) | US6004923A (de) |
EP (1) | EP0874802A1 (de) |
WO (1) | WO1997016408A1 (de) |
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1996
- 1996-10-21 EP EP96937203A patent/EP0874802A1/de not_active Withdrawn
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- 1996-10-21 WO PCT/EP1996/004560 patent/WO1997016408A1/de not_active Application Discontinuation
-
1999
- 1999-07-06 US US09/348,673 patent/US6057283A/en not_active Expired - Fee Related
- 1999-10-25 US US09/425,293 patent/US6380410B1/en not_active Expired - Fee Related
-
2000
- 2000-01-28 US US09/493,253 patent/US6204238B1/en not_active Expired - Fee Related
- 2000-11-14 US US09/710,888 patent/US6320064B1/en not_active Expired - Fee Related
Non-Patent Citations (1)
Title |
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Also Published As
Publication number | Publication date |
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US6057283A (en) | 2000-05-02 |
WO1997016408A1 (de) | 1997-05-09 |
US6004923A (en) | 1999-12-21 |
US6380410B1 (en) | 2002-04-30 |
US6320064B1 (en) | 2001-11-20 |
US6204238B1 (en) | 2001-03-20 |
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