EP0237959B1 - Water soluble mixtures of ammonium salts from fatty acids and polyol-fatty acids, or of their alcali or ammonium salts, process for their production and their use as corrosion inhibitors in aqueous systems - Google Patents

Water soluble mixtures of ammonium salts from fatty acids and polyol-fatty acids, or of their alcali or ammonium salts, process for their production and their use as corrosion inhibitors in aqueous systems Download PDF

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EP0237959B1
EP0237959B1 EP87103577A EP87103577A EP0237959B1 EP 0237959 B1 EP0237959 B1 EP 0237959B1 EP 87103577 A EP87103577 A EP 87103577A EP 87103577 A EP87103577 A EP 87103577A EP 0237959 B1 EP0237959 B1 EP 0237959B1
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Prior art keywords
general formula
fatty acids
water
salts
mixtures
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EP87103577A
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German (de)
French (fr)
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EP0237959A1 (en
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Karl Heinz Dr. Schmid
Alfred Dr. Meffert
Bert Dr. Gruber
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
    • C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
    • C23F11/10—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using organic inhibitors
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
    • C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
    • C23F11/10—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using organic inhibitors
    • C23F11/14—Nitrogen-containing compounds
    • C23F11/141—Amines; Quaternary ammonium compounds
    • C23F11/143—Salts of amines

Definitions

  • the invention relates to water-soluble mixtures of fatty acid-ammonium salts and polyol fatty acids or their alkali metal or ammonium salts, a process for their preparation and the use of such mixtures for corrosion inhibition in aqueous systems.
  • the neutralization product of di-n-butylamine with a 1: 1 mixture of caprylic acid and capric acid has a better corrosion-inhibiting effect than the fatty acids neutralized with alkanolamines.
  • the disadvantage of this product is that it smells extremely unpleasant. Due to the large surfaces that are treated with such corrosion inhibitors, there is an unacceptable odor nuisance.
  • the object of the present invention was to provide a water-soluble corrosion protection agent which leads to good corrosion inhibition on metallic surfaces made of iron or iron-containing alloys.
  • the lowest possible foam tendency and water hardness sensitivity had to be ensured and, furthermore, it had to be ensured that no odor nuisance occurred due to the ingredients contained in such agents.
  • the invention also relates to the use of such water-soluble mixtures of fatty acid-ammonium salts and polyol fatty acids and / or their salts for corrosion inhibition in drilling oils, cutting oils, rolling oils, sleeping oils, solutions for metal cleaning, coolants and lubricants.
  • the water-soluble mixtures for corrosion inhibition according to the invention contain one or more ammonium salts of fatty acids of the above-mentioned general formula (I) as one component.
  • the alkyl radicals are therefore the radicals methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, tert-butyl, and also n-pentyl or n-hexyl and their branched isomers.
  • Suitable hydroxyalkylene radicals are hydroxymethylene or hydroxyethylene radicals or their higher homologues with 3 to 6 carbon atoms in the alkylene radical.
  • Aminoalkylene radicals which can be mentioned are correspondingly aminoomethylene, aminoethylene or aminopropylene radicals or their higher homologs with 4 to 8 C atoms or corresponding aminoalkylene radicals which are substituted on the N atom by C 1-3 alkyl groups.
  • the radical R5 in the general formula (I) represents unbranched and / or branched alkyl radicals having 6 to 10 carbon atoms. Suitable radicals R5 are in particular i-heptyl, i / n-octyl, i-nonyl or n-decyl.
  • the ammonium salts (I) thus originate, for example, from caprylic acid, isononanoic acid or capric acid.
  • ammonium salts of two fatty acids are preferred as the ammonium salt component.
  • Mixtures of two ammonium salts in a weight ratio of 1: 1 have proven particularly useful.
  • Mixtures of ammonium salts (I), which result from the neutralization of a mixture of 50% capric acid and 50% capric acid with amines having 1 to 8 carbon atoms, such as, for example, with di-n-butylamine, have proven particularly advantageous.
  • the water-soluble mixtures according to the invention contain one or more of the ammonium salts of fatty acids with the general formula (I) in amounts of 10 to 90% by weight, based on the total weight of the mixtures according to the invention. Quantities in the range from 10 to 50% by weight are to be regarded as preferred.
  • R6 represents a straight-chain or branched alkyl or alkylene radical having 1 to 19 carbon atoms.
  • m stands for integers in the range from 0 to 18, preferably in the range from 8 to 14.
  • R 6 is n-octyl and m represents 7.
  • the alkoxy radical R 7 O- in the general formula (II) is formed in the course of the process according to the invention described below, in which di- or polyhydroxy compounds of the formula (IV) are added to an epoxide of an unsaturated carboxylic acid (III).
  • the products of the formula (11) also include mixtures of compounds in which two or more Fatty acid molecules are linked together by a di- or polyhydroxy compound of the formula (IV).
  • salts (II) in which M ⁇ represents H ⁇ , their water-soluble salts can also be used.
  • alkali metal salts for example sodium and / or potassium salts, in which M ⁇ is Na ⁇ or K ⁇ , are preferred.
  • salts (II) in which M ⁇ represents an ammonium cation [R i R 2 R 3 R4N] n + , where R 1 , R2, R3, and R4 and n have the meanings given above.
  • One or more polyol fatty acids or their salts of the general formula (II) can be contained in the water-soluble mixtures for corrosion inhibition according to the invention.
  • the total amounts of the compounds (II) mentioned are in the range from 10 to 90% by weight, based on the total weight of the mixtures, preferably in the range from 50 to 90% by weight.
  • unsaturated fatty acids of the general formula (III) or of the di- or polyhydroxy compounds of the formula (IV) also includes unsaturated fatty acids with more than one double bond or di- or polyhydroxy compounds, such as those generally obtained from industrially available oils and fats, such as Soybean oil, linseed oil, rape oil etc. are available.
  • polyol fatty acid or its salts of the general formula (II) obtained in this way is then, if desired, combined with further polyol fatty acids of the general formula mentioned and with one or more ammonium salts of fatty acids with the general formula (I) in a weight ratio of 10: 1 to 1:10, preferably 3: 1, and optionally mixed with water.
  • the water-soluble mixtures according to the invention obtained in this way are outstandingly suitable as agents for inhibiting corrosion in drilling oils, cutting oils, rolling oils, grinding oils, solutions for metal cleaning, coolants and lubricants. It is surprising in the use of such mixtures that polyol fatty acids and their salts of the general formula (11) as such have no corrosion-inhibiting properties. However, in combination with the ammonium salts of fatty acids with the general formula (I), the compounds mentioned have a strong synergistic effect in that they significantly increase their ability to inhibit corrosion on metal surfaces.
  • the concentration of the ammonium salts of fatty acids which as such - as known from the prior art - have corrosion-inhibiting properties by up to 50%, without any deterioration in the corrosion protection.
  • the mixtures according to the invention are also extremely soluble in extremely hard water. This property is also significantly improved in mixtures which, in addition to one or more ammonium salts of fatty acids with the general formula (I), also contain one or more polyol fatty acids and / or their salts of the general formula (II).
  • 150 g of the substance produced according to Example 5 were mixed with 50 g of the neutralizate of 50% by weight of caprylic acid and 50% by weight of capric acid with di-n-butylamine.
  • the commercially available amine salt of a 1: 1 mixture of caprylic acid and capric acid with di-n-butylamine hereinafter referred to as "comparative substance" was used. Its concentration in the application solution was 1 or 2% by weight.
  • the results for corrosion inhibition in the products of Examples 3 and 4 according to the invention are significantly better than in the comparison substance, even in very hard water. Results of the corrosion inhibition that are comparable with the comparison substance are achieved with a reduced use amount of the mixtures according to the invention.
  • Test method 50 ml of a test solution containing 3% of the mixtures according to the invention were shaken ten times in a 100 ml measuring cylinder and the foam volume in ml and the foam disintegration time in min were measured. The results are shown in Table 2 below.
  • the neutralization product of a 1: 1 mixture of caprylic acid and capric acid with di-n-butylamine was again used as the reference substance.
  • Both the product according to Example 4 and that according to Example 3 shows a foam breakdown which is surprisingly rapid for amine soaps in comparison with the comparison substance.
  • the polyol fatty acid in the mixture according to the invention therefore has a synergistic effect on the foam decomposition in the products mentioned.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Preventing Corrosion Or Incrustation Of Metals (AREA)
  • Lubricants (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Anti-Oxidant Or Stabilizer Compositions (AREA)
  • Detergent Compositions (AREA)

Abstract

Water-soluble corrosion-inhibiting mixtures containing (a) one or more ammonium salts of fatty acids corresponding to the following general formula <IMAGE> (I) in which n=1 or 2 while R1, R2, R3 and R4 may be the same or different and represent hydrogen, unbranched or branched C1-C6 alkyl groups, C1-C6 hydroxyalkylene groups or C1-C8 aminoalkylene groups and R5 represents C6-C10 alkyl groups, and (b) one or more polyol fatty acids and/or salts thereof corresponding to the following general formula <IMAGE> (II) in which R6 is a C1-C19 alkyl or alkylene group and R7 represents an organic residue formed from a dihydroxy or polyhydroxy compound by elimination of a hydroxyl group, M(+)=H(+), Na(+), K(+) or an ammonium ion [R1R2R3R4N]n+, as in formula (I), and m is an integer of from 0 to 18, and to a process for preparing these water-soluble mixtures and to the use of these mixtures for inhibiting corrosion in drilling oils, cutting oils, rolling oils, grinding oils, metal-cleaning solutions, coolants and lubricants.

Description

Die Erfindung betrifft wasserlösliche Mischungen von Fettsäure-Ammonium-Salzen und Polyolfettsäuren bzw. deren Alkali- oder Ammoniumsalzen, ein Verfahren zu ihrer Herstellung und die Verwendung derartiger Mischungen zur Korrosionsinhibierung in wässrigen Systemen.The invention relates to water-soluble mixtures of fatty acid-ammonium salts and polyol fatty acids or their alkali metal or ammonium salts, a process for their preparation and the use of such mixtures for corrosion inhibition in aqueous systems.

In technischen Prozessen der Bearbeitung von Metalloberflächen, beispielsweise durch Bohren, Schneiden, Walzen oder Schleifen, sowie der Metallreinigung, treten immer wieder Korrosionsprobleme auf. Hier wie auch in technischen Kühlprozessen, die such in Gegenwart von Wasser oder wasserhaltigen Flüssigkeitsmischungen abspielen, kommen korrosionsgefährdete Metalle, vornehmlich Eisen oder eisenhaltige Legierungen, mit wässrigen technischen Reinigern, Kühlwässern, Kühlschmierstoffen für die Metallbearbeitung etc. in Kontakt und werden unter ungünstigen Bedingungen korrodiert. Dies hat einerseits eine verringerte Lebensdauer der Apparaturen zur Folge, andererseits müssen in Prozessen, in denen die Metalloberflächen anschließend weiterverarbeitet, gegebenenfalls mit korrosionsschützenden Überzügen versehen werden sollen, aufwendige Arbeitsprozesse zwischengeschaltet werden, um die schon korrodierten Metalloberflächen frei von Korrosion für die Folgeprozesse zur Verfügung zu stellen.In technical processes for processing metal surfaces, for example by drilling, cutting, rolling or grinding, as well as in metal cleaning, corrosion problems occur again and again. Here, as well as in technical cooling processes that also play in the presence of water or water-containing liquid mixtures, metals that are at risk of corrosion, primarily iron or iron-containing alloys, come into contact with aqueous technical cleaners, cooling water, cooling lubricants for metalworking, etc. and are corroded under unfavorable conditions. On the one hand, this results in a reduced service life of the equipment, on the other hand, in processes in which the metal surfaces are to be further processed, if necessary with corrosion-protective coatings, complex work processes must be interposed in order to make the already corroded metal surfaces free of corrosion for the subsequent processes put.

Aus der DE-AS 11 49 843 und der EP-PS 0 002 780 sind Aminsalze bzw. Alkanolaminsalze von Maleinamidsäure und ihren Derivaten als Korrosionsinhibitoren in wässrigen Systemen bekannt. Derartige Verbindungen weisen je nach Substituenten eine gute bis für die Verwendung in wässrigen Systemen ausreichende Wasserlöslichkeit auf und zeigen eine für die Anwendungszwecke zufriedenstellende Korrosionsschutzwirkung, haben jedoch den Nachteil, daß sie ausgesprochen stark schäumen. Dies wird vor allem dann beobachtet. wenn die entsprechenden Inhibitoren Kühlwässern oder Kühlschmierstoffen zugesetzt werden. Es war daher im Zusammenhang mit derartigen Verbindungen der Zusatz eines Schaumdämpfers erforderlich. Zudem zeigte sich, daß derartige Verbindungen mitunter ausgesprochen empfindlich auf Schwankungen in der Wasserhärte reagieren.From DE-AS 11 49 843 and EP-PS 0 002 780 amine salts or alkanolamine salts of maleic acid and its derivatives are known as corrosion inhibitors in aqueous systems. Depending on the substituent, such compounds have a good water solubility up to sufficient for use in aqueous systems and have a satisfactory corrosion protection effect for the application purposes, but have the disadvantage that they foam extremely strongly. This is especially observed. if the corresponding inhibitors are added to cooling water or cooling lubricants. It was therefore necessary to add a foam damper in connection with such connections. In addition, it was found that such compounds are sometimes extremely sensitive to fluctuations in water hardness.

Aus der DE-OS 29 43 963 sind Alkanolaminsalze von Alkenylbernsteinsäuren als Korrosionsinhibitoren in wässrigen Systemen bekannt. In der US-PS 3 374 171 wurden außerdem Aminsalze von Fettsäuren mit 6 bis 9 C-Atomen als wasserlösliche Korrosionsinhibitoren offenbart. Es wurden dabei Fettsäuren wie Capron-, Capryl-, Heptan- und Pelargonsäure mit Alkanolaminen neutralisiert und mit Polyoxyalkylenglykolen vermischt.DE-OS 29 43 963 alkanolamine salts of alkenyl succinic acids are known as corrosion inhibitors in aqueous systems. US Pat. No. 3,374,171 also discloses amine salts of fatty acids having 6 to 9 carbon atoms as water-soluble corrosion inhibitors. Fatty acids such as capronic, caprylic, heptane and pelargonic acid were neutralized with alkanolamines and mixed with polyoxyalkylene glycols.

Das Neutralisationsprodukt aus Di-n-butylamin mit einem 1 : 1-Gemisch aus Caprylsäure und Caprinsäure ist im Vergleich zu den mit Alkanolaminen neutralisierten Fettsäuren besser in der korrosionsinhibierenden Wirkung. Nachteilig an diesem Produkt ist jedoch, daß es ausgesprochen unangenehm riecht. Aufgrund der großen Oberflächen, die mit derartigen Korrosionsinhibitoren behandelt werden, kommt es daher zu einer nicht hinnehmbaren Geruchsbelästigung.The neutralization product of di-n-butylamine with a 1: 1 mixture of caprylic acid and capric acid has a better corrosion-inhibiting effect than the fatty acids neutralized with alkanolamines. The disadvantage of this product, however, is that it smells extremely unpleasant. Due to the large surfaces that are treated with such corrosion inhibitors, there is an unacceptable odor nuisance.

Aufgabe der vorliegenden Erfindung war es, ein wasserlösliches Korrosionsschutzmittel zur Verfügung zu stellen, das auf metallischen Oberflächen aus Eisen oder Eisen enthaltenden Legierungen zu einer guten Korrosionsinhibierung führt. Zudem war eine möglichst geringe Schaumneigung und Wasserhärteempfindlicheit sicherzustellen und außerdem zu gewährleisten, daß aufgrund der in derartigen Mitteln enthaltenen Inhaltsstoffe keine Geruchsbelästigung auftritt.The object of the present invention was to provide a water-soluble corrosion protection agent which leads to good corrosion inhibition on metallic surfaces made of iron or iron-containing alloys. In addition, the lowest possible foam tendency and water hardness sensitivity had to be ensured and, furthermore, it had to be ensured that no odor nuisance occurred due to the ingredients contained in such agents.

Die Erfindung betrifft wasserlösliche Mischungen zur Korrosionsinhibierung, die

  • a) ein oder mehrere Ammoniumsalze von Fettsäuren mit der allgemeinen Formel (I)
    Figure imgb0001
    in der n = 1 oder 2 bedeuten; Rl, R2, R3 und R4 gleich oder verschieden sein können und für Wasserstoff, unverzweigte oder verzweigte Alkylreste mit 1 bis 6 C-Atomen, Hydroxyalkylenreste mit 1 bis 6 C-Atomen oder Aminoalkylenreste mit 1 bis 8 C-Atomen stehen und R5 für unverzweigte und/oder verzweigte Alkylreste mit 6 bis 10 C-Atomen steht, in Mengen von 10 bis 90 Gew.-%, bezogen auf das Gesamtgewicht der Mischung, und
  • b) ein oder mehrere Polyolfettsäuren und/oder deren Salze der allgemeinen Formel (11)
    Figure imgb0002
    in der R6 für einen geradkettigen oder verzweigten Alkyl- oder Alkylenrest mit 1 bis 19 C-Atomen und R7 für einen aus einer Di- oder Polyhydroxyverbindung durch Abspaltung einer Hydroxylgruppe entstandenen organischen Rest steht, M¢ = H⊕, Na⊕, K¢ oder ein Ammoniumion [R1R2R3R4N ]n+ wie in Formel (I) bedeutet und m ganze Zahlen im Bereich von 0 bis 18 bedeutet, in Mengen von 10 bis 90 Gew.-%, bezogen auf das Gesamtgewicht der Mischung, enthalten.
The invention relates to water-soluble mixtures for corrosion inhibition, the
  • a) one or more ammonium salts of fatty acids with the general formula (I)
    Figure imgb0001
     in which n = 1 or 2; R 1 , R 2 , R 3 and R 4 may be the same or different and represent hydrogen, unbranched or branched alkyl radicals having 1 to 6 C atoms, hydroxyalkylene radicals having 1 to 6 C atoms or aminoalkylene radicals having 1 to 8 C atoms and R 5 represents unbranched and / or branched alkyl radicals having 6 to 10 carbon atoms, in amounts of 10 to 90% by weight, based on the total weight of the mixture, and
  • b) one or more polyol fatty acids and / or their salts of the general formula (11)
    Figure imgb0002
     in which R6 is a straight-chain or branched alkyl or alkylene radical having 1 to 19 carbon atoms and R7 is an organic radical formed from a di- or polyhydroxy compound by splitting off a hydroxyl group, M ¢ = H⊕, Na⊕, K ¢ or an ammonium ion [R1R2R3R4N] n + as in formula (I) and m means integers in the range from 0 to 18, in amounts of 10 to 90% by weight, based on the total weight of the mixture.

Die Erfindung betrifft außerdem ein Verfahren zur Herstellung derartiger Mischungen, das dadurch gekennzeichnet ist, daß man ungesättigte Fettsäuren der allgemeinen Formel (III)

  • R6 - CH = CH - (CH2)m - COOY (III)
    in der R6 und m die obigen Bedeutungen haben und Y Wasserstoff ist, oder deren Derivate, in denen Y den Rest eines ein- oder mehrwertigen Alkohols wie z.B. des Glycerins oder Methanols bedeutet, nach an sich bekannten Methoden epoxidiert, das erhaltene Epoxid nach an sich bekannten Methoden mit einer Di- oder Polyhydroxyverbindung der allgemeinen Formel (IV)
  • R70H (IV)
    in der R7 für einen aus einer Di- oder Polyhydroxyverbindung durch Abspaltung einer Hydroxylgruppe entstandenen organischen Rest steht, umsetzt, gegebenenfalls die Derivate der erhaltenen Polyolfettsäure mit Basen der allgemeinen Formel M⊕OH⊖, in der Me die oben genannten Bedeutungen hat, oder mit einer Säure verseift und die erhaltene Polyolfettsäure und/oder deren Salze der allgemeinen Formel (11) und gegebenenfalls weitere Polyolfettsäuren der genannten allgemeinen Formel mit einem oder mehreren Ammoniumsalzen von Fettsäuren mit der obigen allgemeinen Formel (I) im Gewichtsverhältnis 10 : 1 bis 1 : 10 sowie gegebenenfalls mit Wasser mischt.
The invention also relates to a process for the preparation of such mixtures, which is characterized in that unsaturated fatty acids of the general formula (III)
  • R 6 - CH = CH - (CH 2 ) m - COOY (III)
    in which R 6 and m have the above meanings and Y is hydrogen, or their derivatives in which Y is the residue of a mono- or polyhydric alcohol, such as glycerol or methanol, epoxidized according to methods known per se, the epoxide obtained according to known methods with a di- or polyhydroxy compound of the general formula (IV)
  • R70H (IV)
    in which R 7 represents an organic radical formed from a di- or polyhydroxy compound by splitting off a hydroxyl group, optionally reacting the derivatives of the polyol fatty acid obtained with bases of the general formula M⊕OH⊖, in which M e has the abovementioned meanings, or saponified with an acid and the polyol fatty acid and / or its salts of the general formula (11) and optionally further polyol fatty acids of the general formula mentioned with one or more ammonium salts of fatty acids with the general formula (I) above in a weight ratio of 10: 1 to 1: 10 and optionally mixed with water.

Die Erfindung betrifft außerdem die Verwendung derartiger wasserlöslicher Mischungen von Fettsäure-Ammonium-Salzen und Polyolfettsäuren und/oder deren Salzen zur Korrosionsinhibierung in Bohrölen, Schneidölen, Walzölen, Schliefölen, Lösungen für die Metallreinigung, Kühlmitteln und Schmiermitteln.The invention also relates to the use of such water-soluble mixtures of fatty acid-ammonium salts and polyol fatty acids and / or their salts for corrosion inhibition in drilling oils, cutting oils, rolling oils, sleeping oils, solutions for metal cleaning, coolants and lubricants.

Die erfindungsgemäßen wasserlöslichen Mischungen zur Korrosionsinhibierung enthalten als eine Komponente ein oder mehrere Ammoniumsalze von Fettsäuren der oben genannten allgemeinen Formel (I). In (I) können n 1 oder 2 bedeuten und einer oder mehrere der Reste R1, R2, R3 und R4 gleich sein oder auch alle Reste voneinander verschieden sein. Sie können dabei für Wasserstoff und unverzweigte oder verzweigte Alkylreste mit 1 bis 6 C-Atomen, Hydroxyalkylenreste mit 1 bis 6 C-Atomen im Alkylenrest oder - mit n = 2 - für Aminoalkylenreste mit 1 bis 8 C-Atomen stehen. Als Alkylreste kommen damit die Reste Methyl, Ethyl, n-Propyl, i-Propyl, n-Butyl, i-Butyl, tert-Butyl, sowie n-Pentyl oder n-Hexyl sowie deren verzweigte Isomere in Frage. Geeignete Hydroxyalkylenreste sind Hydroxymethylenoder Hydroxyethylenreste oder deren höhere Homologe mit 3 bis 6 C-Atomen im Alkylenrest. Als Aminoalkylenreste lassen sich entsprechend Aminomethylen-, Aminoethylen- oder Aminopropylenreste oder deren höhere Homologe mit 4 bis 8 C-Atomen bzw. entsprechende, am N-Atom mit C1-3-Alkylgruppen substituierte Aminoalkylenreste nennen.The water-soluble mixtures for corrosion inhibition according to the invention contain one or more ammonium salts of fatty acids of the above-mentioned general formula (I) as one component. In (I), n can mean 1 or 2 and one or more of the radicals R 1 , R 2 , R 3 and R 4 can be the same or all radicals can be different from one another. They can stand for hydrogen and unbranched or branched alkyl radicals with 1 to 6 carbon atoms, hydroxyalkylene radicals with 1 to 6 carbon atoms in the alkylene radical or - with n = 2 - for aminoalkylene radicals with 1 to 8 carbon atoms. The alkyl radicals are therefore the radicals methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, tert-butyl, and also n-pentyl or n-hexyl and their branched isomers. Suitable hydroxyalkylene radicals are hydroxymethylene or hydroxyethylene radicals or their higher homologues with 3 to 6 carbon atoms in the alkylene radical. Aminoalkylene radicals which can be mentioned are correspondingly aminoomethylene, aminoethylene or aminopropylene radicals or their higher homologs with 4 to 8 C atoms or corresponding aminoalkylene radicals which are substituted on the N atom by C 1-3 alkyl groups.

Bevorzugt werden Verbindungen (I) mit n = 1, in denen ein Rest im Ammoniumkation für einen Alkylrest mit 1 bis 6 C-Atomen und die restlichen Reste für Wasserstoff stehen, oder Verbindungen (I), in denen zwei dieser Reste für eine Alkylgruppe mit 3 oder 4 C-Atomen und die beiden anderen Reste für Wasserstoff stehen. Bevorzugt sind ferner Verbindungen (I) mit n = 2, in denen einer der Reste im Ammoniumkation einen Aminoalkylenrest gemäß der vorstehenden Definition bedeutet und die somit zwei kationische N-Atome aufweisen; einer der anderen Reste steht für einen Alkylrest mit 1 bis 3 C-Atomen, die restlichen beiden Reste für Wasserstoff.Preference is given to compounds (I) with n = 1 in which one radical in the ammonium cation represents an alkyl radical having 1 to 6 carbon atoms and the remaining radicals are hydrogen, or compounds (I) in which two of these radicals represent an alkyl group 3 or 4 carbon atoms and the other two radicals represent hydrogen. Also preferred are compounds (I) with n = 2, in which one of the residues in the ammonium cation denotes an aminoalkylene residue as defined above and which therefore have two cationic N atoms; one of the other radicals stands for an alkyl radical with 1 to 3 carbon atoms, the remaining two radicals for hydrogen.

Besonders bewährt haben sich Ammoniumsalze (1) mit Ammoniumkationen, in denen zwei Reste für eine n-Butylgruppe und die beiden anderen Reste für Wasserstoff stehen, sowie solche Ammoniumsalze (I), in denen das Ammoniumkation für [N,N-Dimethylpropylendiamin-1,3]2+ steht.Ammonium salts (1) with ammonium cations, in which two radicals represent an n-butyl group and the other two radicals are hydrogen, and ammonium salts (I) in which the ammonium cation for [N, N-dimethylpropylenediamine-1, 3] 2+ stands.

Der Rest R5 in der allgemeinen Formel (I) steht für unverzweigte und/oder verzweigte Alkylreste mit 6 bis 10 C-Atomen. Als Reste R5 kommen insbesondere i-Heptyl, i/n-Octyl, i-Nonyl oder n-Decyl in Frage. Die Ammoniumsalze (I) stammen damit beispielsweise von Caprylsäure, Isononansäure oder Caprinsäure.The radical R5 in the general formula (I) represents unbranched and / or branched alkyl radicals having 6 to 10 carbon atoms. Suitable radicals R5 are in particular i-heptyl, i / n-octyl, i-nonyl or n-decyl. The ammonium salts (I) thus originate, for example, from caprylic acid, isononanoic acid or capric acid.

Bevorzugt werden als Ammoniumsalzkomponente Mischungen von Ammoniumsalzen zweier Fettsäuren, die jeweils die allgemeine Formel (I) aufweisen, angesehen. Es haben sich insbesondere Mischungen zweier Ammoniumsalze im Gewichtsverhältnis 1 : 1 bewährt. Als besonders vorteilhaft erwiesen sich Mischungen von Ammoniumsalzen (I), die aus der Neutralisation eines Gemisches von 50 % Caprilsäure und 50 % Caprinsäure mit Aminen mit 1 bis 8 C-Atomen entstehen, wie beispielsweise mit Di-n-butylamin, N,N-Dimethylpropylendiamin-(1,3) oder 2-Amino-2-methylpropanol-1.Mixtures of ammonium salts of two fatty acids, each having the general formula (I), are preferred as the ammonium salt component. Mixtures of two ammonium salts in a weight ratio of 1: 1 have proven particularly useful. Mixtures of ammonium salts (I), which result from the neutralization of a mixture of 50% capric acid and 50% capric acid with amines having 1 to 8 carbon atoms, such as, for example, with di-n-butylamine, have proven particularly advantageous. N, N-dimethylpropylenediamine- (1,3) or 2-amino-2-methylpropanol-1.

Die erfindungsgemäßen wasserlöslichen Mischungen enthalten eines oder mehrere der Ammoniumsalze von Fettsäuren mit der allgemeinen Formel (I) in Mengen von 10 bis 90 Gew.-%, bezogen auf das Gesamtgewicht der erfindungsgemäßen Mischungen. Als bevorzugt sind dabei Mengen im Bereich von 10 bis 50 Gew.-% anzusehen.The water-soluble mixtures according to the invention contain one or more of the ammonium salts of fatty acids with the general formula (I) in amounts of 10 to 90% by weight, based on the total weight of the mixtures according to the invention. Quantities in the range from 10 to 50% by weight are to be regarded as preferred.

Als weitere Komponente sind in den erfindungsgemäßen wasserlöslichen Mischungen eine oder mehrere Polyol fettsäuren und/oder deren Salze der allgemeinen Formel (11) enthalten. In der allgemeinen Formel (11) steht R6 für einen geradkettigen oder verzweigten Alkyl- oder Alkylenrest mit 1 bis 19 C-Atomen. Es kommen also die Reste Methyl, Ethyl, n-Propyl, i-Propyl, n-Butyl, i-Butyl, tert-Butyl sowie n-Pentyl, n-Hexyl, n-Heptyl, n-Octyl, n-Nonyl, n-Decyl, n-Undecyl, n-Dodecyl, n-Tridecyl, n-Tetradecyl, n-Pentadecyl, n-Hexadecyl, n-Heptadecyl, n-Octadecyl oder n-Nonadecyl sowie die verzweigten Isomere der genannten Alkylen- bzw. Alkylreste in Frage. Bevorzugt werden dabei Alkylreste, deren Kohlenstoffzahl im Bereich von 8 bis 15 liegt.One or more polyol fatty acids and / or their salts of the general formula (11) are present as a further component in the water-soluble mixtures according to the invention. In the general formula (11), R6 represents a straight-chain or branched alkyl or alkylene radical having 1 to 19 carbon atoms. So there are the residues methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, tert-butyl and n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n -Decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl or n-nonadecyl and the branched isomers of the alkylene or alkyl radicals mentioned in Question. Alkyl radicals whose carbon number is in the range from 8 to 15 are preferred.

In der genannten allgemeinen Formel (II) steht m für ganze Zahlen im Bereich von 0 bis 18, bevorzugt im Bereich von 8 bis 14. In der Praxis haben sich Verbindungen der Allgemeinen Formel (II) besonders bewährt, in denen der Rest R6 für n-Octyl und m für 7 steht.In the general formula (II) mentioned, m stands for integers in the range from 0 to 18, preferably in the range from 8 to 14. In practice, compounds of the general formula (II) in which the radical R 6 is n-octyl and m represents 7.

In der allgemeinen Formel (II) steht R7 für einen organischen Rest, der formal aus einer Di- oder Polyhydroxyverbindung durch Abspaltung einer Hydroxylgruppe entstanden ist. Als Di- oder Polyhydroxyverbindungen haben sich dabei die Verbindungen aus der folgenden Gruppe besonders bewährt:

  • Ethylenglykol
  • Glycerin
  • Diglycerin
  • Propylenglykol
  • Diethylenglykol
  • Dipropylenglykol
  • Trimethylolethan
  • Trimethylolpropan
  • Neopentylglykol
  • Pentaerythrit
  • Dipentaerythrit
  • Sorbit
  • Sorbitan
  • Diethanolamin
  • Triethanolamin
In the general formula (II), R 7 stands for an organic radical which has formally arisen from a di- or polyhydroxy compound by splitting off a hydroxyl group. The compounds from the following group have proven particularly useful as di- or polyhydroxy compounds:
  • Ethylene glycol
  • Glycerin
  • Diglycerin
  • Propylene glycol
  • Diethylene glycol
  • Dipropylene glycol
  • Trimethylolethane
  • Trimethylolpropane
  • Neopentyl glycol
  • Pentaerythritol
  • Dipentaerythritol
  • Sorbitol
  • Sorbitan
  • Diethanolamine
  • Triethanolamine

PolethylenglykolPolyethylene glycol

Figure imgb0003
Figure imgb0004
Figure imgb0005
Polypropylenglykol
Figure imgb0006
Figure imgb0007
Figure imgb0008
Propylenoxid-Ethylenoxid-Blockpolymere, d.h. Verbindungen der Formel
Figure imgb0009
mit
Figure imgb0010
und Ethylenoxid-Propylenoxid-Blockpolymere, d.h. Verbindungen der Formel
Figure imgb0011
mit
Figure imgb0012
Figure imgb0003
Figure imgb0004
Figure imgb0005
 Polypropylene glycol
Figure imgb0006
Figure imgb0007
Figure imgb0008
 Propylene oxide-ethylene oxide block polymers, ie compounds of the formula
Figure imgb0009
 With
Figure imgb0010
 and ethylene oxide-propylene oxide block polymers, ie compounds of the formula
Figure imgb0011
 With
Figure imgb0012

Der Alkoxyrest R7O- in der allgemeinen Formel (II) entsteht dabei im Zuge des nachfolgend beschriebenen erfindungsgemäßen Verfahrens, in dem Di- oder Polyhydroxyverbindungen der Formel (IV) an ein Epoxid einer ungesättigten Carbonsäure(III) addiert werden.The alkoxy radical R 7 O- in the general formula (II) is formed in the course of the process according to the invention described below, in which di- or polyhydroxy compounds of the formula (IV) are added to an epoxide of an unsaturated carboxylic acid (III).

Unter die Produkte der Formel (11) fallen auch Gemische von Verbindungen, in denen zwei oder mehr Fettsäuremoleküle durch eine Di- oder Polyhydroxyverbindung der Formel (IV) miteinander verknüpft sind.The products of the formula (11) also include mixtures of compounds in which two or more Fatty acid molecules are linked together by a di- or polyhydroxy compound of the formula (IV).

Statt der Polyolfettsäuren der oben angegebenen allgemeinen Formel (II), in denen M⊕ jeweils für H⊕ steht, sind auch deren wasserlösliche Salze verwendbar. Als solche sind bevorzugt Alkalimetallsalze, z.B. Natrium- und/oder Kaliumsalze, in denen M⊕ für Na¢ bzw. K⊕ steht, zu nennen. Mit Vorteil lassen sich auch Salze (II) verwenden, in denen M⊕ für ein Ammoniumkation [RiR2R3R4N]n+ steht, wobei Rl, R2, R3, und R4 sowie n die oben angegebenen Bedeutungen haben.Instead of the polyol fatty acids of the general formula (II) given above, in which M⊕ each represents H⊕, their water-soluble salts can also be used. As such, alkali metal salts, for example sodium and / or potassium salts, in which M⊕ is Na ¢ or K⊕, are preferred. It is also advantageous to use salts (II) in which M⊕ represents an ammonium cation [R i R 2 R 3 R4N] n + , where R 1 , R2, R3, and R4 and n have the meanings given above.

In den erfindungsgemäßen wasserlöslichen Mischungen zur Korrosioninhibierung können ein oder mehrere Polyolfettsäuren oder deren Salze der allgemeinen Formel (II) enthalten sein. Die Gesamtmengen der genannten Verbindungen (II) liegen dabei im Bereich von 10 bis 90 Gew.-%, bezogen auf das Gesamtgewicht der Mischungen, bevorzugt im Bereich von 50 bis 90 Gew.-%.One or more polyol fatty acids or their salts of the general formula (II) can be contained in the water-soluble mixtures for corrosion inhibition according to the invention. The total amounts of the compounds (II) mentioned are in the range from 10 to 90% by weight, based on the total weight of the mixtures, preferably in the range from 50 to 90% by weight.

Das Verfahren zur Herstellung derartiger wasserlöslicher Mischungen zur Korrosionsinhibierung kann als an sich bekannt bezeichnet werden. Die Polyolfettsäuren der allgemeinen Formel (II) werden dabei im wesentlichen nach dem in der DE-OS 33 18 596 beschriebenen Verfahren hergestellt. Dies besteht darin, daß man ungesättigte Fettsäuren der allgemeinen Formel (III)

  • R6 - CH = CH - (CH2)m - COOY (III)
    in der R6 und m die obigen Bedeutungen haben und Y Wasserstoff ist, oder deren Derivate, in denen Y den Rest eines ein- oder mehrwertigen Alkohols wie z.B. des Glycerins oder Methanols bedeutet, nach an sich bekannten Methoden epoxidiert. Dies kann beispielsweise unter Verwendung von Peroxycarbonsäuren nach an sich bekannten Methoden geschehen. Die Epoxydation liefert dabei Epoxide, in denen der Oxiranring die Position im Molekül einnimmt, die im Edukt durch die mit der Doppelbindung verbundenen Kohlenstoffatome vorgegeben ist. Das erhaltene Epoxid wird dann nach ebenfalls an sich bekannten Methoden mit einer Di- oder Polyhydroxyverbindung der allgemeinen Formel (IV)
  • R70H (IV)
    umgesetzt, in der R7 die obigen Bedeutungen hat. Dies kann beispielsweise dadurch geschehen, daß die Epoxide unter Säurekatalyse mit einem Überschuß der genannten Di- oder Polynydroxyverbindung (IV) umgesetzt werden, wobei sich der Oxiranring öffnet und der Epoxidsauerstoff zur Hydroxygruppe wird und das benachbarte Kohlenstoffatom den Alkoxyrest -OR7 der zur Ringöffnung verwendeten Di- oder Polyhydroxyverbindung trägt. Gegebenenfalls wird bei der Umsetzung mit der Di- oder Polyhydroxyverbindung (IV) auch die freie Carboxylgruppe verestert bzw. die mit dem Rest Y veresterte endständige Gruppe -COOY in der allgemeinen Formel (III) umgeestert. Gewünschtenfalls werden dann die Derivate der erhaltenen Polyolfettsäuren, deren Carboxylgruppe regelmäßig verestert ist, mit Basen der allgemeinen Formel M⊕OH, in der M⊕ die oben genannten Bedeutungen von Na⊕, K⊕, [RiR2R3R4N]n+ usw. hat, oder mit einer Säure verseift. Dabei werden dann die freien Polyolfettsäuren der allgemeinen Formel (II), in der M⊕ für das Wasserstoffion steht, oder deren Salze der Formel (11), in der M⊕ für ein Alkalimetallkation wie Na¢ oder K⊕ oder für ein Ammoniumion [R1R2R3R4N]n+ mit den oben angegebenen Bedeutungen für Rl, R2, R3 und R4 sowie n steht, gebildet.
The process for producing such water-soluble mixtures for corrosion inhibition can be described as known per se. The polyol fatty acids of the general formula (II) are essentially prepared by the process described in DE-OS 33 18 596. This consists in that unsaturated fatty acids of the general formula (III)
  • R 6 - CH = CH - (CH 2 ) m - COOY (III)
    in which R6 and m have the meanings given above and Y is hydrogen, or their derivatives in which Y is the residue of a mono- or polyhydric alcohol, such as glycerol or methanol, epoxidized by methods known per se. This can be done, for example, using peroxycarboxylic acids according to methods known per se. Epoxidation provides epoxides in which the oxirane ring occupies the position in the molecule that is specified in the educt by the carbon atoms connected to the double bond. The epoxide obtained is then, using methods which are also known per se, using a di- or polyhydroxy compound of the general formula (IV)
  • R70H (IV)
    implemented in which R 7 has the above meanings. This can be done, for example, by reacting the epoxides with an excess of the di- or polynydroxy compound (IV) mentioned under acid catalysis, the oxirane ring opening and the epoxy oxygen becoming the hydroxyl group and the neighboring carbon atom using the alkoxy radical -OR 7 or for opening the ring Di- or polyhydroxy compound carries. If appropriate, the free carboxyl group is also esterified in the reaction with the di- or polyhydroxy compound (IV) or the terminal group -COOY esterified with the radical Y is transesterified in the general formula (III). If desired, the derivatives of the polyol fatty acids obtained, the carboxyl group of which is regularly esterified, with bases of the general formula M⊕OH, in which M⊕ has the abovementioned meanings of Na⊕, K⊕, [RiR 2 R 3 R4N] n + etc. , or saponified with an acid. The free polyol fatty acids of the general formula (II), in which M⊕ represents the hydrogen ion, or their salts of formula (11), in which M⊕ represents an alkali metal cation such as Na ¢ or K⊕ or an ammonium ion [R 1 R 2 R 3 R 4 N] n + with the meanings given above for R 1 , R 2 , R 3 and R 4 and n is formed.

Unter den Begriff der ungesättigten Fettsäuren der allgemeinen Formel (III) bzw. der Di- oder Polyhydroxyverbindungen der Formel (IV) fallen auch ungesättigte Fettsäuren mit mehr als einer Doppelbindung bzw. Di- oder Polyhydroxyverbindungen, wie sie allgemein aus technisch verfügbaren Ölen und Fetten, wie z.B. Sojaöl, Leinöl, Rüböl etc., erhältlich sind.The term unsaturated fatty acids of the general formula (III) or of the di- or polyhydroxy compounds of the formula (IV) also includes unsaturated fatty acids with more than one double bond or di- or polyhydroxy compounds, such as those generally obtained from industrially available oils and fats, such as Soybean oil, linseed oil, rape oil etc. are available.

Die auf diesem Wege erhaltene Polyolfettsäure oder deren Salze der allgemeinen Formel (II) wird dann gewünschtenfalls mit weiteren Polyolfettsäuren der genannten allgemeinen Formel sowie mit einem oder mehreren Ammoniumsalzen von Fettsäuren mit der allgemeinen Formel (I) im Gewichtsverhältnis 10 : 1 bis 1 : 10, bevorzugt 3 : 1, sowie gegebenenfalls mit Wasser vermischt.The polyol fatty acid or its salts of the general formula (II) obtained in this way is then, if desired, combined with further polyol fatty acids of the general formula mentioned and with one or more ammonium salts of fatty acids with the general formula (I) in a weight ratio of 10: 1 to 1:10, preferably 3: 1, and optionally mixed with water.

Die auf diesem Wege erhaltenen erfindungsgemäßen wasserlöslichen Mischungen sind hervorragend geeignet als Mittel zur Korrosionsinhibierung in Bohrölen, Schneidölen, Walzölen, Schleifölen, Lösungen für die Metallreinigung, Kühlmitteln und Schmiermitteln. Überraschend in der Verwendung derartiger Mischungen ist, daß Polyolfettsäuren und deren Salze der allgemeinen Formel (11) als solche keinerlei korrosionsinhibierende Eigenschaften aufweisen. Die genannten Verbindungen wirken jedoch in Kombination mit den Ammoniumsalzen von Fettsäuren mit der allgemeinen Formel (I) insofern stark synergistisch, als sie deren Vermögen deutlich steigern, die Korrosion auf Metalloberflächen zu inhibieren. So ist es beispielsweise möglich, die Konzentration der Ammoniumsalze von Fettsäuren, die als solche - wie aus dem Stand der Technik bekannt - schon korrosionsinhibierende Eigenschaften aufweisen, um bis zu 50 % zu reduzieren, ohne daß dabei eine Verschlechterung des Korrosionsschutzes eintritt. Es ist weiterhin als Vorteil der erfindungsgemäßen wasserlöslichen Mischungen anzusehen, daß sie eine ausgeprägte Schaumarmut aufweisen und zudem die bei der alleinigen Verwendung der Ammoniumsalze von Fettsäuren mit der allgemeinen Formel (I) beanstandete Geruchsbelästigung nicht auftritt. Zudem sind die erfindungsgemäßen Mischungen auch in ausgesprochen hartem Wasser ausgezeichnet löslich. Auch diese Eigenschaft wird in Mischungen, die neben ein oder mehreren Ammoniumsalzen von Fettsäuren mit der allgemeinen Formel (I) auch eine oder mehrere Polyolfettsäuren und/oder deren Salze der allgemeinen Formel (II) enthalten, deutlich verbessert.The water-soluble mixtures according to the invention obtained in this way are outstandingly suitable as agents for inhibiting corrosion in drilling oils, cutting oils, rolling oils, grinding oils, solutions for metal cleaning, coolants and lubricants. It is surprising in the use of such mixtures that polyol fatty acids and their salts of the general formula (11) as such have no corrosion-inhibiting properties. However, in combination with the ammonium salts of fatty acids with the general formula (I), the compounds mentioned have a strong synergistic effect in that they significantly increase their ability to inhibit corrosion on metal surfaces. For example, it is possible to reduce the concentration of the ammonium salts of fatty acids, which as such - as known from the prior art - have corrosion-inhibiting properties by up to 50%, without any deterioration in the corrosion protection. It is further to be regarded as an advantage of the water-soluble mixtures according to the invention that they have a pronounced lack of foam and, moreover, the odor nuisance objected to when the ammonium salts of fatty acids of the general formula (I) are used alone does not occur. In addition, the mixtures according to the invention are also extremely soluble in extremely hard water. This property is also significantly improved in mixtures which, in addition to one or more ammonium salts of fatty acids with the general formula (I), also contain one or more polyol fatty acids and / or their salts of the general formula (II).

Die Erfindung wird durch die nachstehenden Beispiele näher erläutert.The invention is illustrated by the examples below.

Beispiel 1example 1

Herstellung des Kaliumsalzes einer Polyolfettsäure der allgemeinen Formel (11) (R6 = n-Octyl, m = 7, R7= 2.2-Bis(hydroxymethyl-)butyl, M⊕ = K⊕)Preparation of the potassium salt of a polyol fatty acid of the general formula (11) (R6 = n-octyl, m = 7, R 7 = 2,2-bis (hydroxymethyl-) butyl, M⊕ = K⊕)

670 g 1.1.1-Tris-(hydroxymethyl-)propan (Trimethylolpropan), 1,5 g Schwefelsäure und 1175 g epoxydiertes Sojaöl wurden 1,5 h lang unter Rühren auf 100°C erwärmt. Nach Abkühlen auf 50°C wurde eine wässrige Lösung von 247 g KOH in 623 g Wasser zugesetzt und das Reaktionsgemisch weiter 3 h lang auf 100°C erhitzt. Man erhielt auf diese Weise eine 80 %ige wässrige Lösung des Kaliumsalzes der Polyolfettsäure (II) (R6 = n-Octyl, m = 7, R7 = 2.2-Bis(-hydroxymethyl)-butyl, M9 = K⊕).670 g of 1.1.1-tris (hydroxymethyl) propane (trimethylolpropane), 1.5 g of sulfuric acid and 1175 g of epoxidized soybean oil were heated to 100 ° C. with stirring for 1.5 hours. After cooling to 50 ° C., an aqueous solution of 247 g KOH in 623 g water was added and the reaction mixture was heated at 100 ° C. for a further 3 hours. This gave an 80% aqueous solution of the potassium salt of polyol fatty acid (II) (R 6 = n-octyl, m = 7, R 7 = 2,2-bis (-hydroxymethyl) butyl, M 9 = K⊕).

Beispiel 2Example 2

Herstellung des Kaliumsalzes der Polyolfettsäure (11) mit R6 = n-Octyl, m = 7, R7 = 2.3-Dihydroxypropyl, M⊕ = K®. - Preparation of the potassium salt of polyol fatty acid (11) with R 6 = n-octyl, m = 7, R7 = 2.3-dihydroxypropyl, M⊕ = K ® . -

920 g Glycerin, 3,5 g Schwefelsäure und 1758 g epoxydierter Ölsäuremethylester wurden unter Rühren 2 h lang auf 100°C erhitzt. Nach Abkühlung auf 50°C wurde das heterogene Reaktionsgemisch mit 30 %iger methanolischer Natriummethylatlösung neutralisiert, die Glycerinphase abgetrennt und die verbleibende Phase bei 200°C und einem Druck von 0,01 mbar von ca. 200 g flüchtigen Anteilen befreit. Der Destillationsrückstand bestand aus einem hellgelben Öl.920 g of glycerol, 3.5 g of sulfuric acid and 1758 g of epoxidized oleic acid methyl ester were heated to 100 ° C. for 2 hours with stirring. After cooling to 50 ° C., the heterogeneous reaction mixture was neutralized with 30% methanolic sodium methylate solution, the glycerol phase was separated and the remaining phase was freed from approx. 200 g of volatile components at 200 ° C. and a pressure of 0.01 mbar. The distillation residue consisted of a light yellow oil.

712 g dieses Öls wurden mit einer Lösung von 80 g NaOH in 453 g Wasser bei 100°C 3 h lang erhitzt. Nach Abkühlen auf 70°C wurde das Reaktionsgemisch mit Schwefelsäure auf einen pH-Wert von 2 eingestellt, die wässrige Phase abgetrennt und die organische Phase mit auf 60°C erwärmtem Wasser gewaschen. Auf diese Weise wird eine Polyolfettsäure (II) (R6 = n-Octyl, m = 7, R7 = 2.3-Dihydroxypropyl, M⊕ = H⊕) erhalten. 69,3 g dieser Polyolfettsäure werden mit 16,8 g einer 50 %igen wässrigen Kaliumhydroxidlösung neutralisiert und mit 63,9 g deionisiertem Wasser verdünnt.712 g of this oil was heated with a solution of 80 g NaOH in 453 g water at 100 ° C for 3 hours. After cooling to 70 ° C., the reaction mixture was adjusted to a pH of 2 with sulfuric acid, the aqueous phase was separated off and the organic phase was washed with water heated to 60 ° C. In this way, a polyol fatty acid (II) (R6 = n-octyl, m = 7, R7 = 2,3-dihydroxypropyl, M⊕ = H⊕) is obtained. 69.3 g of this polyol fatty acid are neutralized with 16.8 g of a 50% aqueous potassium hydroxide solution and diluted with 63.9 g of deionized water.

Beispiel 3Example 3

Herstellung einer korrosionsinhibierenden Mischung.Preparation of a corrosion inhibiting mixture.

53 g des Neutralisationsproduktes eines Gemisches aus 50 Gew.-% Carpylsäure und 50 Gew.-% Caprinsäure mit Di-n-butylamin wurden mit 100 g des Produktes aus Beispiel 1 und 60 g Wasser vermischt.53 g of the neutralization product of a mixture of 50% by weight of carpylic acid and 50% by weight of capric acid with di-n-butylamine were mixed with 100 g of the product from Example 1 and 60 g of water.

Beispiel 4Example 4

Herstellung einer weiteren korrosionsinhibierenden Mischung.Production of a further corrosion-inhibiting mixture.

50 g des Neutralisationsprodukts eines Gemisches aus 50 Gew.-% Carpylsäure und 50 Gew.-% Caprinsäure mit Di-n-butylamin wurden mit 150 g des Produktes aus Beispiel 2 vermischt.50 g of the neutralization product of a mixture of 50% by weight of carpylic acid and 50% by weight of capric acid with di-n-butylamine were mixed with 150 g of the product from Example 2.

Beispiel 5Example 5

250 g Trimethylolpropan, 0,56 g konzentrierte Schwefelsäure und 439 g epoxidiertes Sojaöl wurden unter Rühren 1,5 h auf 100°C erhitzt. Nach Abkühlung auf 90°C wurde das Reaktionsgemisch mit 75 ml einer 50 %igen wässrigen Natriumhydroxidlösung versetzt und 3 h bei 100°C verseift. Nach abermaligem Abkühlen auf 90°C wurde das Reaktionsgemisch mit 500 g 30%iger wässriger Phosphorsäure auf pH 2 eingestellt, die wässrige Phase abgetrennt und die verbleibende organische Phase mit 2 x 40 ml Wasser gewaschen. Die auf diese Weise erhaltenen 622 g Polyolfettsäure wurden mit 131 g Diethanoiamin neutralisiert. Das Produkt wurde anschließend mit 653,6 g deionisiertem Wasser verdünnt.250 g of trimethylolpropane, 0.56 g of concentrated sulfuric acid and 439 g of epoxidized soybean oil were heated to 100 ° C. with stirring for 1.5 hours. After cooling to 90 ° C, the reaction mixture was mixed with 75 ml of a 50% aqueous sodium hydroxide solution and saponified at 100 ° C for 3 h. After cooling again to 90 ° C., the reaction mixture was adjusted to pH 2 with 500 g of 30% strength aqueous phosphoric acid, the aqueous phase was separated off and the remaining organic phase was washed with 2 × 40 ml of water. The 622 g of polyol fatty acid obtained in this way were neutralized with 131 g of diethanoiamine. The product was then diluted with 653.6 g of deionized water.

Beispiel 6Example 6

150 g der nach Beispiel 5 hergestellen Substanz wurden vermischt mit 50 g des Neutralisats aus 50 Gew.-% Caprylsäure und 50 Gew.-% Caprinsäure mit Di-n-butylamin.150 g of the substance produced according to Example 5 were mixed with 50 g of the neutralizate of 50% by weight of caprylic acid and 50% by weight of capric acid with di-n-butylamine.

Beispiel 7Example 7

Korrosionstest nach DIN 51360.Corrosion test according to DIN 51360.

Die Mischungen aus den Beispielen 3 und 4 wurden in Konzentrationen von 0,5 und 1 Gew.-%, angegeben als Ammoniumsalz-Polyolfettsäure-Mischung in der Gesamtmenge Wasser, in Wasser unterschiedlicher Härte gegeben, vollständig gelöst und im Korrosionstest nach DIN 51360 auf die korrosionsinhibierende Wirkung überprüft. Die Ergebnisse sind der nachfolgenden Tabelle 1 zu entnehmen.The mixtures from Examples 3 and 4 were given in concentrations of 0.5 and 1 wt .-%, given as ammonium salt-polyol fatty acid mixture in the total amount of water, in water of different hardness, completely dissolved and in the corrosion test according to DIN 51360 on the Corrosion-inhibiting effect checked. The results are shown in Table 1 below.

Als Vergleich wurde das kommerziell erhältliche Aminsalz eines 1 : 1-Gemisches aus Caprylsäure und Caprinsäure mit Di-n-butylamin, nachstehend als "Vergleichssubstanz" bezeichnet, herangezogen. Dessen Konzentration in der Anwendungslösung betrug 1 bzw. 2 Gew.-%.As a comparison, the commercially available amine salt of a 1: 1 mixture of caprylic acid and capric acid with di-n-butylamine, hereinafter referred to as "comparative substance", was used. Its concentration in the application solution was 1 or 2% by weight.

Die Bewertung der Korrosion auf den getesteten Blechen erfolgte nach folgender Skala:

  • 0 = keine Korrosion,
  • 1 = Spuren von Korrosion,
  • 2 = leichte Korrosion,
  • 3 = mäßige Korrosion,
  • 4 = starke Korrosion.
Figure imgb0013
 The evaluation of the corrosion on the tested sheets was based on the following scale:
  • 0 = no corrosion,
  • 1 = traces of corrosion,
  • 2 = slight corrosion,
  • 3 = moderate corrosion,
  • 4 = severe corrosion.
Figure imgb0013

Ergebnis:Result:

Bei einer Konzentration von 1 Gew.-% sind selbst in sehr hartem Wasser die Ergebnisse für die Korrosionsinhibierung bei den erfindungsgemäßen Produkten der Beispiele 3 und 4 deutlich besser als für die Vergleichssubstanz. Mit der Vergleichssubstanz vergleichbare Ergebnisse der Korrosionsinhibierung werden bei auf die Hälfte reduzierter Einsatzmenge der erfindungsgemäßen Mischungen erzielt.At a concentration of 1% by weight, the results for corrosion inhibition in the products of Examples 3 and 4 according to the invention are significantly better than in the comparison substance, even in very hard water. Results of the corrosion inhibition that are comparable with the comparison substance are achieved with a reduced use amount of the mixtures according to the invention.

Beispiel 8Example 8 Schaumtest.Foam test.

Testmethode: 50 ml einer 3 % der erfindungsgemäßen Mischungen enthaltenden Prüflösung wurden in einem 100 ml Meßzylinder zehnmal geschüttelt und das Schaumvolumen in ml sowie die Schaumzerfallzeit in min gemessen. Die Ergebnisse sind der nachfolgenden Tabelle 2 zu entnehmen. Als Vergleichssubstanz wurde wieder das Neutralisationsprodukt einer 1 : 1-Mischung von Caprylsäure und Caprinsäure mit Di-n-butylamin herangezogen.

Figure imgb0014
Test method: 50 ml of a test solution containing 3% of the mixtures according to the invention were shaken ten times in a 100 ml measuring cylinder and the foam volume in ml and the foam disintegration time in min were measured. The results are shown in Table 2 below. The neutralization product of a 1: 1 mixture of caprylic acid and capric acid with di-n-butylamine was again used as the reference substance.
Figure imgb0014

Ergebnis:Result:

Sowohl das Produkt nach Beispiel 4 als auch das nach Beispiel 3 zeigt im Vergleich zur Vergleichssubstanz einen für Aminseifen überraschend schnellen Schaumzerfall. Die Polyolfettsäure in der erfindungsgemäßen Mischung wirkt also bei den genannten Produkten synergistisch in Bezug auf den Schaumzerfall.Both the product according to Example 4 and that according to Example 3 shows a foam breakdown which is surprisingly rapid for amine soaps in comparison with the comparison substance. The polyol fatty acid in the mixture according to the invention therefore has a synergistic effect on the foam decomposition in the products mentioned.

Zudem wurde gefunden, daß die Produkte nach den Beispeilen 3 und 4 in der Geruchsbelästigung dem Vergleichsprodukt deutlich überlegen sind: Während das Vergleichsprodukt ausgesprochen unangenehm riecht, ist eine Geruchsbelästigung bei den Produkten nach den Beispielen 3 und 4 nicht festzustellen.In addition, it was found that the products according to Examples 3 and 4 are clearly superior to the comparison product in terms of odor nuisance: While the comparison product smells extremely unpleasant, no odor nuisance can be found in the products according to Examples 3 and 4.

Claims (24)

1. Water-soluble corrosion-inhibiting mixtures containing
a) one or more ammnonium salts of fatty acids corresponding to the following general formula
Figure imgb0029
in which n = 1 or 2 while Rl, R2, R3 and R4 may be the same or different and represent hydrogen, unbranched or branched C1-6 alkyl groups, C1-6, hydroxyalkylene groups or C1-8 aminoalkylene groups and R5 represents unbranched and/or branched C5-10 alkyl groups, in quantities of from 10 to 90% by weight, based on the mixture as a whole and
b) on or more polyol fatty acids and/or salts thereof corresponding to the following general formula
Figure imgb0030
in which R6 is a straight-chain or branched C1-19 alkyl or alkenylene group and R7 is an organic residue formed from a dihydroxy or polyhydroxy compound by elimination of a hydroxyl group, M9 = H9, Na⊕, K9 or an ammonium ion [R1R2R3R4N]n+, as in formula (I), and m is an integer of from 0 to 18, in quantities of from 10 to 90% by weight, based on the total weight of the mixture.
2. Water-soluble mixtures as claimed in claim 1 containing one or more ammonium salts of fatty acids corresponding to general formula (I), in which n = 1 and one of the substituents R1 to R4 is a C1-6 alkyl group while the other substituents represent hydrogen.
3. Water-soluble mixtures as claimed in claim 1 containing one or more ammonium salts of fatty acids corresponding to general formula (I), in which n = 1 and two of the substituents R1 to R4 represent C3 or C4 alkyl groups while the other substituents represent hydrogen.
4. Water-soluble mixtures as claimed in claim 3, containing one or more ammonium salts of fatty acids corresponding to general formula (I), in which n = 1 and two of the substituents R1 to R4 represent n-butyl.
5. Water-soluble mixures as claimed in claim 1, containing one or more ammonium salts of fatty acids corresponding to general formula (I), in which n = 2 and the ammonium cation [R1R2R3R4N]n+ represents [N,N-dimethyl-1,3-propylenediamine]2+,
6. Water-soluble mixtures as claimed in claims 1 to 5 containing one or more ammonium salts of fatty acids corresponding to general formula (I), in which R5 represents i-heptyl, i/n-octyl, i-nonyl or n-decyl.
7. Water-soluble mixtures as claimed in claims 1 to 6 containing two ammonium salts each of a fatty acid corresponding to general formula (I) in a ratio by weight of 1:1.
8. Water-soluble mixtures as claimed in claim 7 containing a 1:1 mixture of a neutralization product of caprylic acid and di-n-butylamine and also capric acid and di-n-butylamine.
9. Mixtures as claimed in claims 1 to 8 containing one or more ammonium salts of fatty acids corresponding to general formula (I) in quantities of from 10 to 50% by weight, based on the total weight of the mixture.
10. Water-soluble mixtures as claimed in claim 1 containing one or more polyol fatty acids and/or salts thereof corresponding to general formula (II) in which R6 is a straight-chain C8-15 alkyl group.
11. Water-soluble mixtures as claimed in claim 1 containing one or more polyol fatty acids and/or salts thereof corresponding to general formula (II), in which m = 8 to 14.
12. Water-soluble mixtures as claimed in claims 10 and 11 containing one or more polyol fatty acids and/or salts thereof corresponding to general formula (II), in which R6 is n-octyl and m is the number 7.
13. Water-soluble mixtures as claimed in claim 1 containing one or more polyol fatty acids and/or salts thereof corresponding to general formula (II) in which R7 is an organic residue formed by elimination of a hydroxyl group from one of the following compounds: ethylene glycol, glycerol, diglycerol, propylene glycol, diethylene glycol, dipropylene glycol, trimethylol ethane, trimethylol propane, neopentyl glycol, pentaerythritol, dipentaerythritol, sorbitol, sorbitan, diethanolamine, triethanolamine, polyethylene glycol
(H-(OCH2CH2-)nOH with n = 1-10),
polypropylene glycol
Figure imgb0031
 with n = 1-10),
propylene oxide-ethylene oxide block polymers, i.e. compounds corresponding to the formula
Figure imgb0032
with x+ y = 2-10 and ethylene oxide-propylene oxide block polymers, i.e. compounds corresponding to the formula
Figure imgb0033
with x+ y = 2-10.
14. Water-soluble mixtures as claimed in claim 1 containing one or more polyol fatty acids and/or salts thereof corresponding to general formula (II) in quantities of from 50 to 90% by weight, based on the total weight of the mixture.
15. A process for the preparation of water-soluble corrosion-inhibiting mixtures containing one or more ammonium salts of fatty acids corresponding to the following general formula
Figure imgb0034
in which n = 1 or 2 while Rl, R2, R3 and R4 may be the same or different and represent hydrogen, unbranched or branched C1-6 alkyl groups, C1-6 hydroxyalkylene groups or Cl-8 aminoalkylene groups and R5 represents unbranched C5-10 alkyl groups, in quantities of from 10 to 90% by weight, based on the total weight of the mixture and one or more polyol fatty acids and/or salts thereof corresponding to the following general formula
Figure imgb0035
in which R6 is a straight-chain or branched C1-19 alkyl or alkenylene group and R7 is an organic residue formed from a dihydroxy or polyhydroxy compound by elimination of a hydroxyl group, M⊕ = H⊕, NaD, K⊕ or an ammonium ion [R1R2R3R4N]n+, as in formula (I), and m is an integer of from 0 to 18, in quantities of from 10 to 90% by weight, based on the total weight of the mixture, characterized in that
a) unsaturated fatty acids corresponding to the following general formula
Figure imgb0036
in which R6 and mare as defined above and Y is hydrogen, or derivatives thereof, in which Y is the residue of a monohydric or polyhydric alcohol, such as glycerol or methanol for example, are epoxidized by methods known per se,
b) the epoxide obtained is reacted by methods known per se with a dihydroxy or polyhydroxy compound corresponding to the following general formula
Figure imgb0037
in which R7 represents an organic residue formed from a dihydroxy or polyhydroxy compound by elimination of a hydroxyl group,
c) optionally, the derivatives of the polyol fatty acid obtained are saponified with bases corresponding to the following general formula M⊕OH⊕, in which M⊕ is as defined above, or with an acid and d) the polyol fatty acid obtained and/or its salts corresponding to general formula (II) and, optionally, other polyol fatty acids corresponding to the above general formula are mixed with one or more ammonium salts of fatty acids corresponding to general formula (I) above, in which R1, R2, R3, R4, R5 and n are as defined above, in a ratio by weight of from 10:1 to 1:10.
16. A process as claimed in claim 15, characterized in that oleic acid is used as the fatty acid corresponding to general formula (III).
17. A process as claimed in claims 15 and 16, characterized in that a compound from the group comprising ethylene glycol, glycerol, diglycerol, propylene glycol, diethylene glycol, dipropylene glycol, trimethylol ethane, trimethylol propane, neopentyl glycol, pentaerythritol, dipentaerythritol, sorbitol, sorbitan, diethanolamine, triethanolamine, polyethylene glycol, polypropylene glycol and also propylene oxide-ethylene oxide block polymers and ethylene oxide-propylene oxide block polymers is used as the dihydroxy or polyhydroxy compound corresponding to general formula (IV).
18. A process as claimed in claims 15 to 17, characterized in that mixtures of ammonium salts of several fatty acids are used as the ammonium salt component.
19. A process as claimed in claim 18, characterized in that a mixture of the neutralization product of caproic acid with di-n-butylamine and capric acid with di-n-butyl amine in a ratio by weight of 1:1 is used as the ammonium salt component.
20. A process as claimed in claim 18, characterized in that a mixture of the neutralization product of caproic acid eith N,N-dimethyl-1,3-propylenediamine and capric acid with N,N-dimethyl-1,3-propylenediamine in a ratio by weight of 1:1 is used as the ammonium salt component.
21. A process as claimed in claims 15 to 20, characterized in that one or more ammonium salts of fatty acids corresponding to general formula (I) and one or more polyol fatty acids and/or salts thereof corresponding to general formula (II) are mixed with one another in a ratio by weight of 1:3 and water is optionally added.
23. The use of the water-soluble mixtures claimed in claims 1 to 14 for inhibiting corrosion in drilling oils, cutting oils, rolling oils, grinding oils, metal-cleaning solutions, coolants and lubricants.
EP87103577A 1986-03-20 1987-03-12 Water soluble mixtures of ammonium salts from fatty acids and polyol-fatty acids, or of their alcali or ammonium salts, process for their production and their use as corrosion inhibitors in aqueous systems Expired - Lifetime EP0237959B1 (en)

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