EP2363452B1 - Thixotropic corrosion protection additive for conservation liquids and lubricating fats - Google Patents

Thixotropic corrosion protection additive for conservation liquids and lubricating fats Download PDF

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Publication number
EP2363452B1
EP2363452B1 EP11154654.5A EP11154654A EP2363452B1 EP 2363452 B1 EP2363452 B1 EP 2363452B1 EP 11154654 A EP11154654 A EP 11154654A EP 2363452 B1 EP2363452 B1 EP 2363452B1
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EP
European Patent Office
Prior art keywords
fatty acid
corrosion protection
alkyl
coconut fatty
thixotropic
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EP11154654.5A
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German (de)
French (fr)
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EP2363452A1 (en
Inventor
Markus Kuilder
Steffen Sandhöfner
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Rhein Chemie Rheinau GmbH
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Rhein Chemie Rheinau GmbH
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Priority to EP11154654.5A priority Critical patent/EP2363452B1/en
Priority to PL11154654T priority patent/PL2363452T3/en
Publication of EP2363452A1 publication Critical patent/EP2363452A1/en
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M141/00—Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential
    • C10M141/08—Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential at least one of them being an organic sulfur-, selenium- or tellurium-containing compound
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/10—Carboxylix acids; Neutral salts thereof
    • C10M2207/12—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
    • C10M2207/125—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of eight up to twenty-nine carbon atoms, i.e. fatty acids
    • C10M2207/126—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of eight up to twenty-nine carbon atoms, i.e. fatty acids monocarboxylic
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/04—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions containing sulfur-to-oxygen bonds, i.e. sulfones, sulfoxides
    • C10M2219/044—Sulfonic acids, Derivatives thereof, e.g. neutral salts
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
    • C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
    • C10M2223/04—Phosphate esters
    • C10M2223/043—Ammonium or amine salts thereof
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/02—Pour-point; Viscosity index
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/12—Inhibition of corrosion, e.g. anti-rust agents or anti-corrosives
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/20—Metal working

Definitions

  • the invention relates to novel thixotropic anticorrosive additives, to carrier substances containing these anticorrosive additives, to processes for their preparation and to their use for preserving liquids and lubricating greases.
  • Anti-corrosive additives are used in lubricants and form a protective film by chemical reaction and / or attachment of polar compounds to the metal surface.
  • the thixotropic properties promote easier application and adhesion and thus the corrosion protection properties on the metal surface.
  • Sulfonates in particular dialkylbenzene sulfonate, and / or carboxylates or else ashless corrosion protection additives, such as succinic acid monoesters, ammine-neutralized succinic acid derivatives or else amino-neutralized phosphoric acid partial esters are known as corrosion protection additives.
  • film formers such as e.g. oxidized petrolatum or lanolin fatty acid used. It is known that the effectiveness of the corrosion protection increases with the thickness of the film-forming layer, whereby film formers, such as e.g. oxidized petrolatum and lanolin fatty acid are preferred. These often have the disadvantage that the resulting corrosion protection additives have a reduced washability and a lower solubility in the end product.
  • thixotropic corrosion protection additives of coconut fatty acid according to the invention as film formers in combination with dialkylbenzene sulfonic acid do not have the disadvantages of the prior art in washability and especially in the solubility with the carrier substances, but have good corrosion-inhibiting properties.
  • Alkyl in the context of the invention means C 8 -C 24 -alkyl, preferably C 10 -C 14 -alkyl, where the two alkyl radicals within the molecule may be the same or different. Further preferred is the use of mixtures of different Dialkylbenzensulfonaten with alkyl C 8 - C 24 alkyl.
  • the two alkyl radicals can occupy any position within the molecule to the sulfonate group, i. in ortho, meta and / or para position. As a rule, mixtures are used.
  • dialkylbenzene sulfonates may be prepared by sulfonation of the corresponding dialkylbenzene followed by neutralization with suitable bases, e.g. Calcium hydroxide can be prepared by the methods known in the art. These are also commercially available products, e.g. are available from Rhein Chemie Rheinau GmbH under the trade name Additin® RC 4220.
  • Coconut fatty acid is a commercially available product, e.g. is available from the Nordic oil works.
  • the composition can vary depending on the country of origin and manufacturer, but this has no effect on the intended in the course of the invention film-forming properties. Accordingly, all types of coconut fatty acid can be used.
  • the coconut fatty acid is preferably an almost exclusively saturated coconut oil rich in lauric and myristic acid.
  • the ratio of dialkylbenzene sulfonate to coconut fatty acid is from 5 to 1 to 1 to 5. Further usable and also preferred are ratios of 3 to 1 to 1 to 3. In a particularly preferred embodiment of the invention, proportions of 3 to 2 set to 2 to 3.
  • the thixotropic corrosion protection additives may contain further additives, such as demulsifiers, stabilizers, antioxidants, defoamers, wear protection and / or high-pressure additives, but also other known anticorrosion additives, e.g. Sulfonates, carboxylates, naphthenates, etc.
  • Bases according to the invention are alkali metal and / or alkaline earth metal hydroxides, preferably barium or calcium hydroxide.
  • the base is preferably added in excess, but it is also possible to use the base in stoichiometric proportions.
  • reaction / neutralization is preferably carried out at temperatures of 60 to 99 ° C in the presence of small amounts of water.
  • the stirring of the coconut fatty acid should be at temperatures above the melting point of the coconut fatty acid, i. preferably above 40 ° C, most preferably at temperatures around 60 ° C.
  • a filtration step after the completion of the reaction and before the bottling of the product in order to separate off any excess base present.
  • dialkylbenzene sulfonic acid with at least one base in the presence of a partial amount of the intended coconut fatty acid and to add the remaining portion of the coconut fatty acid after neutralization.
  • Another object of the invention are vehicles containing at least one inventive thixotropic corrosion protection additive.
  • Carrier substances within the meaning of the invention are preferably oils, solvents or fats.
  • oils are long-chain, as well as branched oils of any viscosity can be used, such.
  • solvent all known compounds in question, the later field of application is crucial for the selection.
  • solvent here includes e.g. hydrocarbon-containing solvents, e.g. Pentane or all types of gasoline, such as white spirits, and polar solvents, such as ethyl acetate. These are commercially available compounds. Exemplified are e.g. e.g. Boiling petrol 45/60 or 80/110 or Isopar® compounds available from Exxon Mobil Oil.
  • oils can be used any reaction products of the aforementioned oils with thickeners.
  • thickeners which may be mentioned are lithium, sodium, calcium soaps or polymer thickeners.
  • the mixing ratio of oil to thickener is freely selectable and depends on the application.
  • the introduction of the thixotropic corrosion protection additive into the carrier substances preferably takes place at temperatures above 40.degree.
  • the invention also provides the use of the thixotropic corrosion protection additives according to the invention in preservative liquids or greases.
  • the preservative liquids are used in particular for the temporary protection of metallic workpieces, eg on the transport route before production, for storage, etc.
  • blends A, B and C had comparable film strength and washability.
  • the film thickness was determined as the average film thickness from the gravimetric determination of the untreated sheet compared to the coated sheet after a 2-hour drying time after immersion in a 10% solution of the above-mentioned. Samples are determined by isoparaffinic oil Isopar® H from Exxon Mobil Oil.
  • Salt spray tests in the sense of the standard DIN ISO 9227 are tests with a continuously sprayed, aqueous sodium chloride solution with a mass concentration of 5 g / 100 ml as an attacking agent. The spraying happened with the help of compressed air.
  • Steel sheets ST 1405 according to DIN 1623 Part 1 were set up at a temperature in the chamber of 35 ° C.
  • the angle of inclination of the sheets in the chamber was about 25 ° from the vertical position.
  • the steel sheets were precleaned with boiling-point petrol (60/80) and then wiped with a petrol soaked cloth until the cloth showed no more dark discoloration. Now the plates marked with numbers were hung on a hook and dipped 3 times 30s in the sample to be tested. Subsequently, the sheets were stored 2h hanging in the closet. Thereafter, the sheets were transferred to the test fixture and the heated Salzsprühhunt. The assessment was made at the given times. Only the front of the tin was judged. The onset of rust often occurs at the edge of the sheet metal.
  • the thixotrobe corrosion protection additive of dialkylbenzene sulfonate and coconut fatty acid according to the invention achieved the best results in the Salzsprühhunt-life and shows a clear jump in performance over other film formers!
  • This additive also shows good results in the washability test, such as anti-corrosive additives without film-forming agents and is also readily soluble in all tested base oils, such as paraffin-based mineral oils of various viscosities, gasoline, naphthenic base oils and even in short-chain isoparaffins.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Preventing Corrosion Or Incrustation Of Metals (AREA)
  • Lubricants (AREA)

Description

Die Erfindung betrifft neue thixotrope Korrosionsschutzadditive, Trägersubstanzen enthaltend diese Korrosionsschutzadditive, Verfahren zu deren Herstellung und deren Verwendung für Konservierungsflüssigkeiten und Schmierfette.The invention relates to novel thixotropic anticorrosive additives, to carrier substances containing these anticorrosive additives, to processes for their preparation and to their use for preserving liquids and lubricating greases.

Korrosionsschutzadditive werden in Schmierstoffen eingesetzt und bilden einen Schutzfilm durch chemische Reaktion und/oder Anlagerung polarer Verbindungen an die Metalloberfläche. Die thixotropen Eigenschaften fördern die leichtere Applikation und Haftung und damit die Korrosionsschutzeigenschaften auf der Metalloberfläche.Anti-corrosive additives are used in lubricants and form a protective film by chemical reaction and / or attachment of polar compounds to the metal surface. The thixotropic properties promote easier application and adhesion and thus the corrosion protection properties on the metal surface.

Als Korrosionsschutzadditive sind vor allem Sulfonate, insbesondere Dialkylbenzensulfonat, und/oder Carboxylate oder auch aschefreie Korrosionsschutzadditive, wie Bernsteinsäurehalbester, amminneutralisierte Bernsteinsäurederivate oder aber auch aminneutralisierte Phosphorsäurepartialester bekannt.Sulfonates, in particular dialkylbenzene sulfonate, and / or carboxylates or else ashless corrosion protection additives, such as succinic acid monoesters, ammine-neutralized succinic acid derivatives or else amino-neutralized phosphoric acid partial esters are known as corrosion protection additives.

Häufig werden zur Verbesserung des Korrosionsschutzes Filmbildner, wie z.B. oxidiertes Petrolatum oder auch Lanolinfettsäure eingesetzt. Es ist bekannt, dass die Effektivität des Korrosionsschutzes mit der Stärke der filmbildenden Schicht zunimmt, wodurch Filmbildner, wie z.B. oxidiertes Petrolatum und Lanolinfettsäure bevorzugt sind. Diese haben oft den Nachteil, dass die daraus resultierenden Korrosionsschutzadditive eine verminderte Abwaschbarkeit und eine schlechtere Löslichkeit im Endprodukt aufweisen.Frequently, to improve corrosion protection, film formers, such as e.g. oxidized petrolatum or lanolin fatty acid used. It is known that the effectiveness of the corrosion protection increases with the thickness of the film-forming layer, whereby film formers, such as e.g. oxidized petrolatum and lanolin fatty acid are preferred. These often have the disadvantage that the resulting corrosion protection additives have a reduced washability and a lower solubility in the end product.

Alternativ dazu werden in US-A 3981682 Korrosionsschutzadditive auf Basis höherkettiger ungesättigter Dicarbonsäuren in Verbindung mit Fettsäuren, wie Ölsäure oder auch Kokosfettsäure, beschrieben. Kokosfettsäure bildet jedoch nachteiligerweise eine geringere Schichtdicke als Film aus.Alternatively, in US-A 3981682 Anticorrosive additives based on higher-chain unsaturated dicarboxylic acids in combination with fatty acids, such as oleic acid or coconut fatty acid described. However, coconut fatty acid disadvantageously forms a smaller film thickness than film.

Es bestand daher ein großer Bedarf an Korrosionsschutzadditiven, die die Nachteile des Standes der Technik nicht aufweisen.There was therefore a great need for corrosion protection additives which do not have the disadvantages of the prior art.

Überraschenderweise wurde nun gefunden, dass die erfindungsgemäßen thixotropen Korrosionsschutzadditive aus Kokosfettsäure als Filmbildner in Kombination mit Dialkylbenzensulfonsäure, die Nachteile des Standes der Technik in der Abwaschbarkeit und besonders in der Löslichkeit mit den Trägersubstanzen nicht aufweisen, aber über gute korrosionsinhibierende Eigenschaften verfügen.Surprisingly, it has now been found that the thixotropic corrosion protection additives of coconut fatty acid according to the invention as film formers in combination with dialkylbenzene sulfonic acid do not have the disadvantages of the prior art in washability and especially in the solubility with the carrier substances, but have good corrosion-inhibiting properties.

Gegenstand der vorliegenden Erfindung sind daher neue thixotrope Korrosionsschutzadditive, bei denen es sich um eine Mischung von mindestens einem Dialkylbenzensulfonat mit Alkyl = C8 -C24-Alkyl mit Kokosfettsäure handelt, wobei das Mengenverhältnis Dialkylbenzensulfonat zu Kokosfettsäure 5 zu 1 bis 1 zu 5 beträgt.Accordingly, the present invention relates to novel thixotropic corrosion protection additives, which are a mixture of at least one Dialkylbenzensulfonat where alkyl = C 8 - is C 24 alkyl with coconut fatty acid, wherein the amount ratio is Dialkylbenzensulfonat to coconut fatty acid 5: 1 to 1: 5.

Alkyl im Sinne der Erfindung bedeutet C8-C24-Alkyl, bevorzugt C10-C14-Alkyl, wobei die beiden Alkylreste innerhalb des Moleküls gleich oder ungleich sein können. Des Weiteren bevorzugt ist der Einsatz von Mischungen von unterschiedlichen Dialkylbenzensulfonaten mit Alkyl- C8 -C24-Alkyl.Alkyl in the context of the invention means C 8 -C 24 -alkyl, preferably C 10 -C 14 -alkyl, where the two alkyl radicals within the molecule may be the same or different. Further preferred is the use of mixtures of different Dialkylbenzensulfonaten with alkyl C 8 - C 24 alkyl.

Die beiden Alkylreste können innerhalb des Moleküls jede Stellung zur Sulfonatgruppe einnehmen, d.h. in ortho, meta und/oder para-Stellung. In der Regel werden Mischungen eingesetzt.The two alkyl radicals can occupy any position within the molecule to the sulfonate group, i. in ortho, meta and / or para position. As a rule, mixtures are used.

Die Dialkylbenzensulfonate können durch Sulfonierung der entsprechende Dialkylbenzene und anschließender Neutralisation mit geeigneten Basen, wie z.B. Calciumhydroxid nach den dem Fachmann geläufigen Methoden hergestellt werden. Es handelt sich dabei aber auch um handelsübliche Produkte, die z.B. bei der Rhein Chemie Rheinau GmbH unter dem Handelsnamen Additin® RC 4220 erhältlich sind.The dialkylbenzene sulfonates may be prepared by sulfonation of the corresponding dialkylbenzene followed by neutralization with suitable bases, e.g. Calcium hydroxide can be prepared by the methods known in the art. These are also commercially available products, e.g. are available from Rhein Chemie Rheinau GmbH under the trade name Additin® RC 4220.

Kokosfettsäure ist ein kommerziell verfügbares Produkt, das z.B. erhältlich ist bei den Nordischen Ölwerken.Coconut fatty acid is a commercially available product, e.g. is available from the Nordic oil works.

Da es um ein Naturprodukt handelt, kann die Zusammensetzung je nach Herkunftsland und Hersteller schwanken, was aber auf die im Zuge der Erfindung beabsichtigten filmbildenden Eigenschaften keine Auswirkungen hat. Dementsprechend sind alle Arten von Kokosfettsäure einsetzbar.Since it is a natural product, the composition can vary depending on the country of origin and manufacturer, but this has no effect on the intended in the course of the invention film-forming properties. Accordingly, all types of coconut fatty acid can be used.

Bei der Kokosfettsäure handelt es sich vorzugsweise um ein fast ausschließlich gesättigtes Kokosöl, welches reich an Laurin- und Myristinsäure ist.The coconut fatty acid is preferably an almost exclusively saturated coconut oil rich in lauric and myristic acid.

Eine typische Zusammensetzung ist, ohne, dass die Erfindung darauf beschränkt ist, ca. 48% Laurinsäure = C12 -gesättigte Fettsäure ca. 18% Myristinsäure = C14 -gesättigte Fettsäure ca. 9% Palmitinsäure = C16 -gesättigte Fettsäure ca. 7% Caprylsäure = C8 -gesättigte Fettsäure ca. 7% Ölsäure = C18- ungesättigte Fettsäure ca. 6% Caprinsäure = C10 -gesättigte Fettsäure ca. 3% Stearinsäure = C18- gesättigte Fettsäure ca. 2% Linolsäure (< 1% sonstige Ölsäuren). A typical composition is, without the invention being limited thereto, about 48% lauric acid = C 12 -saturated fatty acid about 18% myristic = C 14 -saturated fatty acid about 9% palmitic = C 16 -saturated fatty acid about 7% caprylic = C 8 -saturated fatty acid about 7% oleic acid = C 18 - unsaturated fatty acid about 6% capric acid = C 10 -saturated fatty acid about 3% stearic acid = C 18 - saturated fatty acid about 2% Linoleic acid (<1% other oleic acids).

In den erfindungsgemäßen thixotropen Korrosionsschutzadditiven ist das Mengenverhältnis von Dialkylbenzensulfonat zu Kokosfettsäure von 5 zu 1 bis 1 zu 5. Weiterhin einsetzbar und ebenfalls bevorzugt sind Verhältnisse von 3 zu 1 bis 1 zu 3. In einer besonders bevorzugten Ausführungsform der Erfindung werden Mengenverhältnisse von 3 zu 2 bis 2 zu 3 eingestellt.In the thixotropic corrosion protection additives according to the invention, the ratio of dialkylbenzene sulfonate to coconut fatty acid is from 5 to 1 to 1 to 5. Further usable and also preferred are ratios of 3 to 1 to 1 to 3. In a particularly preferred embodiment of the invention, proportions of 3 to 2 set to 2 to 3.

In einer weiteren Ausführungsform der Erfindung können die thixotropen Korrosionsschutzadditive je nach Anwendungsgebiet weitere Additive, wie Demulgatoren, Stabilisatoren, Antioxidanzien, Entschäumer, Verschleißschutz und/oder Hochdruck-Additive enthalten, aber auch weitere bekannte Korrosionsschutzadditive, z.B. Sulfonate, Carboxylate, Naphtenate etc.In a further embodiment of the invention, depending on the field of application, the thixotropic corrosion protection additives may contain further additives, such as demulsifiers, stabilizers, antioxidants, defoamers, wear protection and / or high-pressure additives, but also other known anticorrosion additives, e.g. Sulfonates, carboxylates, naphthenates, etc.

Gegenstand der vorliegenden Erfindung ist zudem ein Verfahren zur Herstellung von thixotropen Korrosionsschutzadditiven, wonach entweder Dialkylbenzensulfonsäure mit Alkyl = C8 -C24-Alkyl oder Mischungen daraus mit mindestens einer Base umgesetzt und anschließend Kokosfettsäure zugesetzt wird oder alternativ Dialkylbenzensulfonsäure mit Alkyl = C8 -C24-Alkyl oder Mischungen daraus in Gegenwart von Kokosfettsäure mit einer Base neutralisiert wird, wobei das Mengenverhältnis Dialkylbenzensulfonat zu Kokosfettsäure 5 zu 1 bis 1 zu 5 beträgt.The present invention also provides a process for the production of thixotropic corrosion protection additives, after which either Dialkylbenzensulfonsäure where alkyl = C 8 - C therefrom reacted for 24 alkyl, or mixtures with at least a base and subsequently coconut fatty acid is added or alternatively Dialkylbenzensulfonsäure where alkyl = C 8 - C 24- alkyl or mixtures thereof is neutralized in the presence of coconut fatty acid with a base, wherein the ratio of dialkylbenzenesulfonate to coconut fatty acid 5 to 1 to 1 to 5.

Basen im Sinne der Erfindung sind Alkali- und/oder Erdalkalihydroxide, bevorzugt Barium-oder Calciumhydroxid.Bases according to the invention are alkali metal and / or alkaline earth metal hydroxides, preferably barium or calcium hydroxide.

Die Base wird vorzugsweise im Überschuß zugesetzt, möglich ist aber auch der Einsatz der Base in stöchiometrischen Verhältnissen.The base is preferably added in excess, but it is also possible to use the base in stoichiometric proportions.

Die Umsetzung/ Neutralisation erfolgt vorzugsweise bei Temperaturen von 60 bis 99°C in Anwesenheit geringer Mengen Wasser.The reaction / neutralization is preferably carried out at temperatures of 60 to 99 ° C in the presence of small amounts of water.

Das Zurühren der Kokosfettsäure sollte bei Temperaturen oberhalb des Schmelzpunktes der Kokosfettsäure liegen, d.h. vorzugsweise oberhalb von 40°C, ganz besonders bevorzugt bei Temperaturen um die 60°C.The stirring of the coconut fatty acid should be at temperatures above the melting point of the coconut fatty acid, i. preferably above 40 ° C, most preferably at temperatures around 60 ° C.

Weiterhin bevorzugt ist ein Filtrationsschritt nach Abschluß der Umsetzung und vor dem Abfüllen des Produktes, um eventuell vorhandene überschüssige Base abzutrennen.Further preferred is a filtration step after the completion of the reaction and before the bottling of the product in order to separate off any excess base present.

Ebenfalls möglich ist es, die Dialkylbenzensulfonsäure mit mindestens einer Base in Gegenwart einer Teilmenge der beabsichtigten Kokosfettsäure umzusetzen und den restlichen Anteil der Kokosfettsäure nach erfolgter Neutralisation zuzugeben.It is also possible to react the dialkylbenzene sulfonic acid with at least one base in the presence of a partial amount of the intended coconut fatty acid and to add the remaining portion of the coconut fatty acid after neutralization.

Ein weiterer Gegenstand der Erfindung sind Trägersubstanzen, enthaltend mindestens ein erfindungsgemäßes thixotropes Korrosionsschutzadditiv.
Trägersubstanzen im Sinne der Erfindung sind vorzugsweise Öle, Lösungsmittel oder Fette.Another object of the invention are vehicles containing at least one inventive thixotropic corrosion protection additive.
Carrier substances within the meaning of the invention are preferably oils, solvents or fats.

Als Öle sind dabei langkettige, wie auch verzweigte Öle jeglicher Viskosität einsetzbar, wie z.B. Solventraffinate, Polyalphaolefine, Hydrocracked Öle.As oils are long-chain, as well as branched oils of any viscosity can be used, such. Solvent raffinates, polyalphaolefins, hydrocracked oils.

Bei den Lösungsmitteln kommen alle bekannten Verbindungen in Frage, wobei das spätere Anwendungsgebiet für die Auswahl entscheidend ist. Der Begriff Lösungsmittel umfaßt dabei z.B. kohlenwasserstoffhaltige Lösungsmittel, wie z.B. Pentan oder alle Benzinarten, wie Testbenzine, auch polare Lösungsmittel, wie Ethylacetat. Dabei handelt es sich um handelsübliche Verbindungen. Exemplarisch genannt sind z.B. z.B. Siedegrenzbenzin 45/ 60 oder 80/110 oder Isopar® - Verbindungen, erhältlich bei der Firma Exxon Mobil Oil.The solvents all known compounds in question, the later field of application is crucial for the selection. The term solvent here includes e.g. hydrocarbon-containing solvents, e.g. Pentane or all types of gasoline, such as white spirits, and polar solvents, such as ethyl acetate. These are commercially available compounds. Exemplified are e.g. e.g. Boiling petrol 45/60 or 80/110 or Isopar® compounds available from Exxon Mobil Oil.

So sind beispielsweise in brandgefährdeten Bereichen Verbindungen mit Siedetemperaturen deutlich über 50°C bevorzugt, wie z.B. Siedegrenzbenzin 80/110 oder Isopar®H bevorzugt.Thus, for example, in fire-prone areas, compounds with boiling temperatures well above 50 ° C are preferred, e.g. Boiling petrol 80/110 or Isopar®H preferred.

Als Fette einsetzbar sind jedwede Umsetzungsprodukte der vorgenannten Öle mit Verdickern. Als Verdicker seien beispielhaft Lithium-, Natrium-, Calciumseifen oder aber auch Polymerverdicker genannt. Das Mischungsverhältnis von Öl zu Verdicker ist frei wählbar und bestimmt sich nach dem Anwendungszweck.As fats can be used any reaction products of the aforementioned oils with thickeners. Examples of thickeners which may be mentioned are lithium, sodium, calcium soaps or polymer thickeners. The mixing ratio of oil to thickener is freely selectable and depends on the application.

Das Einbringen des thixotropen Korrosionsschutzadditivs in die Trägersubstanzen erfolgt dabei vorzugsweise bei Temperaturen oberhalb 40°C.The introduction of the thixotropic corrosion protection additive into the carrier substances preferably takes place at temperatures above 40.degree.

Gegenstand der Erfindung ist zudem die Verwendung der erfindungsgemäßen thixotropen Korrosionsschutzadditive in Konservierungsflüssigkeiten oder Schmierfetten.The invention also provides the use of the thixotropic corrosion protection additives according to the invention in preservative liquids or greases.

Die Konservierungsflüssigkeiten dienen insbesondere der temporären Schutz von metallischen Werkstücken, z.B. auf dem Transportweg vor der Fertigung, für die Lagerung etc.The preservative liquids are used in particular for the temporary protection of metallic workpieces, eg on the transport route before production, for storage, etc.

Davon mitumfaßt ist dabei auch das Verfahren zum antikorrosiven Ausstattung von Konservierungsflüssigkeiten, bei dem die erfindungsgemäße Mischung aus mindestens einem Dialkylbenzensulfonat mit Kokosfettsäure, der vorgenannten Definitionen, eingesetzt wird.Included hereof is also the process for the anticorrosive equipment of preservative liquids, in which the mixture according to the invention of at least one dialkylbenzene sulphonate with coconut fatty acid, the abovementioned definitions, is used.

Die nachfolgenden Beispiele dienen der Erläuterung der Erfindung, ohne dabei limitierend zu wirken.The following examples serve to illustrate the invention without being limiting.

Ausführungsbeispiele:EXAMPLES

Es wurden die folgenden Proben hergestellt:The following samples were prepared:

Zunächst wurden 60g der korrosionschutzwirksamen Komponente Dialkylbenzensulfonat für die Mischungen A bzw. Phosphorsäurepartialester für die Mischungen B sowie ein Amin neutralisiertes Bernsteinsäurederivat für Mischung C in einem 250mL Becherglas vorgelegt und darauf 40g der verflüssigten Filmbildner Lanolinfettsäure bzw. Kokosfettsäure, bzw. Talgfettsäure, in den nachstehenden Tabellen aufgeführten Mengen, zugegeben. Die jeweiligen Mischungen wurden nun 30 min bei 80°C mittels Rührfisch und Magnetheizplatte homogenisiert. Mischung A Probe1 (VV) Probe2 (VV) Probe 3 Probe 4 (VV) Dialkylbenzensulfonat = ein neutrales Calciumsulfonat mit C 12 Alkylresten, erhältlich bei der Rhein Chemie Rheinau GmbH 100% 60% 60% 60% Lanolinfettsäure 40% Kokosfettsäure 40% Talgfettsäure 40% 40% Aussehen klar fest Leicht trüb Leicht trüb Mischung B Probe1 (VV) Probe2 (VV) Probe 3 (VV) Probe 4 (VV) Additin®RC 4820, ein amminneutralisierter Phosphorsäurepartialester auf Basis aliphatischer Alkohole 100% 60% 60% 60% Lanolinfettsäure 40% Kokosfettsäure 40% Talgfettsäure 40% Aussehen klar klar klar klar Mischung C Probe1 (VV) Probe2 (VV) Probe 3 (VV) Probe 4 (VV) Amin neutralisiertes Bernsteinsäurederivat 100% 60% 60% 60% Lanolinfettsäure 40% Kokosfettsäure 40% Talgfettsäure 40% Aussehen klar klar klar klar VV = Vergleichsbeispiel First, 60 g of the corrosion-protective component dialkylbenzenesulfonate for mixtures A and phosphoric acid partial esters for mixtures B and an amine-neutralized succinic acid derivative for mixture C were placed in a 250 ml beaker and then 40 g of the liquefied film formers lanolin fatty acid or coconut fatty acid or tallow fatty acid, in the tables below listed amounts added. The respective mixtures were then homogenized for 30 minutes at 80 ° C. using a stir bar and magnetic hotplate. Mixture A Sample1 (VV) Sample2 (VV) Sample 3 Sample 4 (VV) Dialkylbenzenesulfonate = a neutral calcium sulfonate with C 12 alkyl radicals, available from Rhein Chemie Rheinau GmbH 100% 60% 60% 60% lanolin 40% coconut fatty acid 40% tallow 40% 40% Appearance clear firmly Slightly cloudy Slightly cloudy Mixture B Sample1 (VV) Sample2 (VV) Sample 3 (VV) Sample 4 (VV) Additin®RC 4820, an amminneutralized phosphoric acid partial ester based on aliphatic alcohols 100% 60% 60% 60% lanolin 40% coconut fatty acid 40% tallow 40% Appearance clear clear clear clear Mixture C Sample1 (VV) Sample2 (VV) Sample 3 (VV) Sample 4 (VV) Amine neutralized succinic acid derivative 100% 60% 60% 60% lanolin 40% coconut fatty acid 40% tallow 40% Appearance clear clear clear clear VV = comparative example

Alle Proben der Mischungen A, B und C wiesen eine vergleichbare Filmstärke und Abwaschbarkeit auf. Die Filmstärke wurde dabei als durchschnittliche Filmstärke aus der gravimetrischen Bestimmung des unbehandelten Bleches im Vergleich zum beschichteten Blech nach einer 2-stündigen Trockenzeit nach Eintauchen in eine 10% Lösung der o.g. Proben indem isoparaffinischen Öl Isopar® H der Firma Exxon Mobil Oil ermittelt.All samples of blends A, B and C had comparable film strength and washability. The film thickness was determined as the average film thickness from the gravimetric determination of the untreated sheet compared to the coated sheet after a 2-hour drying time after immersion in a 10% solution of the above-mentioned. Samples are determined by isoparaffinic oil Isopar® H from Exxon Mobil Oil.

Die Abwaschbarkeit wurde nach einer 1-minütigen Lagerung in 18 Ltr. einer Prüfreinigerlösung, bestehend aus Leitungswasser mit einer Gesamthärte von 10 bis 20°d.H, so wie 80g Prüfreiniger TP 10339* pro Liter Prüfreinigerlösung bestimmt. Bei allen Proben der Mischungen A und B wurde der Film vollständig entfernt.
*Laut VDA 230-201: Gardo TP 10339 der Firma Chemetall GmbHThe washability was determined after 1 minute storage in 18 liters of a test cleaner solution consisting of tap water with a total hardness of 10 to 20 ° dH, as well as 80g test cleaner TP 10339 * per liter of cleaning solution. For all samples of blends A and B, the film was completely removed.
* According to VDA 230-201: Gardo TP 10339 of the company Chemetall GmbH

Es zeigten sich klare Vorteile des erfindungsgemäßen thixotropen Korrosionsschutzadditivs (Mischung A, Probe 3) im Salzsprühkammertest, der als sog. Salzsprühnebelprüfung nach DIN ISO 9227 erfolgte:There were clear advantages of the thixotropic corrosion protection additive according to the invention (mixture A, sample 3) in the salt spray chamber test, which was carried out as a so-called salt spray test according to DIN ISO 9227:

Salzsprühnebelprüfungen im Sinne der Norm DIN ISO 9227 sind Prüfungen mit einer kontinuierlich versprühten, wässrigen Natriumchlorid-Lösung mit einer Massenkonzentration von 5g/100 ml als angreifendes Mittel. Das Versprühen geschah mit Hilfe von Druckluft.Salt spray tests in the sense of the standard DIN ISO 9227 are tests with a continuously sprayed, aqueous sodium chloride solution with a mass concentration of 5 g / 100 ml as an attacking agent. The spraying happened with the help of compressed air.

Für diesen Test wurde eine 5% ige NaCl angesetzt und der pH auf 6,5 bis 7,2 eingestellt. Danach wurde die Temperatur 35 ± 2°C und der Salzsprühnebel überprüft. Es wurden vier 100 ml Messzylinder in der Kammer aufgestellt. In die Zylinder wurde ein Trichter mit einer Auffangfläche von 80 cm2 gestellt. Der Salzsprühnebel wurde über 16h aufgefangen und betrug im Mittel 1,5 ± 0,5 ml pro Stunde. Danach wurde wie folgt verfahren:For this test, a 5% NaCl was prepared and the pH was adjusted to 6.5 to 7.2. Thereafter, the temperature was checked 35 ± 2 ° C and the salt spray. Four 100 ml graduated cylinders were placed in the chamber. Into the cylinders, a funnel with a collecting area of 80 cm 2 was placed. The salt spray was collected over 16 hours and averaged 1.5 ± 0.5 ml per hour. Thereafter, the procedure was as follows:

Es wurden Stahlbleche ST 1405 nach DIN 1623 Teil 1 bei einer Temperatur in der Kammer 35°C aufgestellt. Der Neigungswinkel der Bleche in der Kammer betrug ca. 25° aus vertikaler Position.Steel sheets ST 1405 according to DIN 1623 Part 1 were set up at a temperature in the chamber of 35 ° C. The angle of inclination of the sheets in the chamber was about 25 ° from the vertical position.

Die Stahlbleche wurden mit Siedebenzin (60/80) vorgereinigt und anschließend mit einen benzingetränkten Tuch abgewischt bis das Tuch keinerlei dunkle Verfärbungen mehr zeigte. Nun wurden die mit Nummern gekennzeichneten Bleche an einen Haken gehängt und 3 mal 30s in die zu prüfende Probe getaucht. Anschließend wurden die Bleche 2h im Schrank hängend gelagert. Danach wurden die Bleche in die Prüfhalterung und in die aufgeheizte Salzsprühkammer überführt. Die Beurteilung erfolgte zu den vorgegebenen Zeiten. Beurteilt wurde nur die Blechvorderseite. Der Beginn der Rostbildung erfolgt oftmals am Blechrand.The steel sheets were precleaned with boiling-point petrol (60/80) and then wiped with a petrol soaked cloth until the cloth showed no more dark discoloration. Now the plates marked with numbers were hung on a hook and dipped 3 times 30s in the sample to be tested. Subsequently, the sheets were stored 2h hanging in the closet. Thereafter, the sheets were transferred to the test fixture and the heated Salzsprühkammer. The assessment was made at the given times. Only the front of the tin was judged. The onset of rust often occurs at the edge of the sheet metal.

Die Ergebnisse der Standzeitmessung sind in Figur 1 für Dialkylbenzensulfonat und Amin neutralisierten Phosphorsäurepartialester und in Figur 2 sind die Mischungen A, B und C mit allen 3 Fettsäuren im Vergleich zu 100%igem Monoalkylbenzensulfonat abgebildet. Dargestellt sind dabei die Standzeiten, bei denen bei einer Fläche von < 1mm2 nicht mehr als 3 kleinere Rostpunkte vorliegen.The results of the lifetime measurement are in FIG. 1 for dialkylbenzenesulfonate and amine neutralized phosphoric acid partial esters and in FIG. 2 Mixtures A, B and C are shown with all 3 fatty acids compared to 100% monoalkylbenzenesulfonate. Shown here are the service lives, in which there are no more than 3 smaller rust spots with an area of <1 mm 2 .

Das erfindungsgemäße thixotrobe Korrosionsschutzadditiv aus Dialkylbenzensulfonat und Kokosfettsäure (Mischung A, Probe 3) erzielte die besten Ergebnisse in den Salzsprühkammer-Standzeiten und zeigt gegenüber anderen Filmbildnern einen eindeutigen Leistungssprung! Dieses Additiv zeigt ebenso gute Ergebnisse im Abwaschbarkeitstest, wie Korrosionsschutzadditive ohne Filmbildner und ist zudem in allen getesteten Grundölen, wie paraffinbasischen Mineralölen verschiedenster Viskositäten, Benzin, naphthenischen Grundölen und sogar in kurzkettigen Isoparaffinen gut löslich.The thixotrobe corrosion protection additive of dialkylbenzene sulfonate and coconut fatty acid according to the invention (mixture A, sample 3) achieved the best results in the Salzsprühkammer-life and shows a clear jump in performance over other film formers! This additive also shows good results in the washability test, such as anti-corrosive additives without film-forming agents and is also readily soluble in all tested base oils, such as paraffin-based mineral oils of various viscosities, gasoline, naphthenic base oils and even in short-chain isoparaffins.

Gerade die Löslichkeit in Isoparaffinen stellt normalerweise ein Problem dar, da dieses Trägermaterial sehr stark unpolar ist und das Einlösen von teilweise polaren Additiven entgegenwirkt.Especially the solubility in isoparaffins is usually a problem because this carrier material is very non-polar and counteracts the dissolution of partially polar additives.

Claims (6)

  1. Thixotropic corrosion protection additives, characterized in that they are a mixture of at least one dialkylbenzenesulphonate where alkyl = C8-C24-alkyl with coconut fatty acid, the quantitative ratio of dialkylbenzenesulphonate to coconut fatty acid being 5:1 to 1:5.
  2. Thixotropic corrosion protection additives according to Claim 1, characterized in that a mixture of dialkylbenzenesulphonates where alkyl = C8-C24-alkyl is used.
  3. Process for the preparation of the thixotropic corrosion protection additives, characterized in that either dialkylbenzenesulphonic acid where alkyl = C8-C24-alkyl or mixtures thereof is or are reacted with at least one base and then coconut fatty acid is added, or alternatively dialkylbenzenesulphonic acid where alkyl = C8-C24-alkyl or mixtures thereof is or are neutralized with a base in the presence of coconut fatty acid, the quantitative ratio of dialkylbenzenesulphonate to coconut fatty acid being 5:1 to 1:5.
  4. Carrier substances comprising at least one thixotropic corrosion protection additive according to one or more of Claims 1 to 2.
  5. Carrier substances according to Claim 4, characterized in that these are oils, solvents or fats.
  6. Use of the thixotropic corrosion protection additives according to one of Claims 1 to 2 in preservative liquids or in lubricating greases.
EP11154654.5A 2010-02-23 2011-02-16 Thixotropic corrosion protection additive for conservation liquids and lubricating fats Not-in-force EP2363452B1 (en)

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US3981682A (en) 1973-03-15 1976-09-21 Westvaco Corporation Corrosion inhibiting compositions and process for inhibiting corrosion of metals
US5108641A (en) * 1989-10-10 1992-04-28 Colgate-Palmolive Co. Aqueous liquid automatic dishwasher detergent composition containing dual bleach system
US5726130A (en) * 1994-05-24 1998-03-10 Idemitsu Kosan Co., Ltd. Cutting or grinding oil composition
FR2809116B1 (en) * 2000-05-19 2002-08-30 Usinor USE OF AN OIL COMPOSITION FOR THE TEMPORARY TREATMENT OF METAL SURFACES
US6875731B1 (en) * 2003-03-04 2005-04-05 Patrick Joseph Bence Thixotropic compounds and methods of manufacture
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US8828915B2 (en) 2014-09-09
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