EP2363451A1 - 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
EP2363451A1
EP2363451A1 EP10154383A EP10154383A EP2363451A1 EP 2363451 A1 EP2363451 A1 EP 2363451A1 EP 10154383 A EP10154383 A EP 10154383A EP 10154383 A EP10154383 A EP 10154383A EP 2363451 A1 EP2363451 A1 EP 2363451A1
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EP
European Patent Office
Prior art keywords
corrosion protection
fatty acid
coconut fatty
dialkylbenzene
thixotropic
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Application number
EP10154383A
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German (de)
French (fr)
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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Publication date
Application filed by Rhein Chemie Rheinau GmbH filed Critical Rhein Chemie Rheinau GmbH
Priority to EP10154383A priority Critical patent/EP2363451A1/en
Priority to EP11154654.5A priority patent/EP2363452B1/en
Priority to ES11154654.5T priority patent/ES2535808T3/en
Priority to PL11154654T priority patent/PL2363452T3/en
Priority to US13/030,523 priority patent/US8828915B2/en
Publication of EP2363451A1 publication Critical patent/EP2363451A1/en
Withdrawn legal-status Critical Current

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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.
  • the thixotropic corrosion protection additives of coconut fatty acid according to the invention as film formers in combination with dialkylbenzene sulfonic acid, the disadvantages of the prior art in the washability and especially in solubility with the carrier substances do not have, but have good corrosion inhibiting properties.
  • the present invention therefore relates to novel thixotropic corrosion protection additives which are a mixture of at least one dialkylbenzene sulphonate with coconut fatty acid.
  • 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. Furthermore, the use of mixtures of different dialkylbenzene sulfonates is preferred.
  • the two alkyl radicals can occupy any position within the molecule to the sulfonate group, ie in the ortho, meta and / or para position.
  • mixtures are used.
  • the dialkylbenzene sulphonates can be prepared by sulphonation of the corresponding dialkylbenzene and subsequent neutralization with suitable bases, such as calcium hydroxide, according to methods known to the person skilled in the art. However, these are also commercially available products which are available, for example, from Rhein Chemie Rheinau GmbH under the trade name Additin® RC 4220.
  • coconut fatty acid is a commercially available product that is available, for example, from the Nordische ⁇ lwerke. 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.
  • the coconut fatty acid is preferably an almost exclusively saturated coconut oil rich in lauric and myristic acid.
  • the quantitative ratio of dialkylbenzene sulfonate to coconut fatty acid is arbitrary.
  • ratios of dialkylbenzene sulfonate to coconut fatty acid of from 5 to 1 to 1 to 5 are preferred.
  • proportions of 3 to 2 to 2 to 3 are used set.
  • 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.
  • the present invention further provides a process for the preparation of thixotropic corrosion protection additives, according to which either dialkylbenzene sulfonic acid is reacted with at least one base and then coconut fatty acid is added or, alternatively, dialkylbenzene sulfonic acid is neutralized with a base in the presence of coconut fatty acid.
  • Bases according to the invention are alkali and / or alkaline earth 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.
  • the 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 includes, for example, hydrocarbon-containing solvents, such as pentane or all types of gasoline, such as white spirits, and polar solvents, such as ethyl acetate. These are commercially available compounds. Examples are, for example, boiling mineral spirits 45/60 or 80/110 or Isopar® compounds, available from the company Exxon Mobil Oil. Thus, for example, in fire-prone areas, compounds with boiling points well above 50 ° C. are preferred, for example boiling-point petrol 80/110 or Isopar®H preferred.
  • 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 and B 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 samples in the isoparaffinic oil Isopar® H Exxon Mobil Oil.
  • the washability was determined after a 1-minute storage in 18 liters of a test cleaner solution consisting of tap water with a total hardness of 10 to 20 ° d.H, as well as 80g test cleaner TP 10339 * per liter cleaning solution. For all samples of blends A and B, the film was completely removed.
  • 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.
  • FIG. 1 Shown here are the service lives, in which there are no more than 3 smaller rust spots with an area of ⁇ 1 mm 2 .
  • 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 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)

Abstract

Thixotropic corrosion protection additive comprises a mixture of at least dialkylbenzene sulfonate with a coconut fatty acid. An independent claim is included for producing thixotropic corrosion protection additives, comprising either reacting dialkylbenzene sulfonic acid with at least a base and then adding coconut fatty acid, or neutralizing dialkylbenzene sulfonic acid with a base in the presence of coconut fatty acid.

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.
Gegenstand der vorliegenden Erfindung sind daher neue thixotrope Korrosionsschutzadditive, bei denen es sich um eine Mischung von mindestens einem Dialkylbenzensulfonat mit Kokosfettsäure handelt.
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.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, the disadvantages of the prior art in the washability and especially in solubility with the carrier substances do not have, but have good corrosion inhibiting properties.
The present invention therefore relates to novel thixotropic corrosion protection additives which are a mixture of at least one dialkylbenzene sulphonate with coconut fatty acid.
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. Furthermore, the use of mixtures of different dialkylbenzene sulfonates is preferred.

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.
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 two alkyl radicals can occupy any position within the molecule to the sulfonate group, ie in the ortho, meta and / or para position. As a rule, mixtures are used.
The dialkylbenzene sulphonates can be prepared by sulphonation of the corresponding dialkylbenzene and subsequent neutralization with suitable bases, such as calcium hydroxide, according to methods known to the person skilled in the art. However, these are also commercially available products which are available, for example, 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.
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.
Bei der Kokosfettsäure handelt es sich vorzugsweise um ein fast ausschließlich gesättigtes Kokosöl, welches reich an Laurin- und Myristinsäure ist.
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). Coconut fatty acid is a commercially available product that is available, for example, from the Nordische Ölwerke.
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.
The coconut fatty acid is preferably an almost exclusively saturated coconut oil rich in lauric and myristic acid.
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 approximately 2% Linoleic acid (<1% other oleic acids).

In den erfindungsgemäßen thixotropen Korrosionsschutzadditiven ist das Mengenverhältnis von Dialkylbenzensulfonat zu Kokosfettsäure beliebig wählbar. Bevorzugt sind jedoch Verhältnisse 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 quantitative ratio of dialkylbenzene sulfonate to coconut fatty acid is arbitrary. However, ratios of dialkylbenzene sulfonate to coconut fatty acid of from 5 to 1 to 1 to 5 are preferred. Also usable are ratios of 3: 1 to 1: 3. In a particularly preferred embodiment of the invention, proportions of 3 to 2 to 2 to 3 are used set.

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 mindestens einer Base umgesetzt und anschließend Kokosfettsäure zugesetzt wird oder alternativ Dialkylbenzensulfonsäure in Gegenwart von Kokosfettsäure mit einer Base neutralisiert wird.The present invention further provides a process for the preparation of thixotropic corrosion protection additives, according to which either dialkylbenzene sulfonic acid is reacted with at least one base and then coconut fatty acid is added or, alternatively, dialkylbenzene sulfonic acid is neutralized with a base in the presence of coconut fatty acid.

Basen im Sinne der Erfindung sind Alkali- und/oder Erdalkalihydroxide, bevorzugt Barium- oder Calciumhydroxid.
Die Base wird vorzugsweise im Überschuß zugesetzt, möglich ist aber auch der Einsatz der Base in stöchiometrischen Verhältnissen.
Die Umsetzung/ Neutralisation erfolgt vorzugsweise bei Temperaturen von 60 bis 99°C in Anwesenheit geringer Mengen Wasser.Bases according to the invention are alkali and / or alkaline earth 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.
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.
So sind beispielsweise in brandgefährdeten Bereichen Verbindungen mit Siedetemperaturen deutlich über 50°C bevorzugt, wie z.B. Siedegrenzbenzin 80/110 oder Isopar®H bevorzugt.The solvents all known compounds in question, the later field of application is crucial for the selection. The term solvent here includes, for example, hydrocarbon-containing solvents, such as pentane or all types of gasoline, such as white spirits, and polar solvents, such as ethyl acetate. These are commercially available compounds. Examples are, for example, boiling mineral spirits 45/60 or 80/110 or Isopar® compounds, available from the company Exxon Mobil Oil.
Thus, for example, in fire-prone areas, compounds with boiling points well above 50 ° C. are preferred, for example boiling-point 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.
Die Konservierungsflüssigkeiten dienen insbesondere der temporären Schutz von metallischen Werkstücken, z.B. auf dem Transportweg vor der Fertigung, für die Lagerung etc.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.

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 in einem 250mL Becherglas vorgelegt und darauf 40g der verflüssigten Filmbildner Lanolinfettsäure bzw. Kokosfettsäure, 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 Probe2 Probe 3 (VV) (VV) Dialkylbenzensulfonat = ein neutrales Calciumsulfonat mit C12-Alkylresten erhältlich bei der Rhein Chemie Rheinau GmbH 100% 60% 60% Lanolinfettsäure 40% Kokosfettsäure 40% Aussehen klar fest Leicht trüb Mischung B Probe 1 Probe2 Probe 3 (VV) (VV) (VV) Additin ® RC 4820, ein amminneutralisierter Phosphorsäurepartialester auf Basis aliphatischer Alkohole 100% 60% 60% Lanolinfettsäure 40% Kokosfettsäure 40% Aussehen klar klar klar VV = Vergleichsbeispiel First of all, 60 g of the anticorrosive component dialkylbenzenesulfonate for mixtures A or phosphoric acid partial esters for mixtures B were placed in a 250 ml beaker and then 40 g of the liquefied film formers lanolin fatty acid or coconut fatty acid, in the following tables, were added. The respective mixtures were then homogenized for 30 minutes at 80 ° C. using a stir bar and magnetic hotplate. Mixture A Sample 1 Sample 2 Sample 3 (VV) (VV) Dialkylbenzenesulfonate = a neutral calcium sulfonate with C 12 -alkyl radicals available from Rhein Chemie Rheinau GmbH 100% 60% 60% lanolin 40% coconut fatty acid 40% Appearance clear firmly Slightly cloudy Mixture B Sample 1 Sample 2 Sample 3 (VV) (VV) (VV) Additin ® RC 4820, an amminneutralized phosphoric acid partial ester based on aliphatic alcohols 100% 60% 60% lanolin 40% coconut fatty acid 40% Appearance clear clear clear VV = comparative example

Alle Proben der Mischungen A und B 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 and B 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 samples in the isoparaffinic oil Isopar® H Exxon Mobil Oil.

Die Abwaschbarkeit wurde nach einer 1-minütigen Lagerung in 18 Ltr. einer Prüfreiniger-lösung, 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.The washability was determined after a 1-minute storage in 18 liters of a test cleaner solution consisting of tap water with a total hardness of 10 to 20 ° d.H, as well as 80g test cleaner TP 10339 * per liter cleaning solution. For all samples of blends A and B, the film was completely removed.

*Laut VDA 230-201: Gardo TP 10339 der Firma Chemetall GmbH* 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:

  • 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.
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:
  • Salt spray tests in the sense of the DIN ISO 9227 standard 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:

  • 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.
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:
  • 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 dargestellt. 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 shown. 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 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 (8)

Thixotrope Korrosionsschutzadditive, dadurch gekennzeichnet, dass es sich dabei um eine Mischung von mindestens einem Dialkylbenzensulfonat mit Kokosfettsäure handelt.Thixotropic corrosion protection additives, characterized in that they are a mixture of at least one dialkylbenzene sulphonate with coconut fatty acid. Thixotrope Korrosionsschutzadditive nach Anspruch 1, dadurch gekennzeichnet, dass es sich bei dem Dialkylbenzensulfonat um eine Verbindung oder eine Mischung von Verbindungen mit Alkyl = C8-C24 handelt.Thixotropic corrosion protection additives according to claim 1, characterized in that the dialkylbenzene sulphonate is a compound or a mixture of compounds with alkyl = C 8 -C 24 . Thixotrope Korrosionsschutzadditive nach Anspruch 1, dadurch gekennzeichnet, dass eine Mischung aus Dialkylbenzensulfonaten eingesetzt wird.Thixotropic corrosion protection additives according to claim 1, characterized in that a mixture of dialkylbenzene sulfonates is used. Thixotrope Korrosionsschutzadditive nach einem oder mehreren der Ansprüche 1 bis 3, dadurch gekennzeichnet, dass das Mengenverhältnis Dialkylbenzensulfonat zu Kokosfettsäure 5 zu 1 bis 1 zu 5 beträgt.Thixotropic corrosion protection additives according to one or more of claims 1 to 3, characterized in that the ratio of dialkylbenzenesulfonate to coconut fatty acid is 5: 1 to 1: 5. Verfahren zur Herstellung der thixotropen Korrosionsschutzadditive, dadurch gekennzeichnet, dass entweder Dialkylbenzensulfonsäure mit mindestens einer Base umgesetzt und anschließend Kokosfettsäure zugesetzt wird oder alternativ Dialkylbenzensulfonsäure in Gegenwart von Kokosfettsäure mit einer Base neutralisiert wird.Process for the preparation of thixotropic corrosion protection additives, characterized in that either dialkylbenzene sulfonic acid is reacted with at least one base and then coconut fatty acid is added or alternatively dialkylbenzene sulfonic acid is neutralized in the presence of coconut fatty acid with a base. Trägersubstanzen, enthaltend mindestens ein thixotropes Korrosionsschutzadditiv nach einem oder mehreren der Ansprüche 1 bis 4.Carrier substances containing at least one thixotropic corrosion protection additive according to one or more of claims 1 to 4. Trägersubstanzen nach Anspruch 6, dadurch gekennzeichnet, dass es sich bei diesem um Öle, Lösungsmittel oder Fette handelt.Carrier substances according to claim 6, characterized in that these are oils, solvents or fats. Verwendung der thixotropen Korrosionsschutzadditive nach einem oder mehreren der Ansprüche 1 bis 4 in Konservierungsflüssigkeiten oder in Schmierfetten.Use of the thixotropic corrosion protection additives according to one or more of Claims 1 to 4 in preserving liquids or in lubricating greases.
EP10154383A 2010-02-23 2010-02-23 Thixotropic corrosion protection additive for conservation liquids and lubricating fats Withdrawn EP2363451A1 (en)

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EP10154383A EP2363451A1 (en) 2010-02-23 2010-02-23 Thixotropic corrosion protection additive for conservation liquids and lubricating fats
EP11154654.5A EP2363452B1 (en) 2010-02-23 2011-02-16 Thixotropic corrosion protection additive for conservation liquids and lubricating fats
ES11154654.5T ES2535808T3 (en) 2010-02-23 2011-02-16 Thixotropic anticorrosive additives for preservative liquids and lubricating greases
PL11154654T PL2363452T3 (en) 2010-02-23 2011-02-16 Thixotropic corrosion protection additive for conservation liquids and lubricating fats
US13/030,523 US8828915B2 (en) 2010-02-23 2011-02-18 Thixotropic corrosion protection additives for preservative liquids and lubricating greases

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Citations (4)

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Publication number Priority date Publication date Assignee Title
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
US20050079982A1 (en) * 2003-03-04 2005-04-14 Bence Patrick Joseph Thixotropic compounds and methods of manufacture
US6919302B2 (en) * 2000-05-19 2005-07-19 Usinor Use of an oil composition for temporary treatment of metal surfaces

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5726130A (en) * 1994-05-24 1998-03-10 Idemitsu Kosan Co., Ltd. Cutting or grinding oil composition
DE102004054495A1 (en) * 2004-11-11 2006-05-24 Degussa Ag Sodium percarbonate particles with a thiosulfate containing shell layer

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
US6919302B2 (en) * 2000-05-19 2005-07-19 Usinor Use of an oil composition for temporary treatment of metal surfaces
US20050079982A1 (en) * 2003-03-04 2005-04-14 Bence Patrick Joseph Thixotropic compounds and methods of manufacture

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EP2363452B1 (en) 2015-04-08
EP2363452A1 (en) 2011-09-07

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