EP4130207B1 - Additive mixture for turbine oils - Google Patents

Additive mixture for turbine oils Download PDF

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Publication number
EP4130207B1
EP4130207B1 EP21189406.8A EP21189406A EP4130207B1 EP 4130207 B1 EP4130207 B1 EP 4130207B1 EP 21189406 A EP21189406 A EP 21189406A EP 4130207 B1 EP4130207 B1 EP 4130207B1
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weight
alkyl
additive mixture
oil
formula
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German (de)
French (fr)
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EP4130207A1 (en
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Annette LOOS
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Lanxess Deutschland GmbH
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Lanxess Deutschland GmbH
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Priority to EP21189406.8A priority Critical patent/EP4130207B1/en
Priority to KR1020247003684A priority patent/KR20240040074A/en
Priority to PCT/EP2022/069130 priority patent/WO2023011855A1/en
Priority to CA3227567A priority patent/CA3227567A1/en
Priority to TW111128759A priority patent/TW202328416A/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
    • 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
    • C10M141/10—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 phosphorus-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
    • C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
    • C10M2203/10—Petroleum or coal fractions, e.g. tars, solvents, bitumen
    • C10M2203/102—Aliphatic fractions
    • C10M2203/1025—Aliphatic fractions used as base material
    • 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
    • C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
    • C10M2209/02—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2209/08—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate type
    • C10M2209/084—Acrylate; Methacrylate
    • 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
    • C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
    • C10M2209/10—Macromolecular compoundss obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2209/103—Polyethers, i.e. containing di- or higher polyoxyalkylene groups
    • 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
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/02—Amines, e.g. polyalkylene polyamines; Quaternary amines
    • C10M2215/06—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to carbon atoms of six-membered aromatic rings
    • C10M2215/064—Di- and triaryl amines
    • 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
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/02—Amines, e.g. polyalkylene polyamines; Quaternary amines
    • C10M2215/06—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to carbon atoms of six-membered aromatic rings
    • C10M2215/064—Di- and triaryl amines
    • C10M2215/065—Phenyl-Naphthyl amines
    • 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
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/08—Amides
    • 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
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/22—Heterocyclic nitrogen compounds
    • C10M2215/223—Five-membered rings containing nitrogen and carbon only
    • 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
    • C10M2219/10—Heterocyclic compounds containing sulfur, selenium or tellurium compounds in the ring
    • C10M2219/104—Heterocyclic compounds containing sulfur, selenium or tellurium compounds in the ring containing sulfur and carbon with nitrogen or oxygen in the ring
    • C10M2219/106—Thiadiazoles
    • 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
    • C10M2223/047—Thioderivatives not containing metallic elements
    • 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
    • C10N2030/04—Detergent property or dispersant property
    • 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
    • C10N2030/10—Inhibition of oxidation, e.g. anti-oxidants
    • 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
    • C10N2040/12—Gas-turbines

Definitions

  • the present invention relates to new additive mixtures, processes for their production and their use for turbine oils.
  • Turbines such as steam turbines, gas turbines and water turbines are typically used to convert kinetic energy into electricity. Effective turbine oils are essential as lubricants for trouble-free operation. The key here is the ability to provide reliable lubrication over a longer period of time at high operating temperatures.
  • a suitable turbine oil for general applications has a number of desirable properties to accommodate various operating conditions across several types of modern industrial turbines. These properties include, for example, a high viscosity index (VI), high oxidation stability (and associated long service life), low varnish/sludge formation, good water separation properties, improved rust and/or corrosion resistance and improved air release and foam properties.
  • VIP viscosity index
  • oxidation stability and associated long service life
  • varnish/sludge formation good water separation properties
  • improved rust and/or corrosion resistance improved air release and foam properties.
  • additives for turbine oils which contain nonyl or dinonyl or styrene-substituted N- ⁇ -naphthyl-N-phenylamines and nonyl or dinonyl or styrene-substituted diphenylamines as antioxidants.
  • octyl-substituted N- ⁇ -naphthyl-N-phenylamines are increasingly being used, individually or in combination with various additives, such as US-A 5726135 , whereby these have the disadvantage that they are poorly soluble in a mixture with other additives and a larger amount of a solubilizer is required to obtain a liquid additive mixture.
  • turbine oils are known whose oil contains one or more antioxidants from the group of N- ⁇ -naphthyl-N-phenylamine and diphenylamine as well as sulfur-containing additives as additional components.
  • Sulfur-containing compounds are known to be able to improve oxidation stability in lubricants, as evidenced by results in the Rotation Pressure Vessel Oxidation Test (RPVOT, ASTM D 2272) and the oxidation-corrosion test according to ASTM D 4636. Examples can also be found in WO2019/183187 .
  • many sulfur-containing compounds tend to form sludge, which has a negative impact the results of other oxidation tests such as B. the dry TOST according to ASTM D 7873.
  • the object of the present invention is to provide an improved additive mixture which can be used as a turbine oil in particular in combination with a base oil, this turbine oil meeting both the requirements of the oxidation test according to ASTM D 7873 and passing the corrosion and oxidation test according to ASTM D 4636 .
  • an additive mixture containing one or more C 10 -C 14 alkyl-substituted N- ⁇ -naphthyl-N-phenylamines (APAN), alkyl-substituted diphenylamines (DPA), at least a sulfur-containing compound from the group of C 8 -C 12 alkyl-substituted-2,5,-dimercapto-1,3,4-thiadiazoles and a benzotriazole derivative.
  • APAN alkyl-substituted N- ⁇ -naphthyl-N-phenylamines
  • DPA alkyl-substituted diphenylamines
  • sulfur-containing compound from the group of C 8 -C 12 alkyl-substituted-2,5,-dimercapto-1,3,4-thiadiazoles and a benzotriazole derivative.
  • the preferred position of the radical R 1 is in the p position.
  • the alkyl-substituted diphenylamines (DPA) (b) in the sense of the invention are preferably a mixture of compounds of the formula (II) in which the radicals R 2 - R 5 are in total one, two or correspond to three C 4 or C 8 alkyl radicals. It is particularly preferred that the mixture of compounds of the formula (II) consists of 90% by weight of compounds in which R 2 and R 3 are a C 4 or C 8 alkyl radical.
  • the sulfur-containing compounds (c) in the sense of the invention are preferably C 9 -alkyl-substituted-2,5, dimercapto-1,3,4-thiadiazole.
  • the benzotriazole (d) in the sense of the invention is preferably N,N-bis(2-ethylhexyl)-methyl-1H-benzotriazol-1-methylamine with methyl in position 4, 5 or 6 and/ or N,N-bis(2-ethylhexyl)-methyl-2H-benzotriazole-1-methylamine with methyl in position 4 or 5.
  • the aforementioned benzotriazoles are preferred as mixtures of 1H-benzotriazole and 2H-benzotriazole in a ratio of 60 - 70 % by weight (1H) to 40 - 30% by weight (2H).
  • Component (e) A mineral oil, a synthetic oil or a mixture thereof can be used as oil (e) in the context of the invention.
  • oil (e) there is no particular limitation on the type of mineral oil or synthetic oil.
  • a mineral oil or a synthetic oil with a kinematic viscosity at 40°C of 10-25 cSt is used.
  • the mineral oils include paraffinic mineral oils, intermediate mineral oils and naphthenic mineral oils, as well as synthetic oils or acyclic hydrocarbons.
  • the additive mixture contains at least one corrosion inhibitor, particularly preferably a carboxamide (f).
  • carboxamides preferably amides of carboxylic acids with 4-50 carbon atoms, such as N-oleylsarcosine or succinic acid amides, can be used.
  • the additive mixture contains at least one thiophosphate (g).
  • thiophosphate (g) Neutral, covalently bound thiophosphates as well as ionic thiophosphates such as amine-neutralized thiophosphoric acid derivatives can be used as thiophosphate (g) in the sense of the invention.
  • the additive mixture contains demulsifiers selected from the group of polyglycols and/or defoamers selected from the group of polyacrylates.
  • the polyglycols preferred as demulsifiers are preferably block copolymers of polypropylene glycol and polyethylene glycol.
  • the polyacrylates preferred as defoamers are preferably homo- or copolymers of derivatives of acrylic acid, for example methacrylic acid.
  • a non-polar olefin is preferably used as the comonomer.
  • Dispersants, detergents or flowability-improving additives can also be used as further components of the additive mixture.
  • the present invention also relates to a process for producing the additive mixture according to the invention, according to which the components (a) to (d) and optionally (e) to (g) in any order at temperatures of 20 to 100 ° C, preferably 60 - 80 ° C are mixed. These are preferably stirred until a homogeneous liquid is present.
  • the present invention also relates to a turbine oil containing the additive mixture according to the invention, preferably 0.1 - 2% by weight, in a base oil.
  • API American Petroleum Institute
  • the present invention also relates to a process for producing the turbine oil according to the invention, according to which the additive mixture according to the invention with components (a) to (d) and optionally (e) to (g) at temperatures between 20 and 100 ° C, preferably 40 - 80 °C can be stirred into a base oil.
  • the present invention also relates to the use of the additive mixture according to the invention, preferably in a base oil, as a turbine oil.
  • the compounds (a) to (f) mentioned in Table 1 were mixed together in the amounts specified there (% by weight) at 70 ° C until a homogeneous solution was formed.
  • the mixtures of Examples B to D are liquid.
  • the mixture from example A (comparative example according to EP-A 1730101 ) is solid and therefore cannot be used in oil without first melting it.
  • a test according to ASTM D 4636 is considered to have failed for turbine oils if the change in weight of one of the metals (Al, Fe, Cu, Mg or Cd) is greater than 0.25 mg/cm 2 .
  • a test according to ASTM D 7873 is considered to have been passed, among other things, if after 1000 hours the RPVOT time is still at least 25% of the original RPVOT time and the sludge is below 100 mg/kg after 1000 hours. The following standard tests were carried out: The Dry TOST according to ASTM D 7873, as a standard test method for determining the oxidation stability and the formation of insoluble substances of turbine oils at 120°C without the inclusion of water (dry TOST method) and the oxidation test according to ASTM D 4636.

Description

Die vorliegende Erfindung betrifft neue Additivmischungen, Verfahren zu deren Herstellung und deren Verwendung für Turbinenöle.The present invention relates to new additive mixtures, processes for their production and their use for turbine oils.

Stand der TechnikState of the art

Turbinen, wie beispielsweise Dampfturbinen, Gasturbinen und Wasserturbinen werden in der Regel verwendet, um kinetische Energie in Strom umzuwandeln. Für einen störungsfreien Betrieb sind effektive Turbinenöle als Schmiermittel unerlässlich. Maßgeblich dabei ist die Fähigkeit, bei hohen Betriebstemperaturen über einen längeren Zeitraum eine zuverlässige Schmierung zu bieten.Turbines such as steam turbines, gas turbines and water turbines are typically used to convert kinetic energy into electricity. Effective turbine oils are essential as lubricants for trouble-free operation. The key here is the ability to provide reliable lubrication over a longer period of time at high operating temperatures.

Ein geeignetes Turbinenöl für allgemeine Anwendungen weist eine Reihe wünschenswerter Eigenschaften auf, um verschiedene Betriebsbedingungen bei mehreren Typen moderner Industrieturbinen zu berücksichtigen. Zu diesen Eigenschaften zählen beispielsweise ein hoher Viskositätsindex (VI), hohe Oxidationsstabilität (und damit verbunden lange Lebensdauer), geringe Lack-/Schlammbildung, gutes Wasserabscheidevermögen, verbesserte Rost- und/oder Korrosionsbeständigkeit und verbesserte Luftabgabe- und Schaumeigenschaften.A suitable turbine oil for general applications has a number of desirable properties to accommodate various operating conditions across several types of modern industrial turbines. These properties include, for example, a high viscosity index (VI), high oxidation stability (and associated long service life), low varnish/sludge formation, good water separation properties, improved rust and/or corrosion resistance and improved air release and foam properties.

Aus EP-A 1730101 sind beispielsweise Additive für Turbinenöle bekannt, die als Antioxidantien Nonyl- bzw- Dinonyl, bzw. Styrol-subsituierte N-α-Naphthyl-N-phenylamine und Nonyl- bzw- Dinonyl, bzw. Styrol-substituierte Diphenylamine enthalten.Out of EP-A 1730101 For example, additives for turbine oils are known which contain nonyl or dinonyl or styrene-substituted N-α-naphthyl-N-phenylamines and nonyl or dinonyl or styrene-substituted diphenylamines as antioxidants.

Insbesondere octylsubstituierte N-α-Naphthyl-N-phenylamine finden vermehrt Anwendung, einzeln oder in Kombination mit diversen Additiven, wie beispielsweise US-A 5726135 , wobei diese den Nachteil haben, dass sie in einer Mischung mit anderen Additiven schlecht löslich sind und eine größere Menge eines Lösevermittlers nötig ist, um eine flüssige Additivmischung zu erhalten.In particular, octyl-substituted N-α-naphthyl-N-phenylamines are increasingly being used, individually or in combination with various additives, such as US-A 5726135 , whereby these have the disadvantage that they are poorly soluble in a mixture with other additives and a larger amount of a solubilizer is required to obtain a liquid additive mixture.

Aus WO2019/183187 , EP-A 3712235 und EP-A 2307535 sind beispielsweise Turbinenöle bekannt, deren Öl als weitere Bestandteile einen oder mehrere Antioxidantien aus der Gruppe der N-α-Naphthyl-N-phenylamine and Diphenylamine sowie der Schwefel-haltigen Additive enthält. Von schwefelhaltigen Verbindungen ist bekannt, dass diese in Schmierstoffen die Oxidationsstabilität verbessern können, was durch Ergebnisse im Rotation Pressure Vessel Oxidation Test (RPVOT, ASTM D 2272) und im Oxidations-Korrosionstest nach ASTM D 4636 belegt wird. Beispiele finden sich auch in WO2019/183187 . Gleichzeitig neigen viele schwefelhaltige Verbindungen aber zur Schlammbildung, was sich negativ auf die Ergebnisse von anderen Oxidationstests wie z. B. dem trockenen TOST nach ASTM D 7873 auswirkt.Out of WO2019/183187 , EP-A 3712235 and EP-A 2307535 For example, turbine oils are known whose oil contains one or more antioxidants from the group of N-α-naphthyl-N-phenylamine and diphenylamine as well as sulfur-containing additives as additional components. Sulfur-containing compounds are known to be able to improve oxidation stability in lubricants, as evidenced by results in the Rotation Pressure Vessel Oxidation Test (RPVOT, ASTM D 2272) and the oxidation-corrosion test according to ASTM D 4636. Examples can also be found in WO2019/183187 . At the same time, many sulfur-containing compounds tend to form sludge, which has a negative impact the results of other oxidation tests such as B. the dry TOST according to ASTM D 7873.

Aufgabe der vorliegenden ErfindungObject of the present invention

Aufgabe der vorliegenden Erfindung ist es, eine verbesserte Additivmischung bereitzustellen, die insbesondere in Kombination mit einem Grundöl als Turbinenöl einsetzbar ist, wobei dieses Turbinenöl sowohl die Anforderungen des Oxidationstests nach ASTM D 7873 erfüllt als auch den Korrosions- und Oxidationstest nach ASTM D 4636 bestehen soll.The object of the present invention is to provide an improved additive mixture which can be used as a turbine oil in particular in combination with a base oil, this turbine oil meeting both the requirements of the oxidation test according to ASTM D 7873 and passing the corrosion and oxidation test according to ASTM D 4636 .

Lösung der AufgabeSolution to the task

Es wurde nun überraschend gefunden, dass die Aufgabe gelöst werden kann, mit einer Additivmischung, enthaltend ein oder mehrere C10-C14- alkyl-substituierte N-α-Naphthyl-N-phenylamine (APAN), alkylsubstituierte Diphenylamine (DPA), mindestens eine schwefelhaltige Verbindung aus der Gruppe der C8-C12-alkylsubstituierten-2,5,-Dimercapto-1,3,4-Thiadiazole sowie ein Benzotriazol-Derivat. It has now surprisingly been found that the object can be achieved with an additive mixture containing one or more C 10 -C 14 alkyl-substituted N-α-naphthyl-N-phenylamines (APAN), alkyl-substituted diphenylamines (DPA), at least a sulfur-containing compound from the group of C 8 -C 12 alkyl-substituted-2,5,-dimercapto-1,3,4-thiadiazoles and a benzotriazole derivative.

Gegenstand der ErfindungSubject of the invention

Gegenstand der vorliegenden Erfindung ist eine Additivmischung enthaltend

  1. (a) 35 - 90 Gew.% eines oder mehrerer alkylsubstituierten N-α-Naphthyl-N-phenylamine (APAN) der Formel (I)
    Figure imgb0001
     mit R1 = C10-C14- Alkyl, vorzugsweise C10-C12-Alkyl,
  2. (b) 0,1 - 40 Gew.% eines oder mehrerer alkylsubstituierten Diphenylamine (DPA) der Formel (II)
    Figure imgb0002
     mit R2 bis R5 = unabhängig voneinander H, C4 - C9-Alkyl, vorzugsweise C4 - Alkyl und/oder C8 - C9, mit der Maßgabe, dass mindestens einer der Reste R2 bis R5 ein C8- oder C9-Alkyl-Rest ist,
  3. (c) 0,5 - 10 Gew.% mindestens einer schwefelhaltige Verbindung der Formel (III)
    Figure imgb0003
     und R = C8 - C12- Alkyl, vorzugsweise C9H19
    und
  4. (d) 0,5 - 10 Gew.% mindestens eines Benzotriazols der Formel (IV)
    Figure imgb0004
     in
  5. (e) 0 - 30 Gew.% Öl.
The subject of the present invention is an additive mixture containing
  1. (a) 35 - 90% by weight of one or more alkyl-substituted N-α-naphthyl-N-phenylamines (APAN) of the formula (I)
    Figure imgb0001
     with R 1 = C 10 -C 14 alkyl, preferably C 10 -C 12 alkyl,
  2. (b) 0.1 - 40% by weight of one or more alkyl-substituted diphenylamines (DPA) of the formula (II)
    Figure imgb0002
     with R 2 to R 5 = independently H, C 4 - C 9 -alkyl, preferably C 4 - alkyl and / or C 8 - C 9 , with the proviso that at least one of the radicals R 2 to R 5 is a C 8 - or C 9 -alkyl radical,
  3. (c) 0.5 - 10% by weight of at least one sulfur-containing compound of the formula (III)
    Figure imgb0003
     and R = C 8 - C 12 - alkyl, preferably C 9 H 19
    and
  4. (d) 0.5 - 10% by weight of at least one benzotriazole of the formula (IV)
    Figure imgb0004
     in
  5. (e) 0 - 30% by weight oil.

Komponente (a): Bei den C10-C14- alkyl-substituierten N-α-Naphthyl-N-phenylaminen (APAN) (a) im Sinne der Erfindung handelt es sich vorzugsweise um Verbindungen der Formel (I) mit R1 = C10-C14- Alkyl, bei der mindestens 80 Gew. % der Reste R10 -C12-Alkyl, besonders bevorzugt C12- Alkyl sind. Bevorzugte Stellung des Restes R1 ist in p-Stellung. Component (a): The C 10 -C 14 alkyl-substituted N-α-naphthyl-N-phenylamines (APAN) (a) in the sense of the invention are preferably compounds of the formula (I) where R 1 = C 10 -C 14 alkyl, in which at least 80% by weight of the radicals R 10 -C1 2 alkyl, particularly preferably C 12 alkyl. The preferred position of the radical R 1 is in the p position.

Komponente (b): Bei den alkyl-substituierten Diphenylaminen (DPA) (b) im Sinne der Erfindung handelt es sich vorzugsweise um ein Gemisch aus Verbindungen der Formel (II) bei der die Reste R2 - R5 in Summe einem, zwei oder drei C4- bzw. C8-Alkylresten entsprechen. Besonders bevorzugt ist dabei, dass das Gemisch aus Verbindungen der Formel (II) zu 90 Gew.% aus Verbindungen besteht, bei denen R2 und R3 ein C4- bzw. C8-Alkylrest sind. Component (b): The alkyl-substituted diphenylamines (DPA) (b) in the sense of the invention are preferably a mixture of compounds of the formula (II) in which the radicals R 2 - R 5 are in total one, two or correspond to three C 4 or C 8 alkyl radicals. It is particularly preferred that the mixture of compounds of the formula (II) consists of 90% by weight of compounds in which R 2 and R 3 are a C 4 or C 8 alkyl radical.

Komponente (c): Bei den schwefelhaltigen Verbindungen (c) im Sinne der Erfindung handelt es sich vorzugsweise um C9 - Alkyl-substituiertes-2,5, Dimercapto-1,3,4-Thiadiazol. Component (c): The sulfur-containing compounds (c) in the sense of the invention are preferably C 9 -alkyl-substituted-2,5, dimercapto-1,3,4-thiadiazole.

Komponente (d): Bei dem Benzotriazol (d) im Sinne der Erfindung handelt es sich vorzugsweise N,N-bis(2-ethylhexyl)-methyl-1H-benzotriazol-1-methylamin mit methyl in Position 4, 5 oder 6 und/oder N,N-bis(2-ethylhexyl)-methyl-2H-benzotriazol-1-methylamin mit methyl in Position 4 oder 5. Bevorzugt werden die vorgenannten Benzotriazole als Mischungen von 1H-benzotriazol und 2H-benzotriazol aus im Verhältnis 60 - 70 Gew.% (1H) zu 40 - 30 Gew.% (2H) eingesetzt. Component (d): The benzotriazole (d) in the sense of the invention is preferably N,N-bis(2-ethylhexyl)-methyl-1H-benzotriazol-1-methylamine with methyl in position 4, 5 or 6 and/ or N,N-bis(2-ethylhexyl)-methyl-2H-benzotriazole-1-methylamine with methyl in position 4 or 5. The aforementioned benzotriazoles are preferred as mixtures of 1H-benzotriazole and 2H-benzotriazole in a ratio of 60 - 70 % by weight (1H) to 40 - 30% by weight (2H).

Komponente (e): Als Öl (e) im Sinne der Erfindung kann ein Mineralöl, ein synthetisches Öl oder eine Mischung davon verwendet werden. Es besteht keine besondere Beschränkung hinsichtlich der Art des Mineralöls oder des synthetischen Öls. Im allgemeinen wird jedoch ein Mineralöl oder ein synthetisches Öl mit einer kinematischen Viskosität bei 40°C von 10-25 cSt verwendet. Beispiele der Mineralöle schließen paraffinische Mineralöle, Intermediat-Mineralöle und naphthenische Mineralöle ein, ebenso wie synthetische Öle oder azyklische Kohlenwasserstoffe. Component (e): A mineral oil, a synthetic oil or a mixture thereof can be used as oil (e) in the context of the invention. There is no particular limitation on the type of mineral oil or synthetic oil. However, in general, a mineral oil or a synthetic oil with a kinematic viscosity at 40°C of 10-25 cSt is used. Examples of the mineral oils include paraffinic mineral oils, intermediate mineral oils and naphthenic mineral oils, as well as synthetic oils or acyclic hydrocarbons.

Komponente (f): In einer bevorzugten Ausführungsform der Erfindung enthält die Additivmischung mindestens einen Korrosionsinhibitor, besonders bevorzugt ein Carbonsäureamid (f). Component (f): In a preferred embodiment of the invention, the additive mixture contains at least one corrosion inhibitor, particularly preferably a carboxamide (f).

Als Korrosionsinhibitor (f).im Sinne der Erfindung sind Carbonsäureamide, vorzugsweise Amide von Carbonsäuren mit 4 - 50 Kohlenstoffatomen, wie beispielsweise N-Oleylsarcosin oder Bernsteinsäureamide einsetzbar.As a corrosion inhibitor (f). For the purposes of the invention, carboxamides, preferably amides of carboxylic acids with 4-50 carbon atoms, such as N-oleylsarcosine or succinic acid amides, can be used.

Bevorzugt sind Carbonsäureamide (f) der Formel (V)

Figure imgb0005
mit n = 4-10, vorzugsweise 5-7.Carboxamides (f) of the formula (V) are preferred.
Figure imgb0005
 with n = 4-10, preferably 5-7.

Komponente (g): In einer weiteren bevorzugten Ausführungsform der Erfindung enthält die Additivmischung mindestens ein Thiophosphat (g). Component (g): In a further preferred embodiment of the invention, the additive mixture contains at least one thiophosphate (g).

Als Thiophosphat (g) im Sinne der Erfindung sind neutrale, kovalent gebundene Thiophosphate als auch ionische Thiophosphate wie aminneutralisierte Thiophosphorsäurederivate einsetzbar.Neutral, covalently bound thiophosphates as well as ionic thiophosphates such as amine-neutralized thiophosphoric acid derivatives can be used as thiophosphate (g) in the sense of the invention.

Bevorzugt sind Thiophosphate (g) der Formel (VI)

Figure imgb0006
Thiophosphates (g) of the formula (VI) are preferred
Figure imgb0006

In einer weiteren bevorzugten Ausführungsform der Erfindung enthält die Additivmischung Demulgatoren ausgewählt aus der Gruppe der Polyglykole und/oder Entschäumer ausgewählt aus der Gruppe der Polyacrylate. In a further preferred embodiment of the invention, the additive mixture contains demulsifiers selected from the group of polyglycols and/or defoamers selected from the group of polyacrylates.

Bei den als Demulgatoren bevorzugten Polyglykolen handelt es sich vorzugsweise um Block-Copolymere aus Polypropylenglycol und Polyethylenglycol.The polyglycols preferred as demulsifiers are preferably block copolymers of polypropylene glycol and polyethylene glycol.

Bei den als Entschäumern bevorzugten Polyacrylaten handelt es sich vorzugsweise um Homo- oder Copolymere von Derivaten der Acrylsäure, zum Beispiel Methacrylsäure. Als Comonomer wird bevorzugt ein unpolares Olefin eingesetzt.The polyacrylates preferred as defoamers are preferably homo- or copolymers of derivatives of acrylic acid, for example methacrylic acid. A non-polar olefin is preferably used as the comonomer.

Als weitere Bestandteile der Additivmischung können auch Dispergatoren, Detergenzien oder Fließfähigkeits-verbessernde Additive eingesetzt werden.Dispersants, detergents or flowability-improving additives can also be used as further components of the additive mixture.

Bevorzugt weist die erfindungsgemäße Additivmischung folgende Anteile der Komponenten (a) bis (e) auf:

  • 50 - 70 Gew.% mindestens eines alkyl-substituierten N-α-Naphthyl-N-phenylamins (a) 0,1 - 40 Gew.%, vorzugsweise 5 - 30 Gew.% mindestens eines alkyl-substituierten Diphenylamins (b)
  • 2,5 - 9 Gew.% mindestens einer schwefelhaltigen Verbindung (c),
  • 4 - 9 Gew.% mindestens eines Benzotriazols (d) und
  • 15 - 25 Gew.% mindestens eines Öls (e),
  • wobei die Summe der Bestandteile (a) bis (e) 100 Gew.% beträgt.
The additive mixture according to the invention preferably has the following proportions of components (a) to (e):
  • 50 - 70% by weight of at least one alkyl-substituted N-α-naphthyl-N-phenylamine (a) 0.1 - 40% by weight, preferably 5 - 30% by weight of at least one alkyl-substituted diphenylamine (b)
  • 2.5 - 9% by weight of at least one sulfur-containing compound (c),
  • 4 - 9% by weight of at least one benzotriazole (d) and
  • 15 - 25% by weight of at least one oil (e),
  • where the sum of components (a) to (e) is 100% by weight.

In einer weiteren bevorzugten Ausführungsform der Erfindung weist die erfindungsgemäße Additivmischung folgende Anteile der Komponenten (a) bis (g) auf:

  • 30 - 85 Gew.%, vorzugsweise 45 - 60 Gew.% mindestens eines alkylsubstituierten N-α-Naphthyl-N-phenylamins (a),
  • 0,1 - 30 Gew.%, vorzugsweise 5 - 20 Gew.% mindestens eines alkylsubstituierten Diphenylamins (b),
  • 0,5 - 5 Gew.%, vorzugsweise 2,5 - 4 Gew.% mindestens einer schwefelhaltigen Verbindung (c),
  • 0,5 - 8 Gew.%, vorzugsweise 4 - 6 Gew.% mindestens eines Benzotriazols (d),
  • 0 - 30 Gew.%, vorzugsweise 15 - 25 Gew.% mindestens eines Öls (e),
  • 5 - 15 Gew.%, vorzugsweise 7 - 10 Gew.% mindestens eines Carbonsäureamides (f),
  • 0 - 5 Gew.%, vorzugsweise 1,5 - 3,5 Gew.% mindestens ein Thiophosphates (g),
  • wobei die Summe der Bestandteile (a) bis (g) 100 Gew.% beträgt.
In a further preferred embodiment of the invention, the additive mixture according to the invention has the following proportions of components (a) to (g):
  • 30 - 85% by weight, preferably 45 - 60% by weight of at least one alkyl-substituted N-α-naphthyl-N-phenylamine (a),
  • 0.1 - 30% by weight, preferably 5 - 20% by weight of at least one alkyl-substituted diphenylamine (b),
  • 0.5 - 5% by weight, preferably 2.5 - 4% by weight of at least one sulfur-containing compound (c),
  • 0.5 - 8% by weight, preferably 4 - 6% by weight of at least one benzotriazole (d),
  • 0 - 30% by weight, preferably 15 - 25% by weight of at least one oil (e),
  • 5 - 15% by weight, preferably 7 - 10% by weight, of at least one carboxamide (f),
  • 0 - 5% by weight, preferably 1.5 - 3.5% by weight of at least one thiophosphate (g),
  • where the sum of components (a) to (g) is 100% by weight.

Gegenstand der vorliegenden Erfindung ist zudem ein Verfahren zur Herstellung der erfindungsgemäßen Additivmischung, wonach die Komponenten (a) bis (d) und gegebenenfalls (e) bis (g) in beliebiger Reihenfolge bei Temperaturen von 20 bis 100 °C, vorzugsweise 60 - 80°C gemischt werden. Vorzugsweise werden diese solange gerührt, bis eine homogene Flüssigkeit vorliegt.The present invention also relates to a process for producing the additive mixture according to the invention, according to which the components (a) to (d) and optionally (e) to (g) in any order at temperatures of 20 to 100 ° C, preferably 60 - 80 ° C are mixed. These are preferably stirred until a homogeneous liquid is present.

Als Rührer sind gängige Mischaggregate einsetzbar.Common mixing units can be used as stirrers.

Gegenstand der vorliegenden Erfindung ist zudem ein Turbinenöl, enthaltend die erfindungsgemäße Additivmischung, vorzugsweise zu 0,1 - 2 Gew.%, in einem Grundöl. The present invention also relates to a turbine oil containing the additive mixture according to the invention, preferably 0.1 - 2% by weight, in a base oil.

Als Grundöl sind alle Öle der 5 Hauptgruppen gemäß des Klassifizierung des American Petroleum Institute (API) einsetzbar. Bevorzugt sind Mineralöle der API Gruppe III mit einer Viskosität von 32 oder 46 cSt bei 40°C (ISO Viskositätsklasse 32 oder 46).All oils from the 5 main groups according to the classification of the American Petroleum Institute (API) can be used as base oil . Mineral oils of API Group III with a viscosity of 32 or 46 cSt at 40°C (ISO viscosity class 32 or 46) are preferred.

Gegenstand der vorliegenden Erfindung ist zudem ein Verfahren zur Herstellung des erfindungsgemäßen Turbinenöls, wonach die erfindungsgemäße Additivmischung mit den Komponenten (a) bis (d) und gegebenenfalls (e) bis (g) bei Temperaturen zwischen 20 und 100 °C, vorzugsweise 40 - 80°C in ein Grundöl eingerührt werden.The present invention also relates to a process for producing the turbine oil according to the invention, according to which the additive mixture according to the invention with components (a) to (d) and optionally (e) to (g) at temperatures between 20 and 100 ° C, preferably 40 - 80 °C can be stirred into a base oil.

Als Rührer sind gängige Mischaggregate einsetzbar.Common mixing units can be used as stirrers.

Gegenstand der vorliegenden Erfindung ist zudem die Verwendung der erfindungsgemäßen Additivmischung, vorzugsweise in einem Grundöl, als Turbinenöl.The present invention also relates to the use of the additive mixture according to the invention, preferably in a base oil, as a turbine oil.

Das erfindungsgemäße Verfahren wird anhand der nachfolgenden Beispiele erläutert, ohne dabei auf diese beschränkt zu sein.The process according to the invention is explained using the following examples, without being limited to them.

BeispieleExamples Herstellung der Additivmischung:Preparation of the additive mixture:

Es wurden die in der Tabelle 1 genannten Verbindungen (a) bis (f) in den dort angegebenen Mengen (Gew.%) bei 70°C zusammengemischt bis eine homogene Lösung entstanden ist. Die Mischungen der Beispiele B bis D sind flüssig. Die Mischung aus Beispiel A (Vergleichsbeispiel nach EP-A 1730101 ) ist fest und kann daher nicht ohne vorheriges Schmelzen im Öl eingesetzt werden.The compounds (a) to (f) mentioned in Table 1 were mixed together in the amounts specified there (% by weight) at 70 ° C until a homogeneous solution was formed. The mixtures of Examples B to D are liquid. The mixture from example A (comparative example according to EP-A 1730101 ) is solid and therefore cannot be used in oil without first melting it.

Herstellung des Turbinenöls:Production of turbine oil:

Es wurden die zuvor hergestellten Additivmischungen in den in Tabelle 1 angegebenen Mengen (Gew.%) bei 70°C in Yubase, einem handelsüblichen mineralischen Grundöl der API Gruppe III der Firma SK lubricants Co. eingerührt. Tabelle 1: Beispiel A (V) [Gew.%] B [Gew.%] C (V) [Gew.%] D (V) [Gew.%] (a1) APAN der Formel (I) mit R1 = C10-C12-Alkyl, Anteil C12 =80 Gew% 0,27 0,27 0,27 (a2) APAN der Formel (I) mit R1 = C8-Alkyl 0,27 (b) Diphenylamin DPA der Formel (II) (zu 90 Gew.% mit C4, C8 substituiert) 0,09 0,09 0,09 0,09 (c) S-Verbindung d. Formel (III) = 2,5-Dimercapto-1,3,4-thiadiazol 0,015 0,015 0,039 - (e) Benzoltriazol der Formel (IV)* 0,024 0,024 - 0,06 (f) Korrosionsinhibitor der Formel (V) mit n=5,7 0,042 0,042 0,042 0,042 ASTM D 4636 Fest, nicht einsetzbar Bestanden Nicht bestanden Nicht bestanden Änderung der Säurezahl (mg KOH/g) +0,64 +0,04 +6,10 Änderung der Viskosität bei 40°C (cSt) +3,30 +1,0 +27,7 Al Gewichtsänderung (mg/cm2) 0,0 +0,01 0,00 Fe Gewichtsänderung (mg/cm2) +0,05 +0,04 0,00 Cu Gewichtsänderung (mg/cm2) +0,11 +0,87 0,00 Mg Gewichtsänderung, (mg/cm2) +0,02 0,00 -3,11 Cd Gewichtsänderung (mg/cm2) -0,02 +0,03 -17,29 Dry TOST gemäß ASTM D 7873 Bestanden RPVOT - 0 h (min) nach ASTM D 2272 2754 RPVOT - 1000 h (min) nach ASTM D 2272 800 (29%) Schlamm nach 1000 h (mg/kg) 65 V = Vergleichsbeispiel; RPVOT= Rotation Pressure Vessel Oxidation Test;
*Mischung aus N,N-bis(2-ethylhexyl)-methyl-1H-benzotriazol-1-methylamin mit methyl in Position 4,5 oder 6 und N,N-bis(2-ethylhexyl)-methyl-2H-benzotriazol-1-methylamin mit methyl in Position 4 oder 5 im Verhältnis 68 Gew.% (1H) zu 32 Gew.% (2H). The previously prepared additive mixtures were stirred into Yubase, a commercially available mineral base oil of API Group III from SK lubricants Co., at 70 ° C in the amounts (% by weight) given in Table 1. Table 1: Example A (V) [wt.%] B [wt.%] C (V) [wt.%] D (V) [wt.%] (a1) APAN of the formula (I) with R 1 = C 10 -C 12 alkyl, proportion C 12 =80% by weight 0.27 0.27 0.27 (a2) APAN of the formula (I) with R 1 = C 8 alkyl 0.27 (b) Diphenylamine DPA of the formula (II) (90% by weight substituted with C 4 , C 8 ) 0.09 0.09 0.09 0.09 (c) S-connection d. Formula (III) = 2,5-dimercapto-1,3,4-thiadiazole 0.015 0.015 0.039 - (e) Benzenetriazole of the formula (IV)* 0.024 0.024 - 0.06 (f) Corrosion inhibitor of formula (V) with n=5.7 0.042 0.042 0.042 0.042 ASTM D 4636 Fixed, not usable Passed Failed Failed Change in acid number (mg KOH/g) +0.64 +0.04 +6.10 Change in viscosity at 40°C (cSt) +3.30 +1.0 +27.7 Al weight change (mg/cm 2 ) 0.0 +0.01 0.00 Fe weight change (mg/cm 2 ) +0.05 +0.04 0.00 Cu weight change (mg/cm 2 ) +0.11 +0.87 0.00 Mg weight change, (mg/cm 2 ) +0.02 0.00 -3.11 Cd weight change (mg/cm 2 ) -0.02 +0.03 -17.29 Dry TOST according to ASTM D 7873 Passed RPVOT - 0 h (min) according to ASTM D 2272 2754 RPVOT - 1000 h (min) according to ASTM D 2272 800 (29%) Sludge after 1000 h (mg/kg) 65 V = comparative example; RPVOT= Rotation Pressure Vessel Oxidation Test;
*Mixture of N,N-bis(2-ethylhexyl)-methyl-1H-benzotriazole-1-methylamine with methyl in position 4,5 or 6 and N,N-bis(2-ethylhexyl)-methyl-2H-benzotriazole 1-methylamine with methyl in position 4 or 5 in a ratio of 68% by weight (1H) to 32% by weight (2H).

Ein Test nach ASTM D 4636 gilt für Turbinenöle als nicht bestanden, wenn die Gewichtsänderung eines der Metalle (Al, Fe, Cu, Mg oder Cd) größer als 0,25 mg/cm2 ist. Ein Test nach ASTM D 7873 gilt unter anderem als bestanden, wenn nach 1000 h die RPVOT-Zeit noch mindestens 25% der ursprünglichen RPVOT-Zeit beträgt und der Schlamm nach 1000 h unter 100 mg/kg liegt. Es wurden folgende Standard-Tests durchgeführt:
Der Dry TOST gemäß ASTM D 7873, als Standardtestverfahren zur Bestimmung der Oxidationsstabilität und der Bildung unlöslicher Stoffe von Turbinenölen bei 120°C ohne Einschluss von Wasser (Trocken-TOST-Methode) und der Oxidationstest nach ASTM D 4636.A test according to ASTM D 4636 is considered to have failed for turbine oils if the change in weight of one of the metals (Al, Fe, Cu, Mg or Cd) is greater than 0.25 mg/cm 2 . A test according to ASTM D 7873 is considered to have been passed, among other things, if after 1000 hours the RPVOT time is still at least 25% of the original RPVOT time and the sludge is below 100 mg/kg after 1000 hours. The following standard tests were carried out:
The Dry TOST according to ASTM D 7873, as a standard test method for determining the oxidation stability and the formation of insoluble substances of turbine oils at 120°C without the inclusion of water (dry TOST method) and the oxidation test according to ASTM D 4636.

Es wurde nun überraschend gefunden, dass die erfindungsgemäße Mischung aus den Komponenten (a) bis (d), siehe Beispiel 8, sowohl den Oxidationstest nach ASTM D 4636 und den Dry TOST gemäß ASTM D 7873 für Turbinenöle besteht und eine gute Löslichkeit in Öl aufweisen.It has now surprisingly been found that the mixture according to the invention of components (a) to (d), see Example 8, passes both the oxidation test according to ASTM D 4636 and the dry TOST according to ASTM D 7873 for turbine oils and has good solubility in oil .

Aus den Vergleichsbeispielen ist ersichtlich, dass diese Tests nicht erfüllt werden, sobald eine der Komponenten der erfindungsgemäßen Mischung fehlen, bzw. diese Mischung nicht ohne vorherige Aufarbeitung ins Öl gerührt werden kann, sofern als Komponente (a) ein kürzerkettiges (C8) APAN eingesetzt wird.It can be seen from the comparative examples that these tests are not fulfilled as soon as one of the components of the mixture according to the invention is missing, or this mixture cannot be stirred into the oil without prior processing, provided that a shorter-chain (C 8 ) APAN is used as component (a). becomes.

Claims (10)

  1. Additive mixture comprising
    (a) 35-90% by weight of one or more alkyl-substituted N-α-naphthyl-N-phenylamines of formula (I)
    Figure imgb0013
     where R1 = C10-C14 alkyl, preferably C10-C12 alkyl,
    (b) 0.1-40% by weight of one or more alkyl-substituted diphenylamines of formula (II)
    Figure imgb0014
     where R2 to R5 = independently of one another H, C4-C9 alkyl, preferably C4 or C8-C9 alkyl, with the proviso that at least one of the radicals R2 to R5 is a C8 or C9 alkyl radical,
    (c) 0.5-10% by weight of at least one sulfur-containing compound of formula (III)
    Figure imgb0015
     where R = C8-C12 alkyl, preferably C9H19,
    (d) 0.5-10% by weight of at least one benzotriazole of formula (IV)
    Figure imgb0016
     and 0-30% by weight of oil (e).
  2. Additive mixture according to Claim 1, characterized in that it comprises at least one corrosion inhibitor, preferably a carboxamide (f) of formula (V)
    Figure imgb0017
     where n = 4-10.
  3. Additive mixture according to either of Claims 1 and 2, characterized in that they comprise at least one thiophosphate (g) of formula (VI)
    Figure imgb0018
  4. Additive mixture according to any of Claims 1 to 3, characterized in that they comprise demulsifiers selected from the group of the polyglycols and/or defoamers selected from the group of the polyacrylates.
  5. Additive mixture according to any of Claims 1 to 4, characterized in that they comprise the following additives:
    50-70% by weight of at least one alkyl-substituted N-α-naphthyl-N-phenylamine (a),
    5-30% by weight of at least one alkyl-substituted diphenylamine (b),
    2.5-9% by weight of at least one sulfur-containing compound (c),
    4-9% by weight of at least one benzotriazole (d), 15-25% by weight of at least one oil (e),
    the sum total of all constituents (a) to (e) being 100% by weight.
  6. Additive mixture according to any of Claims 1 to 4, characterized in that they comprise the following additives:
    30-85% by weight, preferably 45-60% by weight, of at least one alkyl-substituted N-α-naphthyl-N-phenylamine (a),
    0.1-30% by weight, preferably 5-20% by weight, of at least one alkyl-substituted diphenylamine (b),
    0.5-5% by weight, preferably 2.5-4% by weight, of at least one sulfur-containing compound (c),
    0.5-8% by weight, preferably 4-6% by weight, of at least one benzotriazole (d),
    0-30% by weight, preferably 15-25% by weight, of at least one oil (e),
    5-15% by weight, preferably 7-10% by weight, of at least one carboxamide (f),
    0-5% by weight, preferably 1.5-3.5% by weight, of at least one thiophosphate (g),
    the sum total of constituents (a) to (g) being 100% by weight.
  7. Process for producing an additive mixture according to any of Claims 1 to 6, characterized in that components (a) to (d) and optionally (e) to (g) are mixed at temperatures of 20-100°C.
  8. Turbine oil comprising the additive mixture of Claims 1 to 6 in at least one base oil.
  9. Turbine oil according to Claim 8, characterized in that the proportion of the additive mixture in a base oil is 0.1-2% by weight, based on the total mixture.
  10. Use of an additive mixture according to any of Claims 1 to 6 in a turbine oil.
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EP4130207A1 (en) 2023-02-08

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