EP4130207A1 - Additive mixture for turbine oils - Google Patents

Additive mixture for turbine oils Download PDF

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Publication number
EP4130207A1
EP4130207A1 EP21189406.8A EP21189406A EP4130207A1 EP 4130207 A1 EP4130207 A1 EP 4130207A1 EP 21189406 A EP21189406 A EP 21189406A EP 4130207 A1 EP4130207 A1 EP 4130207A1
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Prior art keywords
weight
alkyl
additive mixture
oil
formula
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EP21189406.8A
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German (de)
French (fr)
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EP4130207B1 (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 PCT/EP2022/069130 priority patent/WO2023011855A1/en
Priority to KR1020247003684A priority patent/KR20240040074A/en
Priority to CA3227567A priority patent/CA3227567A1/en
Priority to TW111128759A priority patent/TW202328416A/en
Publication of EP4130207A1 publication Critical patent/EP4130207A1/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 at high operating temperatures over a longer period of time.
  • a suitable general purpose turbine oil exhibits a number of desirable properties to address various operating conditions in 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 release properties, improved rust and/or corrosion resistance and improved air release and foaming properties.
  • VIP viscosity index
  • oxidation stability and associated long service life
  • low varnish/sludge formation good water release properties
  • improved rust and/or corrosion resistance improved air release and foaming properties.
  • additives for turbine oils which contain nonyl- or dinonyl or styrene-substituted Na-naphthyl-N-phenylamine and nonyl- or dinonyl or styrene-substituted diphenylamine as antioxidants.
  • octyl-Na-naphthyl-N-phenylamines are increasingly used, individually or in combination with various additives, such as US-A 5726135 , these having 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-phenylamines and diphenylamines as well as sulfur-containing additives as further components.
  • Sulfur-containing compounds are known to improve oxidation stability in lubricants, as evidenced by results from the Rotation Pressure Vessel Oxidation Test (RPVOT, ASTM D 7727) and ASTM D 4636 Oxidation Corrosion Test. Examples can also be found in WO2019/183187 .
  • many sulphur-containing compounds tend to form sludge, which has a negative impact the results of other oxidation tests such as e.g. B. the dry TOST according to ASTM D 7873 affects.
  • 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, with this turbine oil meeting the requirements of the oxidation test according to ASTM D 7873 and 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.
  • carboxylic acid amides preferably amides of carboxylic acids having 4-50 carbon atoms, such as, for example, N-oleylsarcosine or succinic acid amides, can be used as corrosion inhibitors (f) .
  • the additive mixture contains at least one thiophosphate (g).
  • thiophosphate (g) For the purposes of the invention, neutral, covalently bonded thiophosphates and also ionic thiophosphates such as amine-neutralized thiophosphoric acid derivatives can be used as thiophosphate (g) .
  • 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 preparing the additive mixture according to the invention, according to which components (a) to (d) and optionally (e) to (g) are mixed in any order at temperatures from 20 to 100° C., preferably 60-80° C to be mixed. These are preferably stirred until a homogeneous liquid is obtained.
  • the subject matter of the present invention is also a turbine oil containing the additive mixture according to the invention, preferably at 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) is heated at temperatures between 20 and 100° C., preferably 40-80 °C are stirred into a base oil.
  • the subject matter of the present invention is also the use of the additive mixture according to the invention, preferably in a base oil, as a turbine oil.
  • the compounds (a) to (f) specified in Table 1 were mixed together in the amounts (% by weight) specified there 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 the oil without first melting it.
  • Turbine oils fail a test according to ASTM D 4636 if the weight change 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 passed if, after 1000 h, the RPVOT time is at least 25% of the original RPVOT time and the sludge is below 100 mg/kg after 1000 h.
  • 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 inclusion of water (dry TOST method) and the oxidation test according to ASTM D 4636.

Abstract

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.

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 at high operating temperatures over a longer period of time.

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 general purpose turbine oil exhibits a number of desirable properties to address various operating conditions in 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 release properties, improved rust and/or corrosion resistance and improved air release and foaming properties.

Aus EP-A 1730101 sind beispielsweise Additive für Turbinenöle bekannt, die als Antioxidantien Nonyl- bzw- Dinonyl, bzw. Styrol-subsituierte N-a-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 Na-naphthyl-N-phenylamine and nonyl- or dinonyl or styrene-substituted diphenylamine as antioxidants.

Insbesondere octylsubstituierte N-a-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-Na-naphthyl-N-phenylamines are increasingly used, individually or in combination with various additives, such as US-A 5726135 , these having 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 7727) 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-phenylamines and diphenylamines as well as sulfur-containing additives as further components. Sulfur-containing compounds are known to improve oxidation stability in lubricants, as evidenced by results from the Rotation Pressure Vessel Oxidation Test (RPVOT, ASTM D 7727) and ASTM D 4636 Oxidation Corrosion Test. Examples can also be found in WO2019/183187 . At the same time, however, many sulphur-containing compounds tend to form sludge, which has a negative impact the results of other oxidation tests such as e.g. B. the dry TOST according to ASTM D 7873 affects.

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, with this turbine oil meeting the requirements of the oxidation test according to ASTM D 7873 and the corrosion and oxidation test according to ASTM D 4636 .

Lösung der Aufgabesolution of 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. Surprisingly, it has now 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) ein oder mehrere alkylsubstituierte N-a-Naphthyl-N-phenylamine (APAN) der Formel (I)
    Figure imgb0001
     mit R1 = C10―C14- Alkyl, vorzugsweise C10―C12-Alkyl,
  2. (b) ein oder mehrere alkylsubstituierte 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) mindestens eine schwefelhaltige Verbindung der Formel (III)
    Figure imgb0003
     und R = C8 - C12- Alkyl, vorzugsweise C9H19
    und
  4. (d) mindestens ein Benzotriazol der Formel (IV)
    Figure imgb0004
     in (e) gegebenenfalls einem Öl.
  • 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.
  • 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.
  • Komponente (c): Bei den schwefelhaltigen Verbindungen (c) im Sinne der Erfindung handelt es sich vorzugsweise um Cg - Alkyl-substituiertes-2,5, Dimercapto-1,3,4-Thiadiazol. 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.
  • 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.
  • Komponente (f): In einer bevorzugten Ausführungsform der Erfindung enthält die Additivmischung mindestens einen Korrosionsinhibitor, besonders bevorzugt ein Carbonsäureamid (f).
The present invention relates to an additive mixture containing
  1. (a) one or more alkyl-substituted Na-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) one or more alkyl-substituted diphenylamines (DPA) of formula (II)
    Figure imgb0002
     with R 2 to R 5 = independently of one another 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) at least one sulfur-containing compound of formula (III)
    Figure imgb0003
     and R = C 8 - C 12 - alkyl, preferably C 9 H 19
    and
  4. (d) at least one benzotriazole of formula (IV)
    Figure imgb0004
     in (e) optionally an oil.
  • Component (a): The C 10 -C 14 - alkyl-substituted N-α-naphthyl-N-phenylamines (APAN) (a) for the purposes 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 -C 12 -alkyl, particularly preferably C 12 - are alkyl. The preferred position of the radical R 1 is in the p-position.
  • Component (b): In the context of the invention, the alkyl-substituted diphenylamines (DPA) (b) are preferably a mixture of compounds of the formula (II) in which the total of the radicals R 2 -R 5 is one, two or three C 4 - or C 8 -alkyl radicals correspond. 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.
  • Component (c): The sulfur-containing compounds (c) for the purposes of the invention are preferably Cg-alkyl-substituted-2,5,dimercapto-1,3,4-thiadiazole. Component (d): The benzotriazole (d) according to the invention is preferably N,N-bis(2-ethylhexyl)methyl-1H-benzotriazole-1-methylamine with methyl in position 4, 5 or 6 and/or 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 sense of the invention. There is no particular limitation on the kind of mineral oil or synthetic oil. In general, however, a mineral oil or a synthetic oil having 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.
  • Component (f): In a preferred embodiment of the invention, the additive mixture contains at least one corrosion inhibitor, particularly preferably a carboxylic acid amide (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.
Bevorzugt sind Carbonsäureamide (f) der Formel (V)

Figure imgb0005
mit n = 4-10, vorzugsweise 5-7.For the purposes of the invention, carboxylic acid amides, preferably amides of carboxylic acids having 4-50 carbon atoms, such as, for example, N-oleylsarcosine or succinic acid amides, can be used as corrosion inhibitors (f) .
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.For the purposes of the invention, neutral, covalently bonded thiophosphates and also ionic thiophosphates such as amine-neutralized thiophosphoric acid derivatives can be used as thiophosphate (g) .

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:

  • 35 - 90 Gew.%, vorzugsweise 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)
  • 0,5 - 10 Gew.%, vorzugsweise 2,5 - 9 Gew.% mindestens einer schwefelhaltigen Verbindung (c),
  • 0,5 - 10 Gew.%, vorzugsweise 4 - 9 Gew.%, mindestens eines Benzotriazols (d) und
  • 0 - 30 Gew.%, vorzugsweise 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):
  • 35-90% by weight, preferably 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)
  • 0.5-10% by weight, preferably 2.5-9% by weight, of at least one sulfur-containing compound (c),
  • 0.5-10% by weight, preferably 4-9% by weight, of at least one benzotriazole (d) and
  • 0-30% by weight, preferably 15-25% by weight, of at least one oil(s),
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 Korrosionsschutzadditivs, vorzugsweise 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(s),
  • 5-15% by weight, preferably 7-10% by weight, of at least one anti-corrosion additive, preferably a 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 preparing the additive mixture according to the invention, according to which components (a) to (d) and optionally (e) to (g) are mixed in any order at temperatures from 20 to 100° C., preferably 60-80° C to be mixed. These are preferably stirred until a homogeneous liquid is obtained.

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 subject matter of the present invention is also a turbine oil containing the additive mixture according to the invention, preferably at 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 . API Group III mineral oils 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) is heated at temperatures between 20 and 100° C., preferably 40-80 °C are 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 subject matter of the present invention is also 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 examples below, without being restricted to these.

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) specified in Table 1 were mixed together in the amounts (% by weight) specified there 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 the oil without first melting it.

Herstellung des Turbinenöls:Production of the 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) B C (V) D (V) [Gew.%] [Gew.%] [Gew.%] [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., in the amounts (% by weight) given in Table 1 at 70.degree. Table 1: Example A (V) B C (V) D (V) [% by weight] [% by weight] [% by weight] [% by weight] (a1) APAN of the formula (I) with R 1 = C 10 -C 12 -alkyl, proportion of C 12 = 80% by weight 0.27 0.27 0.27 (a2) APAN of 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 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) per 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 the ratio 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 (AI, 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.Turbine oils fail a test according to ASTM D 4636 if the weight change 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 passed if, after 1000 h, the RPVOT time is at least 25% of the original RPVOT time and the sludge is below 100 mg/kg after 1000 h. 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 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 B, 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.Surprisingly, it has now been found that the mixture of components (a) to (d) according to the invention, see Example B, passes both the ASTM D 4636 oxidation test and the ASTM D 7873 dry TOST 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.From the comparative examples it can be seen that these tests are not met 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 work-up if a shorter-chain (C 8 ) APAN is used as component (a). becomes.

Claims (10)

Additivmischung enthaltend (a) ein oder mehrere alkyl-substituierte N-a-Naphthyl-N-phenylamine der Formel (I)
Figure imgb0007
 mit R1 = C10―C14- Alkyl, vorzugsweise C10―C12-Alkyl, (b) ein oder mehrere alkyl-substituierte Diphenylamine der Formel (II)
Figure imgb0008
 mit R2 bis R5 = unabhängig voneinander H, C4 - C9-Alkyl, vorzugsweise C4- oder C8 - C9-Alkyl, mit der Maßgabe, dass mindestens einer der Reste R2 bis R5 ein C8- oder C9-Alkyl-Rest ist, (c) mindestens eine schwefelhaltige Verbindung der Formel (III)
Figure imgb0009
 mit R = C8 -C12- Alkyl, vorzugsweise C9H19, (d) mindestens ein Benzotriazol der Formel (IV)
Figure imgb0010
 und gegebenenfalls Öl (e). containing additive mixture (a) one or more alkyl-substituted Na-naphthyl-N-phenylamines of formula (I)
Figure imgb0007
 with R 1 = C 10 -C 14 -alkyl, preferably C 10 -C 12 -alkyl, (b) one or more alkyl-substituted diphenylamines of formula (II)
Figure imgb0008
 with R 2 to R 5 = independently of one another H, C 4 - C 9 -alkyl, preferably C 4 - or C 8 - C 9 -alkyl, with the proviso that at least one of the radicals R 2 to R 5 is a C 8 - or C 9 -alkyl radical, (c) at least one sulfur-containing compound of formula (III)
Figure imgb0009
 with R = C 8 -C 12 - alkyl, preferably C 9 H 19 , (d) at least one benzotriazole of formula (IV)
Figure imgb0010
 and optionally oil (s). Additivmischung nach Anspruch, dadurch gekennzeichnet, dass diese mindestens einen Korrosionsinhibitor, vorzugsweise ein Carbonsäureamid (f) der Formel (V)
Figure imgb0011
 mit n = 4-10, enthält.Additive mixture according to claim, characterized in that this at least one corrosion inhibitor, preferably a carboxamide (f) of the formula (V)
Figure imgb0011
 with n = 4-10. Additivmischung nach einem der Ansprüche 1 bis 2, dadurch gekennzeichnet, dass diese mindestens ein Thiophosphat (g) der Formel (VI)
Figure imgb0012
 enthalten.Additive mixture according to one of Claims 1 to 2, characterized in that this contains at least one thiophosphate (g) of the formula (VI)
Figure imgb0012
 contain. Additivmischung nach einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, dass diese Demulgatoren ausgewählt aus der Gruppe der Polyglykole und/oder Entschäumer ausgewählt aus der Gruppe der Polyacrylate enthalten.Additive mixture according to one of Claims 1 to 3, characterized in that these contain demulsifiers selected from the group of polyglycols and/or defoamers selected from the group of polyacrylates. Additivmischung nach einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, dass diese folgende Additive aufweisen: 35 - 90 Gew.%, vorzugsweise 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), 0,5 - 10 Gew.%, vorzugsweise 2,5 - 9 Gew.% mindestens einer schwefelhaltigen Verbindung (c), 0,5 - 10 Gew.%, vorzugsweise 4 - 9 Gew.% mindestens eines Benzotriazols (d), 0 - 30 Gew.%, vorzugsweise 15 - 25 Gew.% mindestens eines Öls (e), wobei die Summe aller Bestandteile (a) bis (e) 100 Gew.% beträgt.Additive mixture according to one of claims 1 to 4, characterized in that they have the following additives: 35-90% by weight, preferably 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), 0.5-10% by weight, preferably 2.5-9% by weight, of at least one sulfur-containing compound (c), 0.5-10% by weight, preferably 4-9% by weight, of at least one benzotriazole (d), 0-30% by weight, preferably 15-25% by weight, of at least one oil(s), where the sum of all components (a) to (e) is 100% by weight. Additivmischung nach einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, dass diese folgende Additive aufweisen: 30 - 85 Gew.%, vorzugsweise 45 - 60 Gew.% mindestens eines alkylsubstitutierten N-α-Naphthyl-N-phenylamins (a), 0,1 - 30 Gew.%, vorzugsweise 5 - 20 Gew.% mindestens eines alkylsubstitutierten 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 Korrosionsschutzadditivs, vorzugsweise 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.Additive mixture according to one of claims 1 to 4, characterized in that they have 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(s), 5-15% by weight, preferably 7-10% by weight, of at least one anti-corrosion additive, preferably a 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. Verfahren zur Herstellung einer Additivmischung nach einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, dass die Komponenten (a) bis (d) und gegebenenfalls (e) bis (g) bei Temperaturen von 20 - 100°C gemischt werden.Process for producing an additive mixture according to one of Claims 1 to 4, characterized in that components (a) to (d) and optionally (e) to (g) are mixed at temperatures of 20 - 100°C. Turbinenöl enthaltend die Additivmischung der Ansprüche 1 bis 6 in mindestens einem Grundöl.Turbine oil containing the additive mixture of Claims 1 to 6 in at least one base oil. Turbinenöl gemäß Anspruch 7, dadurch gekennzeichnet, dass der Anteil der Additivmischung 0,1 - 2 Gew.%, bezogen auf die Gesamtmischung, in einem Grundöl beträgt.Turbine oil according to Claim 7, characterized in that the proportion of the additive mixture is 0.1-2% by weight, based on the total mixture, in a base oil. Verwendung einer Additivmischung nach einem der Ansprüche 1 bis 6 in einem Turbinenöl.Use of an additive mixture according to any one of Claims 1 to 6 in a turbine oil.
EP21189406.8A 2021-08-03 2021-08-03 Additive mixture for turbine oils Active EP4130207B1 (en)

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EP21189406.8A EP4130207B1 (en) 2021-08-03 2021-08-03 Additive mixture for turbine oils
PCT/EP2022/069130 WO2023011855A1 (en) 2021-08-03 2022-07-08 Novel additive mixture
KR1020247003684A KR20240040074A (en) 2021-08-03 2022-07-08 New additive mixture
CA3227567A CA3227567A1 (en) 2021-08-03 2022-07-08 New additive mixture
TW111128759A TW202328416A (en) 2021-08-03 2022-08-01 New additive mixture

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Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5726135A (en) 1996-12-11 1998-03-10 Khorramian; Behrooz A. Phosphorus-free and ashless oil for aircraft and turbo engine application
EP1730101A1 (en) 2004-04-01 2006-12-13 CIBA SPECIALTY CHEMICALS HOLDING INC. Patent Departement Alkylated pana and dpa compositions
EP2307535A1 (en) 2008-07-14 2011-04-13 Chemtura Corporation Liquid additives for the stabilization of lubricant compositions
US20160068781A1 (en) * 2014-09-04 2016-03-10 Vanderbilt Chemicals, Llc Liquid ashless antioxidant additive for lubricating compositions
CN109135894A (en) * 2018-10-09 2019-01-04 中国石油化工股份有限公司 Turbine oil composition and application thereof
WO2019183187A1 (en) 2018-03-20 2019-09-26 Basf Se Lubricant composition
EP3712235A1 (en) 2019-03-20 2020-09-23 Basf Se Lubricant composition

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5726135A (en) 1996-12-11 1998-03-10 Khorramian; Behrooz A. Phosphorus-free and ashless oil for aircraft and turbo engine application
EP1730101A1 (en) 2004-04-01 2006-12-13 CIBA SPECIALTY CHEMICALS HOLDING INC. Patent Departement Alkylated pana and dpa compositions
EP2307535A1 (en) 2008-07-14 2011-04-13 Chemtura Corporation Liquid additives for the stabilization of lubricant compositions
US20160068781A1 (en) * 2014-09-04 2016-03-10 Vanderbilt Chemicals, Llc Liquid ashless antioxidant additive for lubricating compositions
WO2019183187A1 (en) 2018-03-20 2019-09-26 Basf Se Lubricant composition
CN109135894A (en) * 2018-10-09 2019-01-04 中国石油化工股份有限公司 Turbine oil composition and application thereof
EP3712235A1 (en) 2019-03-20 2020-09-23 Basf Se Lubricant composition

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Title
DATABASE WPI Week 201917, Derwent World Patents Index; AN 2019-054679, XP002805218 *

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