EP0406825A1 - Lubricant composition - Google Patents

Lubricant composition Download PDF

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Publication number
EP0406825A1
EP0406825A1 EP90112761A EP90112761A EP0406825A1 EP 0406825 A1 EP0406825 A1 EP 0406825A1 EP 90112761 A EP90112761 A EP 90112761A EP 90112761 A EP90112761 A EP 90112761A EP 0406825 A1 EP0406825 A1 EP 0406825A1
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EP
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Prior art keywords
hydrogen
alkyl
formula
composition according
benzyl
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EP90112761A
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German (de)
French (fr)
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EP0406825B1 (en
Inventor
Samuel Dr. Evans
Rolf Dr. Schumacher
Paul Dr. Dubs
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Novartis AG
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Ciba Geigy AG
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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
    • C10M133/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen
    • C10M133/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen having a carbon chain of less than 30 atoms
    • C10M133/38—Heterocyclic nitrogen compounds
    • C10M133/40—Six-membered ring 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
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/22—Heterocyclic nitrogen compounds
    • 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
    • C10M2215/221—Six-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
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/22—Heterocyclic nitrogen compounds
    • C10M2215/225—Heterocyclic nitrogen compounds the rings containing both nitrogen and oxygen
    • 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
    • C10M2215/225—Heterocyclic nitrogen compounds the rings containing both nitrogen and oxygen
    • C10M2215/226—Morpholines
    • 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
    • C10M2215/30—Heterocyclic compounds
    • 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
    • C10N2040/25—Internal-combustion engines
    • 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
    • C10N2040/25—Internal-combustion engines
    • C10N2040/251—Alcohol fueled engines
    • 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
    • C10N2040/25—Internal-combustion engines
    • C10N2040/255—Gasoline engines
    • 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
    • C10N2040/25—Internal-combustion engines
    • C10N2040/255—Gasoline engines
    • C10N2040/28—Rotary engines

Abstract

Lubricants can be stabilised against oxidation by the addition of a sterically hindered amine of the formula I <IMAGE> in which n is 1 or 2, R is hydrogen or methyl, R1 is hydrogen, C1-C12-alkyl, allyl, benzyl, -CO-R4, -OR5 or -O-CO-R6, R2 is hydrogen, C1-C12-alkyl, C5-C12-cycloalkyl, C2-C5-hydroxyalkyl or a group of the formula II <IMAGE> R3 is, if n is 1, hydrogen, C1-C18-alkyl, C5-C12-cycloalkyl, C2-C5-hydroxyalkyl, C3-C18-alkoxyalkyl or C4-C20-dialkylaminoalkyl and, if n is 2, is C2-C12-alkylene, 2-hydroxy-1,3-propylene or xylylene, and R4 is hydrogen, C1-C12-alkyl or phenyl.

Description

Die vorliegende Erfindung betrifft Schmierstoffzusammensetzungen, die gegen oxidativen Abbau stabilisiert sind. Die Stabilisierung erfolgt durch Zusatz eines sterisch gehinderten Amins von spezifischer Struktur.The present invention relates to lubricant compositions that are stabilized against oxidative degradation. Stabilization is achieved by adding a sterically hindered amine with a specific structure.

Es ist bekannt und üblich, zu Schmierstoffen auf Basis von Mineralölen oder synthetischen Oelen Zusatzstoffe zur Verbesserung ihrer Gebrauchs­eigenschaften zuzusetzen. Von besonderer Bedeutung sind Zusatzstoffe gegen oxidativen Abbau der Schmierstoffe, sogenannte Antioxidantien. Der oxidative Abbau von Schmierstoffen spielt vor allem bei Motorenölen eine grosse Rolle, da im Verbrennungsraum der Motoren hohe Temperaturen herrschen und neben Sauerstoff Stickoxide (NOx) vorhanden sind, welche als Oxidationskatalysatoren wirken.It is known and customary to add additives to lubricants based on mineral oils or synthetic oils to improve their performance properties. Additives against oxidative degradation of the lubricants, so-called antioxidants, are of particular importance. The oxidative degradation of lubricants plays a major role, especially in the case of engine oils, since the engine's combustion chamber has high temperatures and, in addition to oxygen, nitrogen oxides (NO x ) are present, which act as oxidation catalysts.

Als Antioxidantien für Schmierstoffe werden vor allem organische Schwe­fel- und Phosphorverbindungen verwendet, aber auch aromatische Amine und Phenole, insbesondere sterisch gehinderte Phenole (siehe z.B. Ullmanns Encyklopädie der technischen Chemie, 4. Auflage, Verlag Chemie, Band 20 (1981); Seite 541-43). Es wurden auch schon sterisch gehinderte Amine zur Stabilisierung von Schmierölen vorgeschlagen, z.B. in der US-A-4 069 199 oder der JP-A-85/28496.Organic antioxidants for lubricants are primarily organic sulfur and phosphorus compounds, but also aromatic amines and phenols, especially sterically hindered phenols (see, for example, Ullmanns Encyklopadie der Technische Chemie, 4th edition, Verlag Chemie, Volume 20 (1981); page 541- 43). Sterically hindered amines for stabilizing lubricating oils have also been proposed, e.g. in US-A-4 069 199 or JP-A-85/28496.

In der EP-A-356 677 werden Gemische von aromatischen Aminen und sterisch gehinderten Aminen als Antioxidantien für Schmierstoffe vorgeschlagen, wobei diesen Gemischen auch phenolische Antioxidantien zugesetzt werden können.EP-A-356 677 proposes mixtures of aromatic amines and sterically hindered amines as antioxidants for lubricants, it also being possible to add phenolic antioxidants to these mixtures.

Es wurde jetzt gefunden, dass sich bestimmte sterisch gehinderte Amine auch allein, d.h. in Abwesenheit eines aromatischen Amins oder eines phenolischen Antioxidans zur antioxidativen Stabilisierung von Schmier­stoffen besonders eignen.It has now been found that certain sterically hindered amines can also stand alone, i.e. particularly suitable for the antioxidative stabilization of lubricants in the absence of an aromatic amine or a phenolic antioxidant.

Die Erfindung betrifft eine Schmierstoffzusammensetzung, enthaltend
(A) ein mineralisches oder synthetisches Oel oder ein Gemisch solcher Oele und
(B) als antioxidativen Stabilisator ein sterisch gehindertes Amin der Formel I,

Figure imgb0001
worin n 1 oder 2 ist,
R Wasserstoff oder Methyl ist,
R₁ Wasserstoff, C₁-C₁₂-Alkyl, Allyl, Benzyl, -CO-R₄, -OR₅ oder -O-CO-R₆ bedeutet,
R₂ Wasserstoff, C₁-C₁₂-Alkyl, C₅-C₁₂-Cycloalkyl, C₂-C₅-Hydroxyalkyl oder eine Gruppe der Formel II bedeutet,
Figure imgb0002
 R₃, wenn n 1 ist, Wasserstoff, C₁-C₁₈-Alkyl, C₅-C₁₂-Cycloalkyl, C₂-C₅-Hydroxyalkyl, C₃-C₁₈-Alkoxyalkyl oder C₄-C₂₀-Dialkylaminoalkyl bedeutet,
und wenn n 2 ist, C₂-C₁₂-Alkylen, 2-Hydroxy-1,3-propylen oder Xylylen bedeutet,
R₄ Wasserstoff, C₁-C₁₂-Alkyl oder Phenyl bedeutet,
R₅ Wasserstoff, C₁-C₁₂-Alkyl, C₅-C₁₂-Cycloalkyl oder Benzyl bedeutet und
R₆ C₁-C₁₂-Alkyl, C₁-C₁₂-Alkoxy oder Phenyl bedeutet,
in Abwesenheit eines aromatischen Amins oder eines phenolischen Antioxidans.The invention relates to a lubricant composition containing
(A) a mineral or synthetic oil or a mixture of such oils and
(B) a sterically hindered amine of the formula I as antioxidative stabilizer,
Figure imgb0001
 where n is 1 or 2,
R is hydrogen or methyl,
R₁ is hydrogen, C₁-C₁₂-alkyl, allyl, benzyl, -CO-R₄, -OR₅ or -O-CO-R₆,
R₂ is hydrogen, C₁-C₁₂-alkyl, C₅-C₁₂-cycloalkyl, C₂-C₅-hydroxyalkyl or a group of the formula II,
Figure imgb0002
 R₃, when n is 1, is hydrogen, C₁-C₁₈-alkyl, C₅-C₁₂-cycloalkyl, C₂-C₅-hydroxyalkyl, C₃-C₁₈-alkoxyalkyl or C₄-C₂₀-dialkylaminoalkyl,
and when n is 2 is C₂-C₁₂ alkylene, 2-hydroxy-1,3-propylene or xylylene,
R₄ is hydrogen, C₁-C₁₂-alkyl or phenyl,
R₅ is hydrogen, C₁-C₁₂-alkyl, C₅-C₁₂-cycloalkyl or benzyl and
R₆ is C₁-C₁₂-alkyl, C₁-C₁₂-alkoxy or phenyl,
in the absence of an aromatic amine or a phenolic antioxidant.

Wenn R₁, R₃, R₄, R₅ oder R₆ C₁-C₁₂-Alkyl bedeuten, so kann dies lineares oder verzweigtes Alkyl sein, wie z.B. Methyl, Ethyl, Propyl, Isopropyl, Butyl, Isoamyl, Hexyl, Heptyl, Octyl, Nonyl, Decyl, Undecyl oder Dodecyl. R₃ als C₁-C₁₈-Alkyl kann darüber hinaus z.B. Tetradecyl, Hexadecyl oder Octadecyl sein. R₁, R₄, R₅ und R₆ als Alkyl sind vorzugsweise unverzweigtes C₁-C₄-Alkyl.If R₁, R₃, R₄, R₅ or R₆ are C₁-C₁₂-alkyl, this can be linear or branched alkyl, e.g. Methyl, ethyl, propyl, isopropyl, butyl, isoamyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl or dodecyl. R₃ as C₁-C₁₈ alkyl can also e.g. Tetradecyl, hexadecyl or octadecyl. R₁, R₄, R₅ and R₆ as alkyl are preferably unbranched C₁-C₄ alkyl.

Wenn R₂, R₃ oder R₅ C₅-C₁₂-Cycloalkyl bedeuten, so kann dies z.B. Cyclopentyl, Cyclohexyl, Methylcyclohexyl, Cyclooctyl oder Cyclododecyl sein, bevorzugt jedoch Cyclohexyl.If R₂, R₃ or R₅ are C₅-C₁₂-cycloalkyl, this can e.g. Cyclopentyl, cyclohexyl, methylcyclohexyl, cyclooctyl or cyclododecyl, but preferably cyclohexyl.

Wenn R₂ oder R₃ C₂-C₅-Hydroxyalkyl sind, so kann das z.B. 2-Hydroxyethyl, 2-Hydroxypropyl, 3-Hydroxypropyl oder 2-Hydroxybutyl sein, bevorzugt jedoch 2-Hydroxyethyl.If R₂ or R₃ are C₂-C₅-hydroxyalkyl, this can e.g. 2-Hydroxyethyl, 2-hydroxypropyl, 3-hydroxypropyl or 2-hydroxybutyl, but preferably 2-hydroxyethyl.

R₃ als C₃-C₁₈-Alkoxyalkyl kann z.B. 2-Methoxyethyl, 2-Ethoxyethyl, 3-Methoxypropyl, 3-Ethoxypropyl, 3-Isopropoxypropyl, 3-Butoxypropyl oder 3-Dodecyloxypropyl sein.R₃ as C₃-C₁₈ alkoxyalkyl can e.g. 2-methoxyethyl, 2-ethoxyethyl, 3-methoxypropyl, 3-ethoxypropyl, 3-isopropoxypropyl, 3-butoxypropyl or 3-dodecyloxypropyl.

R₃ als C₄-C₂₀-Dialkylaminoalkyl kann z.B. 2-Dimethylaminoethyl, 3-Dimethylaminopropyl, 3-Di(isopropyl)aminopropyl oder 3-Di(octyl)­aminopropyl sein.R₃ as C₄-C₂₀ dialkylaminoalkyl can e.g. 2-Dimethylaminoethyl, 3-dimethylaminopropyl, 3-di (isopropyl) aminopropyl or 3-di (octyl) aminopropyl.

R₆ als C₁-C₁₂-Alkoxy ist vorzugsweise C₁-C₄-Alkoxy, insbesondere Methoxy oder Ethoxy.R₆ as C₁-C₁₂ alkoxy is preferably C₁-C₄ alkoxy, especially methoxy or ethoxy.

R₃ als C₂-C₁₂-Alkylen kann linear oder verzweigt sein, wie z.B. Di-, Tri-, Tetra-, Hexa-, Octa-, Deca- und Dodecamethylen, 2,2-Dimethyl-­1,3-propylen oder 2,2-Dimethyl-4-methyl-hexamethylen.R₃ as C₂-C₁₂ alkylene can be linear or branched, e.g. Di-, tri-, tetra-, hexa-, octa-, deca- and dodecamethylene, 2,2-dimethyl-1,3-propylene or 2,2-dimethyl-4-methyl-hexamethylene.

Bevorzugt ist als Komponente (B) eine Verbindung der Formel I, worin n 1 oder 2 ist, R Wasserstoff ist, R₁ Wasserstoff, C₁-C₄-Alkyl, Allyl, Benzyl, Acetyl oder -OR₅ bedeutet, R₂ Wasserstoff, C₁-C₄-Alkyl oder eine Gruppe der Formel II ist, R₃, wenn n 1 ist, Wasserstoff, C₁-C₈-Alkyl oder C₃-C₁₀-Alkoxyalkyl bedeutet, und wenn n 2 ist, C₂-C₈-Alkylen bedeutet, und R₅ C₆-C₁₀-Alkyl, Cyclohexyl oder Benzyl bedeutet.Preferred as component (B) is a compound of the formula I in which n is 1 or 2, R is hydrogen, R₁ is hydrogen, C₁-C₄-alkyl, allyl, benzyl, acetyl or -OR₅, R₂ is hydrogen, C₁-C₄- Is alkyl or a group of the formula II, R₃ if n is 1, is hydrogen, C₁-C₈-alkyl or C₃-C₁ Alk-alkoxyalkyl and if n is 2, is C₂-C₈-alkylene, and R₅ C₆-C₁₀- Means alkyl, cyclohexyl or benzyl.

Besonders bevorzugt ist als Komponente (B) eine Verbindung der Formel I, worin n 1 oder 2 ist, R Wasserstoff ist, R₁ Wasserstoff, Methyl oder Acetyl bedeutet, R₂ Wasserstoff ist und R₃, wenn n 1 ist, Wasserstoff oder C₃-C₈-Alkoxyalkyl bedeutet, und wenn n 2 ist, C₂-C₆-Alkylen bedeutet.A particularly preferred component (B) is a compound of the formula I in which n is 1 or 2, R is hydrogen, R₁ is hydrogen, methyl or acetyl, R₂ is hydrogen and R₃, if n is 1, is hydrogen or C₃-C₈- Alkoxyalkyl means, and when n is 2, means C₂-C₆ alkylene.

Bevorzugt sind weiterhin als Komponente (B) die Verbindungen der Formel I, worin n 2 ist und R₃ C₂-C₆-Alkylen bedeutet.Also preferred as component (B) are the compounds of the formula I in which n is 2 and R₃ is C₂-C₆alkylene.

Die Verbindungen der Formel I sind bekannte Verbindungen die z.B. in den US-Patenten 3 684 765, 3 904 581 und 4 104 248 beschrieben sind. Sie werden als Lichtschutzmittel für organische Polymere verwendet.The compounds of formula I are known compounds which e.g. in U.S. Patents 3,684,765, 3,904,581 and 4,104,248. They are used as light stabilizers for organic polymers.

Beispiele für einzelne Verbindungen der Formel I sind:
2,2,6,6-Tetramethyl-4-butylaminopiperidin
2,2,6,6-Tetramethyl-4-octylaminopiperidin
2,2,6,6-Tetramethyl-4-cyclohexylaminopiperidin
2,2,6,6-Tetramethyl-4-(N-hydroxyethyl-butylamino)-piperidin
2,2,6,6-Tetramethyl-4-(3-methoxypropylamino)-piperidin
2,2,6,6-Tetramethyl-4-(3-dimethylaminopropylamino)-piperidin
Bis(2,2,6,6-tetramethylpiperidin-4-yl)amin
2,3,6-Trimethyl-2,6-diethyl-4-isopropylaminopiperidin
1,2,2,6,6-Pentamethyl-4-dodecylaminopiperidin
1,2,2,6,6-Pentamethyl-4-(N-methyl-dodecylamino)-piperidin
1-Acetyl-2,2,6,6-tetramethyl-4-butylaminopiperidin
1,2,3,6-Tetramethyl-2,6-diethyl-4-(3-ethoxypropylamino)-piperidin
1-Octyloxy-2,2,6,6-tetramethyl-4-hexylaminopiperidin
1-Cyclohexyloxy-2,2,6,6-tetramethyl-4-cyclohexylaminopiperidin
N,N′-Bis(2,2,6,6-tetramethylpiperidin-4-yl)-1,2-diaminoethan
N,N′-Bis(2,2,6,6-tetramethylpiperidin-4-yl)-hexamethylendiamin
N,N′-Bis(1,2,2,6,6-pentamethylpiperidin-4-yl)-hexamethylendiamin
N,N′-Bis( 1-acetyl-2,2,6,6-tetramethylpiperidin-4-yl)-hexamethylendiamin
N,N′-Bis(1-benzyl-2,2,6,6-tetramethylpiperidin-4-yl)-m-xylylendiamin
N,N′-Bis(1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl)-2-hydroxy-­1,3-diaminopropanExamples of individual compounds of the formula I are:
2,2,6,6-tetramethyl-4-butylaminopiperidine
2,2,6,6-tetramethyl-4-octylaminopiperidine
2,2,6,6-tetramethyl-4-cyclohexylaminopiperidine
2,2,6,6-tetramethyl-4- (N-hydroxyethylbutylamino) piperidine
2,2,6,6-tetramethyl-4- (3-methoxypropylamino) piperidine
2,2,6,6-tetramethyl-4- (3-dimethylaminopropylamino) piperidine
Bis (2,2,6,6-tetramethylpiperidin-4-yl) amine
2,3,6-trimethyl-2,6-diethyl-4-isopropylaminopiperidine
1,2,2,6,6-pentamethyl-4-dodecylaminopiperidine
1,2,2,6,6-pentamethyl-4- (N-methyldodecylamino) piperidine
1-acetyl-2,2,6,6-tetramethyl-4-butylaminopiperidine
1,2,3,6-tetramethyl-2,6-diethyl-4- (3-ethoxypropylamino) piperidine
1-octyloxy-2,2,6,6-tetramethyl-4-hexylaminopiperidine
1-cyclohexyloxy-2,2,6,6-tetramethyl-4-cyclohexylaminopiperidine
N, N'-bis (2,2,6,6-tetramethylpiperidin-4-yl) -1,2-diaminoethane
N, N'-bis (2,2,6,6-tetramethylpiperidin-4-yl) hexamethylene diamine
N, N'-bis (1,2,2,6,6-pentamethylpiperidin-4-yl) hexamethylene diamine
N, N'-bis (1-acetyl-2,2,6,6-tetramethylpiperidin-4-yl) hexamethylene diamine
N, N'-bis (1-benzyl-2,2,6,6-tetramethylpiperidin-4-yl) -m-xylylenediamine
N, N'-bis (1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl) -2-hydroxy-1,3-diaminopropane

Die Komponente (A) ist ein mineralisches oder synthetische Basisöl, wie es zur Bereitung von Schmierstoffen üblich ist. Synthetische Oele können z.B. Ester von Polycarbonsäuren oder von Polyolen sein, sie können aliphatische Polyester sein oder Poly-α-olefine, Silicone, Phosphor­säureester oder Polyalkylenglykole. Der Schmierstoff kann auch ein Fett auf Basis eines Oeles und eines Verdickungsmittels sein. Solche Schmier­stoffe sind z.B. in D. Klamann "Schmierstoffe und artverwandte Produkte", Verlag Chemie, Weinheim 1982, beschrieben.Component (A) is a mineral or synthetic base oil, as is common for the preparation of lubricants. Synthetic oils can e.g. Esters of polycarboxylic acids or of polyols, they can be aliphatic polyesters or poly-α-olefins, silicones, phosphoric acid esters or polyalkylene glycols. The lubricant can also be a grease based on an oil and a thickener. Such lubricants are e.g. described in D. Klamann "Lubricants and related products", Verlag Chemie, Weinheim 1982.

Die Komponente (B) wird dem Basisöl vorzugsweise in einer Menge von 0,05 bis 5, insbesondere 0,1 bis 2 Gew.-%, bezogen auf das Basisöl, zugesetzt. Der Zusatz kann direkt erfolgen oder man stellt zuerst eine konzentrierte Lösung von (B) im Oel oder in einem anderen Lösungsmittel her und setzt diese Lösung dem Oel zu.Component (B) is preferably added to the base oil in an amount of 0.05 to 5, in particular 0.1 to 2% by weight, based on the base oil. The addition can take place directly or a concentrated solution of (B) in the oil or in another solvent is first prepared and this solution is added to the oil.

Der Zusatz von (B) zum Basisöl bewirkt eine Stabilisierung gegen dessen oxidativen Abbau und bewirkt in Motorenölen eine Verminderung der Schlammbildung.The addition of (B) to the base oil stabilizes it against its oxidative degradation and reduces the formation of sludge in motor oils.

Die Schmiermittelzusammensetzung kann zusätzlich andere Additive enthalten, wie z.B. Phosphor-III-ester, Metalldesaktivatoren, Rostinhibitoren, Viskositätsindex-Verbesserer, Stockpunktserniedriger, Dispergiermittel, Tenside oder Verschleiss-schutz-Additive.The lubricant composition may additionally contain other additives such as e.g. Phosphorus III esters, metal deactivators, rust inhibitors, viscosity index improvers, pour point depressants, dispersants, surfactants or wear protection additives.

Beispiele für Phosphor-III-ester sind:
Triphenylphosphit, Decyl-diphenylphosphit, Phenyl-didecylphosphit, Tris-(nonylphenyl)-phosphit, Trilaurylphosphit, Trioctadecylphosphit, Distearyl-pentaerythritdiphosphit, Tris-(2,4-di-tert.butylphenyl)-­phosphit, Diisodecylpentaerythrit-diphosphit, Bis-(2,4-di-tert.butyl­phenyl)-pentaerythritdiphosphit , Tristearyl-sorbit-triphosphit, Tetrakis-(2,4-di-tert .butylphenyl)-4,4′-biphenylen-diphosphonit, Bis-(2,6-di-tert.butyl-4-methyl-phenyl)-pentaerythrit-diphosphit.Examples of phosphorus III esters are:
Triphenyl phosphite, decyl diphenyl phosphite, phenyl didecyl phosphite, tris- (nonylphenyl) phosphite, trilauryl phosphite, trioctadecyl phosphite, distearyl-pentaerythritol diphosphite, tris- (2,4-di-tert.butylphenyl) -phosphite, diisodechritol , 4-di-tert.butylphenyl) pentaerythritol diphosphite, tristearyl sorbitol triphosphite, tetrakis (2,4-di-tert. Butylphenyl) -4,4′-biphenylene diphosphonite, bis- (2,6-di- tert-butyl-4-methylphenyl) pentaerythritol diphosphite.

Beispiele für Metall-Desaktivatoren, z.B. für Kupfer, sind:
Triazole, Benztriazole und deren Derivate, Tolutriazole und deren Derivate, 2-Mercaptobenzthiazol, 2-Mercaptobenztriazol, 2,5-Dimercapto­benztriazol, 2,5-Dimercaptobenzthiadiazol, 5,5′-Methylenbisbenz­triazol, 4,5,6,7-Tetrahydrobenztriazol, Salicyliden-propylendiamin, Salicylaminoguanidin und dessen Salze.Examples of metal deactivators, for example for copper, are:
Triazoles, benzotriazoles and their derivatives, tolutriazoles and their derivatives, 2-mercaptobenzthiazole, 2-mercaptobenztriazole, 2,5-dimercaptobenztriazole, 2,5-dimercaptobenzthiadiazole, 5,5'-methylenebisbenzotriazole, 4,5,6,7-tetrahydrobenztriazole, salicylides -propylenediamine, salicylaminoguanidine and its salts.

Beispiele für Rost-Inhibitoren sind:

  • a) Organische Säuren, ihre Ester, Metallsalze und Anhydride, z.B.:
    N-Oleoyl-sarcosin, Sorbitan-mono-oleat, Blei-naphthenat, Alkenyl­bernsteinsäureanhydrid, z.B. Dodecenylbernsteinsäure-anhydrid, Alkenylbernsteinsäure-Teilester und -Teilamide, 4-Nonylphenoxy­essigsäure.
  • b) Stickstoffhaltige Verbindungen, z.B.:
    • I. Primäre, sekundäre oder tertiäre aliphatische oder cycloali­phatische Amine und Amin-Salze von organischen und anorganischen Säuren, z.B. öllösliche Alkylammoniumcarboxylate.
    • II. Heterocyclische Verbindungen, z.B.:
      Substituierte Imidazoline und Oxazoline.
  • c) Phosphorhaltige Verbindungen, z.B.:
    Aminsalze von Phosphorsäurepartialestern oder Phosphonsäurepartial­estern, Zinkdialkyldithiophosphate.
  • d) Schwefelhaltige Verbindungen, z.B.:
    Barium-dinonylnaphthalin-sulfonate, Calciumpetroleum-sulfonate.
Examples of rust inhibitors are:
  • a) Organic acids, their esters, metal salts and anhydrides, for example:
    N-oleoyl-sarcosine, sorbitan mono-oleate, lead naphthenate, alkenylsuccinic anhydride, for example dodecenylsuccinic anhydride, alkenylsuccinic acid partial esters and partial amides, 4-nonylphenoxyacetic acid.
  • b) nitrogen-containing compounds, for example:
    • I. Primary, secondary or tertiary aliphatic or cycloaliphatic amines and amine salts of organic and inorganic acids, for example oil-soluble alkylammonium carboxylates.
    • II. Heterocyclic compounds, for example:
      Substituted imidazolines and oxazolines.
  • c) phosphorus-containing compounds, for example:
    Amine salts of phosphoric acid partial esters or phosphonic acid partial esters, zinc dialkyldithiophosphates.
  • d) sulfur-containing compounds, for example:
    Barium dinonylnaphthalene sulfonates, calcium petroleum sulfonates.

Beispiele für Viskositätsindex-Verbesserer sind:
Polyacrylate, Polymethacrylate, Vinylpyrrolidon/methacrylat-Copolymere, Polyvinylpyrrolidone, Polybutene, Olefin-Copolymere, Styrol/Acrylat-­Copolymere, Polyether.Examples of viscosity index improvers are:
Polyacrylates, polymethacrylates, vinyl pyrrolidone / methacrylate copolymers, polyvinyl pyrrolidones, polybutenes, olefin copolymers, styrene / acrylate copolymers, polyethers.

Beispiele für Stockpunkterniedriger sind:
Polymethacrylat, alkylierte Naphthalinderivate.Examples of pour point depressants are:
Polymethacrylate, alkylated naphthalene derivatives.

Beispiele für Dispergiermittel/Tenside sind:
Polybutenylbernsteinsäureamide oder -imide, Polybutenylphosphon­säurederivate, basische Magnesium-, Calcium-, und Bariumsulfonate und -phenolate.Examples of dispersants / surfactants are:
Polybutenylsuccinic acid amides or imides, polybutenylphosphonic acid derivatives, basic magnesium, calcium and barium sulfonates and phenolates.

Beispiele für Verschleiss-schutz-Additive sind:
Schwefel und/oder Phosphor und/oder Halogen enthaltende Verbindungen, wie geschwefelte pflanzliche Oele, Zinkdialkyldithiophosphate, Tritolyl-phosphat, chlorierte Paraffine, Alkyl- und Aryldi- und tri-sulfide, Triphenylphosphorothionate, Diethanolaminomethyltolyl­triazol, Di(2-ethylhexyl)aminomethyltolyltriazol.Examples of wear protection additives are:
Compounds containing sulfur and / or phosphorus and / or halogen, such as sulfurized vegetable oils, zinc dialkyldithiophosphates, tritolyl phosphate, chlorinated paraffins, alkyl and aryl di- and tri-sulfides, triphenyl phosphorothionates, diethanolaminomethyltolyltriazole, di (2-ethyltylylolyl) aminol.

Der Schmierstoff kann auch feste Schmierstoffe enthalten, wie z.B. Graphit oder Molybdänsulfid.The lubricant can also contain solid lubricants, e.g. Graphite or molybdenum sulfide.

Die folgenden Beispiele erläutern die Erfindung näher. Darin bedeuten % Gewichts-%.The following examples illustrate the invention. Therein% means% by weight.

Beispiel 1:Example 1:

Mittels eines Differential-Scanning-Calorimeters (Thermoanalysator 1090 der Fa. Du Pont) wird die Induktionszeit der Oxidation von Oelproben durch Luft, die 400 ppm NO₂ enthält, unter isothermen Bedingungen gemessen. Die Messung geschieht bei 170°C unter einem Druck von 8 bar. Als Basisöl wird ein Standard-Mineralöl (Aral® 136) verwendet, dem 1 Vol-% 1-Decen zur Steigerung der Sauerstoffempfindlichkeit zugesetzt wird. Zum Oel werden die folgenden Amin-Stabilisatoren zugesetzt.

  • A-1 2,2,6,6-Tetramethyl-4-(3-methoxypropylamino)-piperidin
  • A-2 N,N′-Bis(2,2,6,6-tetramethylpiperidin-4-yl)-pentamethylendiamin
  • A-3 N,N′-Bis(2,2,6,6-tetramethylpiperidin-4-yl)-hexamethylendiamin
  • A-4 Bis(2,2,6,6-tetramethylpiperidin-4-yl)-amin
  • A-4 2,2,6,6-Tetramethyl-4-butylaminopiperidin
Using a differential scanning calorimeter (thermal analyzer 1090 from Du Pont), the induction time of the oxidation of oil samples by air containing 400 ppm NO₂ is measured under isothermal conditions. The measurement takes place at 170 ° C under a pressure of 8 bar. A standard mineral oil (Aral® 136) is used as the base oil, to which 1% by volume 1-decene is added to increase the sensitivity to oxygen. The following amine stabilizers are added to the oil.
  • A-1 2,2,6,6-tetramethyl-4- (3-methoxypropylamino) piperidine
  • A-2 N, N'-bis (2,2,6,6-tetramethylpiperidin-4-yl) pentamethylene diamine
  • A-3 N, N'-bis (2,2,6,6-tetramethylpiperidin-4-yl) hexamethylene diamine
  • A-4 bis (2,2,6,6-tetramethylpiperidin-4-yl) amine
  • A-4 2,2,6,6-tetramethyl-4-butylaminopiperidine

In Tabelle 1 sind die Induktionszeiten angegeben. Je höher die Induktionszeit ist, desto höher ist die antioxidative Wirkung des geprüften Stabilisators. Tabelle 1 Stabilisator Induktionszeit (min) 0,55 % A-1 72 0,55 % A-2 132 0,55 % A-3 107 0,55 % A-4 115 0,55 % A-5 77 ohne 35 Table 1 shows the induction times. The longer the induction time, the higher the antioxidant effect of the tested stabilizer. Table 1 stabilizer Induction time (min) 0.55% A-1 72 0.55% A-2 132 0.55% A-3 107 0.55% A-4 115 0.55% A-5 77 without 35

Claims (9)

1. Schmierstoffzusammensetzung, enthaltend
(A) ein mineralisches oder synthetisches Oel oder ein Gemisch solcher Oele und
(B) als antioxidativen Stabilisator ein sterisch gehindertes Amin der Formel I,
Figure imgb0003
 worin n 1 oder 2 ist,
R Wasserstoff oder Methyl ist,
R₁ Wasserstoff, C₁-C₁₂-Alkyl, Allyl, Benzyl, -CO-R₄, -OR₅ oder -O-CO-R₆ bedeutet,
R₂ Wasserstoff, C₁-C₁₂-Alkyl, C₅-C₁₂-Cycloalkyl, C₂-C₅-Hydroxyalkyl oder eine Gruppe der Formel II bedeutet,
Figure imgb0004
 R₃, wenn n 1 ist, Wasserstoff, C₁-C₁₈-Alkyl, C₅-C₁₂-Cycloalkyl, C₂-C₅-Hydroxyalkyl, C₃-C₁₈-Alkoxyalkyl oder C₄-C₂₀-Dialkylaminoalkyl bedeutet,
und wenn n 2 ist, C₂-C₁₂-Alkylen, 2-Hydroxy-1,3-propylen oder Xylylen bedeutet,
R₄ Wasserstoff, C₁-C₁₂-Alkyl oder Phenyl bedeutet,
R₅ Wasserstoff, C₁-C₁₂-Alkyl, C₅-C₁₂-Cycloalkyl oder Benzyl bedeutet und
R₆ C₁-C₁₂-Alkyl, C₁-C₁₂-Alkoxy oder Phenyl bedeutet,
in Abwesenheit eines aromatischen Amins und eines phenolischen Anti­oxidans.1. Lubricant composition containing
(A) a mineral or synthetic oil or a mixture of such oils and
(B) a sterically hindered amine of the formula I as antioxidative stabilizer,
Figure imgb0003
 where n is 1 or 2,
R is hydrogen or methyl,
R₁ is hydrogen, C₁-C₁₂-alkyl, allyl, benzyl, -CO-R₄, -OR₅ or -O-CO-R₆,
R₂ is hydrogen, C₁-C₁₂-alkyl, C₅-C₁₂-cycloalkyl, C₂-C₅-hydroxyalkyl or a group of the formula II,
Figure imgb0004
 R₃, when n is 1, is hydrogen, C₁-C₁₈-alkyl, C₅-C₁₂-cycloalkyl, C₂-C₅-hydroxyalkyl, C₃-C₁₈-alkoxyalkyl or C₄-C₂₀-dialkylaminoalkyl,
and when n is 2 is C₂-C₁₂ alkylene, 2-hydroxy-1,3-propylene or xylylene,
R₄ is hydrogen, C₁-C₁₂-alkyl or phenyl,
R₅ is hydrogen, C₁-C₁₂-alkyl, C₅-C₁₂-cycloalkyl or benzyl and
R₆ is C₁-C₁₂-alkyl, C₁-C₁₂-alkoxy or phenyl,
in the absence of an aromatic amine and a phenolic antioxidant. 2. Zusammensetzung gemäss Anspruch 1, worin (B) eine Verbindung der Formel I ist, worin n 1 oder 2 ist, R Wasserstoff ist, R₁ Wasserstoff, C₁-C₄-Alkyl, Allyl, Benzyl, Acetyl oder -OR5 bedeutet, R₂ Wasserstoff, C₁-C₄-Alkyl oder eine Gruppe der Formel II bedeutet, R₃, wenn n 1 ist, Wasserstoff, C₁-C₈-Alkyl oder C₃-C₁₀-Alkoxyalkyl bedeutet, und wenn n 2 ist, C₂-C₈-Alkylen bedeutet, und R₅ C₆-C₁₀-Alkyl, Cyclohexyl oder Benzyl bedeutet.2. Composition according to claim 1, wherein (B) is a compound of formula I, wherein n is 1 or 2, R is hydrogen, R₁ is hydrogen, C₁-C₄-alkyl, allyl, benzyl, acetyl or -OR5, R₂ is hydrogen , C₁-C₄-alkyl or a group of formula II means R₃, if n is 1, is hydrogen, C₁-C₈-alkyl or C₃-C₁₀-alkoxyalkyl, and if n is 2, is C₂-C₈-alkylene, and R₅ is C₆-C₁₀-alkyl, cyclohexyl or benzyl. 3. Zusammensetzung gemäss Anspruch 1, worin (B) eine Verbindung der Formel I ist, worin n 1 oder 2 ist, R Wasserstoff ist, R₁ Wasserstoff, Methyl oder Acetyl bedeutet, R₂ Wasserstoff ist und R₃, wenn n 1 ist, Wasserstoff oder C₃-C₈-Alkoxyalkyl bedeutet, und wenn n 2 ist, C₂-C₆-­Alkylen bedeutet.3. Composition according to claim 1, wherein (B) is a compound of formula I, wherein n is 1 or 2, R is hydrogen, R₁ is hydrogen, methyl or acetyl, R₂ is hydrogen and R₃, if n is 1, is hydrogen or C₃-C₈-alkoxyalkyl means, and when n is 2, means C₂-C₆-alkylene. 4. Zusammensetzung gemäss Anspruch 3, worin (B) eine Verbindung der Formel I ist, worin n 2 ist und R₃ C₂-C₆-Alkylen bedeutet.4. The composition according to claim 3, wherein (B) is a compound of formula I, wherein n is 2 and R₃ is C₂-C₆ alkylene. 5. Zusammensetzung gemäss Anspruch 4, worin (B) die Verbindung N,N′-Bis(2,2,6,6-tetramethylpiperidin-4-yl)-hexamethylendiamin ist.5. The composition according to claim 4, wherein (B) is the compound N, N'-bis (2,2,6,6-tetramethylpiperidin-4-yl) hexamethylene diamine. 6. Zusammensetzung gemäss Anspruch 1, enthaltend 0,1 bis 2 Gew.-% (B), bezogen auf (A).6. The composition according to claim 1, containing 0.1 to 2 wt .-% (B), based on (A). 7. Verwendung einer Zusammensetzung gemäss Anspruch 1 als Motorenöl.7. Use of a composition according to claim 1 as motor oil. 8. Verwendung von Verbindungen der Formel I, gemäss Definition in Anspruch 1, zum Stabilisieren von Schmierstoffen gegen deren oxidativen Abbau, wobei die Schmierstoffe kein aromatisches Amin und kein phenolisches Antioxidans enthalten.8. Use of compounds of formula I, as defined in claim 1, for stabilizing lubricants against their oxidative degradation, the lubricants containing no aromatic amine and no phenolic antioxidant. 9. Verwendung gemäss Anspruch 8 zur Verminderung der Schlammbildung in Motorenölen.9. Use according to claim 8 for reducing sludge formation in motor oils.
EP90112761A 1989-07-07 1990-07-04 Lubricant composition Expired - Lifetime EP0406825B1 (en)

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EP3066179B1 (en) 2013-11-04 2019-02-27 Basf Se Lubricant composition

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