WO2008015116A2

WO2008015116A2 - Lubricant composition

Info

Publication number: WO2008015116A2
Application number: PCT/EP2007/057552
Authority: WO
Inventors: David Eliezer Chasan; Patricia Roberta Wilson; Marc Ribeaud
Original assignee: Ciba Holding Inc.
Priority date: 2006-07-31
Filing date: 2007-07-23
Publication date: 2008-02-07
Also published as: KR20090033358A; CN101495605A; JP5546858B2; IL196250A; BRPI0714961A2; MX2009001124A; PL2049630T3; CA2657382C; CA2657382A1; EP2049630B1; AU2007280548B2; IL196250A0; CN101495605B; BRPI0714961B1; RU2009106723A; RU2462505C2; KR101433140B1; JP2014139313A; AU2007280548A1; WO2008015116A3

Abstract

Certain NH sterically hindered amine compounds of the formula where R is a straight or branched alkyl group of from 7 to 17 carbon atoms and where n is a numeral from 6 to 18 are suitable for use as stabilizers in lubricant compositions. The sterically hindered amines are non-aggressive towards fluoroelastomer O-rings or seals.

Description

Lubricant Composition

The present invention relates to lubricant compositions stabilized against oxidative degradation via the incorporation of certain sterically hindered amine stabilizers. The lubricant compositions exhibit excellent results regarding seal swell. U.S. Pat. Nos. 5,073,278 and 5,273,669 teach the stabilization of lubricant compositions with a certain aromatic amine and at least one sterically hindered amine.

U.S. Pat. No. 5,268, 113 discloses lubricants stabilized by the addition of a sterically hindered amine and a phenol.

It is known to add stabilizers to lubricants based on mineral or synthetic oils in order to im- prove their performance characteristics. Antioxidants are of particular importance. Oxidative degradation of lubricants plays a significant role especially in motor oils because of the high temperatures prevailing in the combustion chambers of the engines and the presence, in addition to oxygen, of oxides of nitrogen which act as oxidation catalysts.

Hindered amine compounds are effective stabilizers for lubricants. However, they are gener- ally not employed due to detrimental effects such as seal swell.

The present invention relates to the stabilization of lubricant compositions with a specific class of hindered amine compounds. The present lubricant compositions are non-aggressive towards seals.

The present invention relates to a stabilized lubricant composition which comprises A mineral or a synthetic base oil or a mixture of a mineral and a synthetic base oil; and At least one sterically hindered amine compound of the formula

HN (H),

where R is a straight or branched alkyl group of from 7 to 17 carbon atoms and n is a numeral from 6 to 18.

The alkyl group R is linear or branched and consist of for example 7, 8, 9, 10, 1 1 , 12, 13, 14, 15, 16 or 17 carbons. The numeral n is for example 6, 8, 10, 12, 14, 16 or 18.

The sterically hindered amines are known and are prepared according to methods known in the art. For example, the present hindered amines are 2,2,6,6-tetramethylpiperidin-4-ol esters of aliphatic carboxylic acids, for example the esters of lauric acid or stearic acid.

According to a preferred embodiment, the invention relates to compositions wherein the hindered amines of the formula

are present.

Lubricants according to the present invention are functional fluids, that is lubricants, hydraulic fluids or metal working fluids.

Lubricants are in particular mineral oil based (API classifications Groups I, II, III, Group IV including gas to liquid (GTL) oils) or synthetic base oils, such as is normally used for the production of lubricants. Synthetic oils may be, for example, esters of polycarboxylic acids or of polyols; they may also be aliphatic polyesters or poly-α-olefins, silicones, phosphoric acid esters or polalkylene glycols. The lubricant may also be a grease based on an oil and a thickener. Such lubricants are described, for example in D. Klamann "Schmierstoffe und art- verwandte Producte", Verlag Chemie, Weinheim, 1982.

Examples are lubricants and hydraulic fluids based on mineral oil or synthetic lubricants or hydraulic fluids, in particular those which are derivatives of carboxylic esters and which are used at temperatures of 200⁰C and above. Examples of synthetic lubricants embrace lubricants based on a diester of a dibasic acid with a monovalent alcohol, for example dioctyl sebacate or dinonyl adipate, a triester of trimethy- lolpropane with a monobasic acid or a mixture of such acids, for example trimethylolpropane tripelargonate, trimethylolpropane tricaprylate or mixtures of these, a tetraester of pentae- rythritol with a monobasic acid or with a mixture of such acids, for example pentaerythritol tetracaprylate, or a complex ester of monobasic and dibasic acids with polyhydric alcohols, for example a complex ester of trimethylolpropane with caprylic and sebacic acid or a mixture of these.

Particularly suitable are, besides mineral oils, for example poly-α-olefins, lubricants based on esters, or phosphates, glycols, polyglycols and polalkyene glycols and mixtures of these with water.

The sterically hindered amines of this invention are in particular non-aggressive toward elastomeric seals.

The seals are in particular a fluoropolymer elastomer used in O-rings and other goods. The "fluoroelastomers" are categorized under ASTM D1418 and ISO 1629 designation of FKM for example. The fluoroelastomers comprise copolymers of hexafluoropropylene (HFP) and vi- nylidene fluoride (VDF of VF2), terpolymers of tetrafluoroethylene (TFE), vinylidene fluoride and hexafluoropropylene, perfluoromethylvinylether (PMVE), copolymers of TFE and propylene and copolymers of TFE, PMVE and ethylene. The fluorine content varies for example between about 66 to about 70% by weight.

FKM is fluoro rubber of the polymethylene type having substituent fluoro and perflouroalkyl or perfluoroalkoxy groups on the polymer chain.

Accordingly, a preferred subject of the invention is a stabilized lubricant composition which is in contact with a fluoroelastomer and which comprises A mineral or a synthetic base oil or a mixture of a mineral and a synthetic base oil and At least one sterically hindered amine compounds of the formula (I) or (II), where R is a straight or branched alkyl group of from 7 to 17 carbon atoms and n is a numeral from 6 to 18.

The sterically hindered amines according to this invention are admixed with the lubricants in an amount of about 0.01 to about 5% by weight, for example from about 0.05 to about 3% by weight, for instance from about 0.1 to about 2% by weight, based on the weight of the lubricant. - A -

The lubricants can additionally comprise other additives which are added to improve the basic properties of lubricants even further; these include antioxidants, metal passivators, rust inhibitors, viscosity index improvers, pour point depressors, dispersants, detergents, high pressure additives, antifriction additives and antiwear additives. These additional additives are for example:

1. Antioxidants

1.1. Alkylated monophenols, for example 2,6-di-tert-butyl-4-methylphenol, 2-tert-butyl -4,6- dimethylphenol, 2,6-di-tert-butyl-4-ethylphenol, 2,6-di-tert-butyl-4-n-butylphenol, 2,6-di-tert- butyl-4-isobutylphenol, 2,6-dicyclopentyl-4-methylphenol, 2-(α-methylcyclohexyl)-4,6-dimeth- ylphenol, 2,6-dioctadecyl-4-methylphenol, 2,4,6-tricyclohexylphenol, 2,6-di-tert-butyl-4-meth- oxymethylphenol, 2,6-di-nonyl-4-methylphenol, 2,4-dimethyl -6(1'-methylundec-1 '-yl)phenol, 2,4-dimethyl-6-(1 '-methylheptadec-1 '-yl)phenol, 2,4-dimethyl-6-(1 '-methyltridec-1 '-yl)phenol and mixtures thereof.

1.2. Alkylthiomethylphenols, for example 2,4-dioctylthiomethyl-6-tert-butylphenol, 2,4-dioc- tylthiomethyl-6-methylphenol, 2,4-dioctylthiomethyl-6-ethylphenol, 2,6-didodecylthiomethyl-4- nonylphenol.

1.3. Hydroquinones and alkylated hydroquinones, for example 2,6-di-tert-butyl-4-methoxy- phenol, 2,5-di-tert-butylhydroquinone, 2,5-di-tert-amylhydroquinone, 2,6-diphenyl-4-octade- cyloxyphenol, 2,6-di-tert-butylhydroquinone, 2,5-di-tert-butyl-4-hydroxyanisole, 3,5-di-tert- butyl-4-hydroxyanisole, 3,5-di-tert-butyl-4-hydroxyphenyl stearate, bis-(3 , 5-d i-tert-buty l-4-hy- droxyphenyl) adipate.

1.4. Hydroxylated thiodiphenyl ethers, for example 2,2'-thiobis(6-tert-butyl-4-methylphenol), 2,2'-thiobis(4-octylphenol), 4,4'-thiobis(6-tert-butyl-3-methylphenol), 4,4'-thiobis(6-tert-butyl-2- methylphenol), 4,4'-thiobis-(3,6-di-sec-amylphenol), 4,4'-bis-(2,6-dimethyl-4-hydroxyphenyl) disulfide.

1.5. Alkylidenebisphenols, for example 2,2'-methylenebis(6-tert-butyl-4-methylphenol), 2,2'- methylenebis(6-tert-butyl-4-ethylphenol), 2,2'-methylenebis[4-methyl-6-(α-methylcyclo- hexyl)phenol], 2,2'-methylenebis(4-methyl-6-cyclohexylphenol), 2,2'-methylenebis(6-nonyl-4- methylphenol), 2,2'-methylenebis(4,6-di-tert-butylphenol), 2,2'-ethylidenebis (4,6-di-tert-butyl- phenol), 2,2'-ethylidenebis(6-tert-butyl-4-isobutylphenol), 2,2'-methylenebis [6-(α-methylben- zyl)-4-nonylphenol], 2,2'-methylenebis[6-(α,α-dimethylbenzyl) -4-nonylphenol], 4,4'-methyle- nebis(2,6-di-tert-butylphenol), 4,4'-methylenebis(6-tert-butyl-2-methylphenol),1 ,1-bis(5-tert- butyl-4-hydr oxy-2-methylphenyl)butane, 2,6-bis(3-tert-butyl-5-methyl-2-hydroxybenzyl)-4- methylphenol, 1 ,1 ,3-tris(5-tert-butyl-4-hydroxy -2-methylphenyl)butane, 1 ,1-bis(5-tert-butyl-4- hydroxy-2-methyl-phenyl)-3-n-dodecylmercaptobutane, ethylene glycol bis[3,3-bis(3'-tert-bu- tyl-4'-hydroxyphenyl)butyrate], bis(3-tert-butyl-4-hydroxy-5-methyl-phenyl)dicyclopentadiene, bis[2-(3'-tert-butyl -2'-hydroxy-5'-methylbenzyl) -6-tert-butyl-4-methylphenyl]terephthalate, 1 ,1-bis-(3,5-dimethyl-2-hydroxyphenyl)butane, 2,2-bis-( 3,5-di-tert-butyl-4-hydroxy- phenyl)propane, 2,2-bis-(5-tert-butyl-4-hydroxy2-methylphenyl)-4-n-dodecylmercaptobutane, 1 ,1 ,5,5-tetra-(5-tert -butyl-4-hydroxy2-methylphenyl)pentane.

1.6. O-, N- and S-benzyl compounds, for example 3,5,3',5'-tetra-tert-butyl-4,4'-dihydroxy- dibenzyl ether, octadecyl-4-hydroxy-3,5-dimethylbenzylmercaptoacetate, tris-(3,5-di-tert -bu- tyl-4-hydroxybenzyl)amine, bis(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)dithioterephthalate, bis(3,5-di-tert-butyl-4-hydroxybenzyl)sulfide, isooctyl-3,5di-tert-butyl-4-hydroxybenzylmer- captoacetate.

1.7. Hydroxybenzylated malonates, for example dioctadecyl-2,2-bis-(3,5-di-tert-butyl-2-hy- droxybenzyl)-malonate, di-octadecyl-2-(3-tert-butyl-4-hydroxy-5-methylbenzyl)-malonate, di- dodecylmercaptoethyl-2,2-bis-(3,5-di-tert-butyl-4-hydroxybenzyl)malonat e, bis [4-(1 , 1 ,3,3- tetramethylbutyl)phenyl]-2,2-bis(3,5-di-tert-butyl-4-hydroxybe nzyl)malonate. 1.8. Aromatic hydroxybenzyl compounds, for example 1 ,3,5-tris-(3,5-di-tert-butyl-4-hydroxy- benzyl)-2,4,6-trimethylbenzene, 1 ,4-bis(3,5-di-tert-butyl-4-hydroxybenzyl)-2,3,5,6-tetrame- thylbenzene, 2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)phenol. 1.9. Triazine Compounds, for example 2,4-bis(octylmercapto)-6-(3,5-di-tert-butyl-4-hy- droxyanilino)-1 ,3,5-triazine, 2-octylmercapto-4,6-bis(3,5-di-tert-butyl-4-hydroxyanilino) -1 ,3,5- triazine, 2-octylmercapto-4,6-bis(3,5-di-tert-butyl-4-hydroxyphenoxy) -1 ,3,5-triazine, 2,4,6- tris(3,5-di-tert-butyl-4-hydroxyphenoxy)-1 ,2,3-triazine, 1 ,3,5-tris(3,5-di-tert-butyl-4-hydroxy- benzyl)isocyanurate, 1 ,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl 2,4,6-tris(3,5-di-tert- butyl-4-hydroxyphenylethyl)-1 ,3,5-triazine, 1 ,3,5-tris(3,5-di-tert-butyl-4-hydroxyphenylpropio- nyl)-hexahydro-1 ,3,5-triazine, 1 ,3,5-tris(3,5-dicyclohexyl-4-hydroxybenzyl)isocyanurate. 1.10. Benzylphosphonates, for example dimethyl-2,5-di-tert-butyl-4-hydroxybenzylphospho- nate, diethyl-3,5-di-tert-butyl-4-hydroxybenzylphosphonate, dioctadecyl3,5-di-tert-butyl -A- hydroxybenzylphosphonate, dioctadecyl-δ-tert-butyM-hydroxyS-methylbenzylphosphonate, the calcium salt of the monoethyl ester of 3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid.

1.1 1. Acylaminophenols, for example 4-hydroxylauranilide, 4-hydroxystearanilide, octyl N- (3,5-di-tert-butyl-4-hydroxyphenyl)carbamate.

1.12. Esters of [3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid with mono- or polyhydric alcohols, e.g. with methanol, ethanol, octadecanol, 1 ,6-hexanediol, 1 ,9-nonanediol, ethylene glycol, 1 ,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl) isocyanurate, N,N'-bis(hydroxyethyl)oxamide, 3-thi- aundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl- 1-phospha-2,6,7-trioxabicyclo[2.2.2]octane. 1.13. Esters of β-(5-tert-butyl-4-hydroxy-3-methylphenyl)propionic acid with mono- or polyhy- dric alcohols, e.g. with methanol, ethanol, octadecanol, 1 ,6-hexanediol, 1 ,9-nonanediol, ethylene glycol, 1 ,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl) isocyanurate, N, N'- bis(hydroxyethyl)oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.

1.14 Esters of IS-^δ-dicyclohexyM-hydroxyphenyOpropionic acid with mono- or polyhydric alcohols, e.g. with methanol, ethanol, octadecanol, 1 ,6-hexanediol, 1 ,9-nonanediol, ethylene glycol, 1 ,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl) isocyanurate, N,N'-bis(hydroxyethyl)oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl- 1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.

1.15 Esters of 3,5-di-tert-butyl-4-hydroxyphenyl acetic acid with mono- or polyhydric alcohols, e.g. with methanol, ethanol, octadecanol, 1 ,6-hexanediol, 1 ,9-nonanediol, ethylene glycol, 1 ,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl) isocyanurate, N,N'-bis(hydroxyethyl)oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1- phospha-2,6,7-trioxabicyclo[2.2.2]octane. 1.16. Amides of β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid e.g. N,N'-bis(3,5-di-tert- butyl-4-hydroxyphenylpropionyl)hexamethylenediamine, N,N'-bis(3,5-di-tert-butyl -4-hydroxy- phenylpropionyl)trimethylenediamine, N,N'-bis(3,5-di-tert-butyl-4-hydroxyphenylpropio- nyl)hydrazine. Aminic antioxidants: N,N'-diisopropyl-p-phenylenediamine, N,N'-di-sec-butyl-p-phenylenediamine, N,N'-bis (1 ,4- dimethylpentyl)-p-phenylenediamine, N,N'-bis(1-ethyl-3-methylpentyl)-p-phenylenediamine, N,N'-bis(1-methylheptyl)-p-phenylenediamine, N,N'-dicyclohexyl-p-phenylenediamine, N, N'- diphenyl-p-phenylenediamine, N,N'-bis(2-naphthyl)-p-phenylenediamine, N-isopropyl-N'- phenyl-p-phenylenediamine, N-(1 ,3-dimethyl-butyl)-N'-phenyl-p-phenylenediamine, N-(1- methylheptyl)-N'-phenyl-p-phenylenediamine, N-cyclohexyl-N'-phenyl-p-phenylenediamine, 4-(p-toluenesulfamoyl)diphenylamine, N,N'-dimethyl-N,N'-di-sec-butyl-p-phenylenediamine, diphenylamine, N-allyldiphenylamine, 4-isopropoxydiphenylamine, N-phenyl-1-naphthyl- amine, N-phenyl-2-naphthylamine, octylated diphenylamine, for example p , p'-d i-tert-octy Id i- phenylamine, 4-n-butylaminophenol, 4-butyrylaminophenol, 4-nonanoylaminophenol, 4-do- decanoylaminophenol, 4-octadecanoylaminophenol, bis(4-methoxyphenyl)amine, 2,6-di-tert- butyl-4-dimethylaminomethylphenol, 2,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl- methane, N,N,N',N'-tetramethyl -4,4'-diaminodiphenylmethane, 1 ,2-bis[(2-methyl- phenyl)amino]ethane, 1 ,2-bis(phenylamino)propane, (o-tolyl)biguanide, bis[4-(1 ',3'-dimethyl- butyl)phenyl]amine, tert-octylated N-phenyl-1-naphthylamine, a mixture of mono- and dialky- lated tert-butyl/tert-octyldiphenylamines, a mixture of mono- and dialkylated isopro- pyl/isohexyldiphenylamines, mixtures of mono- and dialkylated tert-butyldiphenylamines, 2,3- dihydro-3,3-dimethyl -4H-1 ,4-benzothiazine, phenothiazine, N-allylphenothiazine, N, N, N', N'- tetraphenyl -1 ,4-diaminobut-2-ene, N,N-bis(2,2,6,6-tetramethylpiperid-4-yl-hexamethyl- enediamine, bis(2,2,6,6 -tetramethylpiperid-4-yl)sebacate, 2,2,6,6-tetramethylpiperidin-4-one and 2,2,6,6-tetramethylpiperidin-4-ol. Examples of other antioxidants: Aliphatic or aromatic phosphites, esters of thiodipropionic acid or of thiodiacetic acid, or salts of dithiocarbamic or dithiophosphoric acid, 2,2,12,12-tetramethyl-5,9-dihydroxy -3,7,1 1 - trithiatridecane and 2,2,15,15- tetramethyl-5,12-dihydroxy-3,7,10,14-tetrathiahexadecane. Examples of metal deactivators, for example for copper, are: a) Benzotriazoles and derivatives thereof, for example 4- or 5-alkylbenzotriazoles (e.g. tolu- triazole) and derivatives thereof, 4,5,6,7-tetrahydrobenzotriazole and 5,5'-methylenebisben- zotriazole; Mannich bases of benzotriazole or tolutriazole, e.g. 1-[bis(2-ethyl- hexyl)aminomethyl)tolutriazole and 1-[bis(2-ethylhexyl)aminomethyl)benzotriazole; and alkoxyalkylbenzotriazoles such as 1-(nonyloxymethyl)benzotriazole, 1-(1 -bu- toxyethyl)benzotriazole and 1 -(1 -cyclohexyloxybuty^tolutriazole. b) 1 ,2,4-Triazoles and derivatives thereof, for example 3-alkyl(or aryl)-1 ,2,4-triazoles, and Mannich bases of 1 ,2,4-triazoles, such as 1-[bis(2-ethylhexyl)aminomethyl -1 ,2,4-triazole; alkoxyalkyl-1 ,2,4-triazoles such as 1-(1-butoxyethyl)-1 ,2,4-triazole; and acylated 3-amino- 1 ,2,4-triazoles. c) Imidazole derivatives, for example 4,4'-methylenebis(2-undecyl-5-methylimidazole) and bis[(N-methyl)imidazol-2-yl]carbinol octyl ether. d) Sulfur-containing heterocyclic compounds, for example 2-mercaptobenzothiazole, 2,5- dimercapto-1 ,3,4-thiadiazole and derivatives thereof; and 3,5-bis[di(2-ethyl- hexyl)aminomethyl]-1 ,3,4-thiadiazolin-2-one. e) Amino compounds, for example salicylidenepropylenediamine, salicylaminoguanidine and salts thereof.

Examples of rust inhibitors and friction modifiers are: a) Organic acids, their esters, metal salts, amine salts and anhydrides, for example alkyl- and alkenylsuccinic acids and their partial esters with alcohols, diols or hydroxycarboxylic acids, partial amides of alkyl- and alkenylsuccinic acids, 4-nonylphenoxyacetic acid, alkoxy- and alkoxyethoxycarboxylic acids such as dodecyloxyacetic acid, dodecyloxy(ethoxy)acetic acid and the amine salts thereof, and also N-oleoylsarcosine, sorbitan monooleate, lead naphthenate, alkenylsuccinic anhydrides, for example dodecenylsuccinic anhydride, 2-car- boxymethyl-1-dodecyl-3-methylglycerol and the amine salts thereof. 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, and also 1-[N, N- bis(2-hydroxyethyl)amino]-3-(4-nonylphenoxy)propan-2-ol.

II. Heterocyclic compounds, for example: substituted imidazolines and oxazolines, and 2- heptadecenyl-1-(2-hydroxyethyl)imidazoline. c) Phosphorus-containing compounds, for example: Amine salts of phosphoric acid partial esters or phosphonic acid partial esters, and zinc dialkyldithiophosphat.es. d) Molybdenum- containing compounds, such as Molydbenum dithiocarbamate and other sulphur and phosphorus containing derivatives e) Sulfur-containing compounds, for example: barium dinonylnaphthalenesulfonat.es, calcium petroleum sulfonates, alkylthio-substituted aliphatic carboxylic acids, esters of aliphatic 2- sulfocarboxylic acids and salts thereof. f) Glycerol derivatives, for example: glycerol monooleate, 1-(alkylphenoxy)-3-(2-hy- droxyethyl)glycerols, 1-(alkylphenoxy)-3-(2,3-dihydroxypropyl)glycerols and 2-carboxyalkyl- 1 ,3-dialkylglycerols.

Examples of viscosity index improvers are: Polyacrylates, polymethacrylates, vinylpyrrolidone/methacrylate copolymers, polyvinylpyrrolidones, polybutenes, olefin copolymers, styrene/acrylate copolymers and polyethers. Examples of pour-point depressants are: Polymethacrylate and alkylated naphthalene derivatives. Examples of dispersants/surfactants are: Polybutenylsuccinic amides or -imides, polybutenylphosphonic acid derivatives and basic magnesium, calcium and barium sulfonates and phenolates. Examples of antiwear additives are:

Sulfur- and/or phosphorus- and/or halogen-containing compounds, e.g. sulfurised olefins and vegetable oils, zinc dialkyldithiophosphat.es, alkylated triphenyl phosphates, tritolyl phos- phate, tricresyl phosphate, chlorinated paraffins, alkyl and aryl di- and trisulfides, amine salts of mono- and dialkyl phosphates, amine salts of methylphosphonic acid, diethanolami- nomethyltolyltriazole, bis(2-ethylhexyl)aminomethyltolyltriazole, derivatives of 2,5-dimer- capto-1 ,3,4-thiadiazole, ethyl 3-[(diisopropoxyphosphinothioyl)thio]propionate, triphenyl thio- phosphate (triphenylphosphorothioate), tris(alkylphenyl) phosphorothioate and mixtures thereof (for example tris(isononylphenyl) phosphorothioate), diphenyl monononylphenyl phosphorothioate, isobutylphenyl diphenyl phosphorothioate, the dodecylamine salt of 3-hy- droxy-1 ,3-thiaphosphetane 3-oxide, trithiophosphoric acid 5,5,5-tris[isooctyl 2-acetate], derivatives of 2-mercaptobenzothiazole such as 1-[N,N-bis (2-ethylhexyl)aminomethyl]-2-mer- capto-1 H-1 ,3-benzothiazole, and ethoxycarbonyl-5-octyldithiocarbamate. The examples which follow illustrate the invention in greater detail. Parts and percentages are by weight, unless otherwise indicated.

Example

The superiority of the claimed sterically hindered amines over other similar sterically hindered amine additives is illustrated by the following example. A 5W-30 engine oil containing 0.08 %P is supplemented with sufficient sterically hindered amine additive to raise the total base number, as measured by ASTM D 4739 by two units. Amine additive A is added at a treat level of 1.0 weight percent and amine additive B is added at a treat level of 1.2%. The oils are stirred at 6O⁰C for one hour to insure homogeneity. The formulations are tested according to elastomer compatibility procedure CEC- L-39-T-96. The results of the CEC- L-39- T-96 testing of these formulations with an FKM fluorinated rubber are found below. Both amines affected the rubber elastomer.

1 2 3

Material wt% wt% wt%

Base formulation 100 99.0 98.8

Amine A 0 1.0 0

Amine B 0 0 1.2

Results

FKM rubber ACEA Spec

Hardness [DIDC, points] -1 3 0 -1/+5

Tensile strength [%] -17 -51 -33 -40/+ 10

Elongation at rupture [%] -29 -75 -55 -5-/+ 10

Volume variation [%] 0.7 1.1 1.1 -1/+5

The magnitude of the effect of amine A on tensile strength and elongation at rupture made it totally unsuitable for use relative to specifications such as that of ACEA. Amine B has much less of an effect on the fluorinated rubber - indicating it is suitable for use in engine oils. Amine Ais

Claims

1. A stabilized lubricant composition which comprises

A mineral or a synthetic base oil or a mixture of a mineral and a synthetic base oil and At least one sterically hindered amine compounds of the formula

2. A composition according to claim 1 where R is a straight or branched alkyl group of 1 1 or 17 carbon atoms and n is a numeral from 6 or 8.

3. A compositon according to claim 1 where the hindered amine is of the formula (I).

4. A composition according to claim 1 where the hindered amine is of the formula (II).

5. A composition according to claim 1 where the hindered amine is of the formula

6. A stabilized lubricant composition according to claim 1 where the hindered amine is of the formula

7. A composition according to claim 1 where the hindered amine is present from about 0.01 to about 5% by weight, based on the weight of the lubricant.

8. A composition according to claim 1 where the hindered amine is present from about 0.05 to about 3% by weight, based on the weight of the lubricant.

9. A composition according to claim 1 where the hindered amine is present from about 0.1 to about 2% by weight, based on the weight of the lubricant.

10. A stabilized lubricant composition which is in contact with a fluoroelastomer and which comprises At least one mineral or a synthetic base oil or a mixture of a mineral and a synthetic base oil and

At least one or more sterically hindered amine compounds of the formula (I) or (II), where R is a straight or branched alkyl group of from 7 to 17 carbon atoms and n is a numeral from 6 to 18.