CA2657382C - Lubricant compositions comprising tetramethylpiperidines - Google Patents
Lubricant compositions comprising tetramethylpiperidines Download PDFInfo
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- CA2657382C CA2657382C CA2657382A CA2657382A CA2657382C CA 2657382 C CA2657382 C CA 2657382C CA 2657382 A CA2657382 A CA 2657382A CA 2657382 A CA2657382 A CA 2657382A CA 2657382 C CA2657382 C CA 2657382C
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Classifications
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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
- C10M133/04—Amines, e.g. polyalkylene polyamines; Quaternary amines
- C10M133/06—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to acyclic or cycloaliphatic carbon atoms
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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
- C10M3/00—Liquid compositions essentially based on lubricating components other than mineral lubricating oils or fatty oils and their use as lubricants; Use as lubricants of single liquid substances
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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
- C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2215/02—Amines, e.g. polyalkylene polyamines; Quaternary amines
- C10M2215/04—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to acyclic or cycloaliphatic carbon atoms
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- 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
- C10N2030/36—Seal compatibility, e.g. with rubber
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/20—Metal working
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Chemistry (AREA)
- Lubricants (AREA)
- Anti-Oxidant Or Stabilizer Compositions (AREA)
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
= - CA 02657382 2014-02-18 29052-6 .
, LUBRICANT COMPOSITIONS COMPRISING TETRAMETHYLPIPERIDINES
The present invention relates to lubricant compositions stabilized against oxidative degrada-tion via the incorporation of certain sterically hindered amine stabilizers.
The lubricant com-positions 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 ad-dition 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 0)L R
---¨ (I) or )L
(ID, ---) _ where R is a straight or branched alkyl group of from 7 to 17 carbon atoms and n is a nu-meral from 6 to 18.
The alkyl group R is linear or branched and consist of for example 7, 8, 9, 10, 11, 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 es-ters 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 hin-dered amines of the formula HN 0)L C11H23 Or K(CH2)8/\
HN 0 0¨Cc!..\____IFI----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, Ill, Group IV in-cluding gas to liquid (GTL) oils) or synthetic base oils, such as is normally used for the pro-duction of lubricants. Synthetic oils may be, for example, esters of polycarboxylic acids or of polyols; they may also be aliphatic polyesters or poly-a-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 200 C and above.
, LUBRICANT COMPOSITIONS COMPRISING TETRAMETHYLPIPERIDINES
The present invention relates to lubricant compositions stabilized against oxidative degrada-tion via the incorporation of certain sterically hindered amine stabilizers.
The lubricant com-positions 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 ad-dition 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 0)L R
---¨ (I) or )L
(ID, ---) _ where R is a straight or branched alkyl group of from 7 to 17 carbon atoms and n is a nu-meral from 6 to 18.
The alkyl group R is linear or branched and consist of for example 7, 8, 9, 10, 11, 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 es-ters 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 hin-dered amines of the formula HN 0)L C11H23 Or K(CH2)8/\
HN 0 0¨Cc!..\____IFI----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, Ill, Group IV in-cluding gas to liquid (GTL) oils) or synthetic base oils, such as is normally used for the pro-duction of lubricants. Synthetic oils may be, for example, esters of polycarboxylic acids or of polyols; they may also be aliphatic polyesters or poly-a-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 200 C 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-a-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 0-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 propyl-ene 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 nu-meral 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 lubri-cant.
Particularly suitable are, besides mineral oils, for example poly-a-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 0-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 propyl-ene 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 nu-meral 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 lubri-cant.
The lubricants can additionally comprise other additives which are added to improve the ba-sic 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-dicyclopenty1-4-methylphenol, 2-(a-methylcyclohexyl)-4,6-dimeth-ylphenol, 2,6-dioctadecy1-4-methylphenol, 2,4,6-tricyclohexylphenol, 2,6-di-tert-butyl-4-meth-oxymethylphenol, 2,6-di-nony1-4-methylphenol, 2,4-dimethyl -6(11-methylundec-11-yl)phenol, 2,4-dimethy1-6-(11-methylheptadec-11-y1)phenol, 2,4-dimethy1-6-(11-methyltridec-11-yl)phenol and mixtures thereof.
1.2. Alkylthiomethylphenols, for example 2,4-dioctylthiomethy1-6-tert-butylphenol, 2,4-dioc-tylthiomethy1-6-methylphenol, 2,4-dioctylthiomethy1-6-ethylphenol, 2,6-didodecylthiomethy1-4-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-dipheny1-4-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-di-tert-butyl-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-dimethy1-4-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-(a-methylcyclo-hexyl)phenol], 2,2'-methylenebis(4-methyl-6-cyclohexylphenol), 2,2'-methylenebis(6-nony1-4-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-(a-methylben-zy1)-4-nonylphenol], 2,2'-methylenebis[6-(a,a-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-hydroxybenzyI)-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-ty1-4'-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-dimethy1-2-hydroxyphenyl)butane, 2,2-bis-( 3 ,5-d i-tert-buty1-4-hydroxy-phenyl)propane, 2,2-bis-(5-tert-buty1-4-hydroxy2-methylpheny1)-4-n-dodecylmercaptobutane, 1,1,5,5-tetra-(5-tert -butyl-4-hydroxy2-methylphenyl)pentane.
1.6. 0-, N- and S-benzyl compounds, for example 3,5,3',5'-tetra-tert-buty1-4,4'-dihydroxy-dibenzyl ether, octadecy1-4-hydroxy-3,5-di methyl benzylmercaptoacetate, tris-(3,5-di-tert -bu-ty1-4-hydroxybenzyl)amine, bis(4-tert-butyl-3-hyd roxy-2,6-di methyl benzyl)d ithioterephthalate, bis(3,5-di-tert-buty1-4-hydroxybenzyl)sulfide, isoocty1-3 ,5d i-tert-buty1-4-hydroxybenzylmer-captoacetate.
1.7. Hydroxybenzylated malonates, for example dioctadecy1-2,2-bis-(3,5-di-tert-buty1-2-hy-droxybenzy1)-malonate, di-octadecy1-2-(3-tert-buty1-4-hydroxy-5-methylbenzy1)-malonate, di-dodecylmercaptoethy1-2,2-bis-(3,5-di-tert-buty1-4-hydroxybenzyl)malonat e, bis [4-(1 ,1,3,3-tetramethylbutyl)pheny1]-2,2-bis(3,5-di-tert-buty1-4-hydroxybe nzyl)malonate.
1.8. Aromatic hydroxybenzyl compounds, for example 1,3,5-tris-(3,5-di-tert-buty1-4-hydroxy-benzy1)-2,4,6-trimethylbenzene, 1,4-bis(3,5-di-tert-buty1-4-hydroxybenzy1)-2,3,5,6-tetrame-thyl benzene, 2,4 ,6-tris(3,5-d i-tert-butyl-4-hyd roxybenzyl)phenol.
1.9. Triazine Compounds, for example 2,4-bis(octylmercapto)-6-(3,5-di-tert-buty1-4-hy-droxyanilino)-1,3,5-triazine, 2-octylmercapto-4,6-bis(3,5-d i-tert-buty1-4-hyd roxyani lino) -1,3,5-triazine, 2-octylmercapto-4,6-bis(3,5-di-tert-buty1-4-hydroxyphenoxy) -1,3,5-triazine, 2,4,6-tris(3 ,5-d i-tert-butyl-4-hyd roxyphenoxy)-1,2 ,3-triazine, 1,3,5-tris(3,5-d i-tert-buty1-4-hydroxy-benzyl)isocyanu rate, 1,3,5-tris(4-tert-buty1-3-hydroxy-2,6-dimethylbenzyl 2 ,4,6-tris(3,5-d i-tert-buty1-4-hyd roxyphenylethyl)-1,3 ,5-triazine, 1,3,5-tris(3,5-di-tert-buty1-4-hydroxyphenylpropio-ny1)-hexahydro-1,3,5-triazine, 1,3,5-tris(3,5-dicyclohexy1-4-hydroxybenzyl)isocyanurate.
1.10. Benzylphosphonates, for example dimethy1-2,5-di-tert-buty1-4-hydroxybenzylphospho-nate, diethyl-3,5-di-tert-buty1-4-hydroxybenzylphosphonate, dioctadecyI3,5-di-tert-butyl -4-hydroxybenzylphosphonate, dioctadecy1-5-tert-butyl-4-hydroxy3-methylbenzylphosphonate, the calcium salt of the monoethyl ester of 3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid.
1.11. Acylaminophenols, for example 4-hydroxylauranilide, 4-hydroxystearanilide, octyl N-(3 ,5-d i-tert-butyl-4-hyd roxyphenyl)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) isocyanu rate, N,N'-bis(hydroxyethyl)oxamide, 3-thi-aundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethy1-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.
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-dicyclopenty1-4-methylphenol, 2-(a-methylcyclohexyl)-4,6-dimeth-ylphenol, 2,6-dioctadecy1-4-methylphenol, 2,4,6-tricyclohexylphenol, 2,6-di-tert-butyl-4-meth-oxymethylphenol, 2,6-di-nony1-4-methylphenol, 2,4-dimethyl -6(11-methylundec-11-yl)phenol, 2,4-dimethy1-6-(11-methylheptadec-11-y1)phenol, 2,4-dimethy1-6-(11-methyltridec-11-yl)phenol and mixtures thereof.
1.2. Alkylthiomethylphenols, for example 2,4-dioctylthiomethy1-6-tert-butylphenol, 2,4-dioc-tylthiomethy1-6-methylphenol, 2,4-dioctylthiomethy1-6-ethylphenol, 2,6-didodecylthiomethy1-4-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-dipheny1-4-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-di-tert-butyl-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-dimethy1-4-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-(a-methylcyclo-hexyl)phenol], 2,2'-methylenebis(4-methyl-6-cyclohexylphenol), 2,2'-methylenebis(6-nony1-4-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-(a-methylben-zy1)-4-nonylphenol], 2,2'-methylenebis[6-(a,a-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-hydroxybenzyI)-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-ty1-4'-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-dimethy1-2-hydroxyphenyl)butane, 2,2-bis-( 3 ,5-d i-tert-buty1-4-hydroxy-phenyl)propane, 2,2-bis-(5-tert-buty1-4-hydroxy2-methylpheny1)-4-n-dodecylmercaptobutane, 1,1,5,5-tetra-(5-tert -butyl-4-hydroxy2-methylphenyl)pentane.
1.6. 0-, N- and S-benzyl compounds, for example 3,5,3',5'-tetra-tert-buty1-4,4'-dihydroxy-dibenzyl ether, octadecy1-4-hydroxy-3,5-di methyl benzylmercaptoacetate, tris-(3,5-di-tert -bu-ty1-4-hydroxybenzyl)amine, bis(4-tert-butyl-3-hyd roxy-2,6-di methyl benzyl)d ithioterephthalate, bis(3,5-di-tert-buty1-4-hydroxybenzyl)sulfide, isoocty1-3 ,5d i-tert-buty1-4-hydroxybenzylmer-captoacetate.
1.7. Hydroxybenzylated malonates, for example dioctadecy1-2,2-bis-(3,5-di-tert-buty1-2-hy-droxybenzy1)-malonate, di-octadecy1-2-(3-tert-buty1-4-hydroxy-5-methylbenzy1)-malonate, di-dodecylmercaptoethy1-2,2-bis-(3,5-di-tert-buty1-4-hydroxybenzyl)malonat e, bis [4-(1 ,1,3,3-tetramethylbutyl)pheny1]-2,2-bis(3,5-di-tert-buty1-4-hydroxybe nzyl)malonate.
1.8. Aromatic hydroxybenzyl compounds, for example 1,3,5-tris-(3,5-di-tert-buty1-4-hydroxy-benzy1)-2,4,6-trimethylbenzene, 1,4-bis(3,5-di-tert-buty1-4-hydroxybenzy1)-2,3,5,6-tetrame-thyl benzene, 2,4 ,6-tris(3,5-d i-tert-butyl-4-hyd roxybenzyl)phenol.
1.9. Triazine Compounds, for example 2,4-bis(octylmercapto)-6-(3,5-di-tert-buty1-4-hy-droxyanilino)-1,3,5-triazine, 2-octylmercapto-4,6-bis(3,5-d i-tert-buty1-4-hyd roxyani lino) -1,3,5-triazine, 2-octylmercapto-4,6-bis(3,5-di-tert-buty1-4-hydroxyphenoxy) -1,3,5-triazine, 2,4,6-tris(3 ,5-d i-tert-butyl-4-hyd roxyphenoxy)-1,2 ,3-triazine, 1,3,5-tris(3,5-d i-tert-buty1-4-hydroxy-benzyl)isocyanu rate, 1,3,5-tris(4-tert-buty1-3-hydroxy-2,6-dimethylbenzyl 2 ,4,6-tris(3,5-d i-tert-buty1-4-hyd roxyphenylethyl)-1,3 ,5-triazine, 1,3,5-tris(3,5-di-tert-buty1-4-hydroxyphenylpropio-ny1)-hexahydro-1,3,5-triazine, 1,3,5-tris(3,5-dicyclohexy1-4-hydroxybenzyl)isocyanurate.
1.10. Benzylphosphonates, for example dimethy1-2,5-di-tert-buty1-4-hydroxybenzylphospho-nate, diethyl-3,5-di-tert-buty1-4-hydroxybenzylphosphonate, dioctadecyI3,5-di-tert-butyl -4-hydroxybenzylphosphonate, dioctadecy1-5-tert-butyl-4-hydroxy3-methylbenzylphosphonate, the calcium salt of the monoethyl ester of 3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid.
1.11. Acylaminophenols, for example 4-hydroxylauranilide, 4-hydroxystearanilide, octyl N-(3 ,5-d i-tert-butyl-4-hyd roxyphenyl)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) isocyanu rate, N,N'-bis(hydroxyethyl)oxamide, 3-thi-aundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethy1-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.
1.13. Esters of 13-(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, eth-ylene 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-hydroxymethy1-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.
1.14 Esters of 13-(3,5-dicyclohexy1-4-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) isocyanu rate, N,N'-bis(hydroxyethyl)oxamide, 3-thi-aundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethy1-1-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-thiaunde-canol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethy1-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.
1.16. Amides of [3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid e.g. N,N1-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hexamethylenediamine, N,N1-bis(3,5-di-tert-butyl -4-hydroxy-phenylpropionyl)trimethylenediamine, N,N1-bis(3,5-di-tert-butyl-4-hydroxyphenylpropio-nyphydrazine.
Aminic antioxidants:
N,N'-diisopropyl-p-phenylenediamine, N,N'-di-sec-butyl-p-phenylenediamine, N,N'-bis (1,4-dimethylpentyI)-p-phenylenediamine, N,N1-bis(1-ethyl-3-methylpenty1)-p-phenylenediamine, N,N1-bis(1-methylhepty1)-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-methylheptyI)-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'-di-tert-octyldi-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-tetramethy1-5,9-dihydroxy -3,7,11 -trithiatridecane and 2,2,15,15- tetramethy1-5,12-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-cyclohexyloxybutyl)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;
alkoxyalky1-1,2,4-triazoles such as 1-(1-butoxyethyl)-1,2,4-triazole; and acylated 3-amino-1,2,4-triazoles.
c) lmidazole derivatives, for example 4,4'-methylenebis(2-undecy1-5-methylimidazole) and bis[(N-methypimidazol-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)aminomethy1]-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-boxymethy1-1-dodecy1-3-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-heptadeceny1-1-(2-hydroxyethypimidazoline.
c) Phosphorus-containing compounds, for example: Amine salts of phosphoric acid partial esters or phosphonic acid partial esters, and zinc dialkyldithiophosphates.
d] Molybdenum- containing compounds, such as Molydbenum dithiocarbamate and other sulphur and phosphorus containing derivatives e) Sulfur-containing compounds, for example: barium dinonylnaphthalenesulfonates, 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, polyvinylpyrroli-dones, 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 dialkyldithiophosphates, 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], de-rivatives of 2-mercaptobenzothiazole such as 1-[N,N-bis (2-ethylhexyl)aminomethyI]-2-mer-capto-1H-1,3-benzothiazole, and ethoxycarbony1-5-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 hin-dered 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 60 C for one hour to insure homogeneity. The formulations are tested ac-cording to elastomer compatibility procedure CEO- L-39-T-96. The results of the CEO- L-39-T-96 testing of these formulations with an FKM fluorinated rubber are found below. Both amines affected the rubber elastomer.
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.
K
Amine A is H3C¨N 0 (rs......,,_, 2)8 0 N¨CH3 .
, Amine B is HN 0 C 11H 23
1.14 Esters of 13-(3,5-dicyclohexy1-4-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) isocyanu rate, N,N'-bis(hydroxyethyl)oxamide, 3-thi-aundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethy1-1-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-thiaunde-canol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethy1-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.
1.16. Amides of [3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid e.g. N,N1-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hexamethylenediamine, N,N1-bis(3,5-di-tert-butyl -4-hydroxy-phenylpropionyl)trimethylenediamine, N,N1-bis(3,5-di-tert-butyl-4-hydroxyphenylpropio-nyphydrazine.
Aminic antioxidants:
N,N'-diisopropyl-p-phenylenediamine, N,N'-di-sec-butyl-p-phenylenediamine, N,N'-bis (1,4-dimethylpentyI)-p-phenylenediamine, N,N1-bis(1-ethyl-3-methylpenty1)-p-phenylenediamine, N,N1-bis(1-methylhepty1)-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-methylheptyI)-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'-di-tert-octyldi-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-tetramethy1-5,9-dihydroxy -3,7,11 -trithiatridecane and 2,2,15,15- tetramethy1-5,12-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-cyclohexyloxybutyl)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;
alkoxyalky1-1,2,4-triazoles such as 1-(1-butoxyethyl)-1,2,4-triazole; and acylated 3-amino-1,2,4-triazoles.
c) lmidazole derivatives, for example 4,4'-methylenebis(2-undecy1-5-methylimidazole) and bis[(N-methypimidazol-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)aminomethy1]-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-boxymethy1-1-dodecy1-3-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-heptadeceny1-1-(2-hydroxyethypimidazoline.
c) Phosphorus-containing compounds, for example: Amine salts of phosphoric acid partial esters or phosphonic acid partial esters, and zinc dialkyldithiophosphates.
d] Molybdenum- containing compounds, such as Molydbenum dithiocarbamate and other sulphur and phosphorus containing derivatives e) Sulfur-containing compounds, for example: barium dinonylnaphthalenesulfonates, 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, polyvinylpyrroli-dones, 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 dialkyldithiophosphates, 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], de-rivatives of 2-mercaptobenzothiazole such as 1-[N,N-bis (2-ethylhexyl)aminomethyI]-2-mer-capto-1H-1,3-benzothiazole, and ethoxycarbony1-5-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 hin-dered 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 60 C for one hour to insure homogeneity. The formulations are tested ac-cording to elastomer compatibility procedure CEO- L-39-T-96. The results of the CEO- L-39-T-96 testing of these formulations with an FKM fluorinated rubber are found below. Both amines affected the rubber elastomer.
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.
K
Amine A is H3C¨N 0 (rs......,,_, 2)8 0 N¨CH3 .
, Amine B is HN 0 C 11H 23
Claims (7)
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 where R is a straight or branched alkyl group of from 7 to 17 carbon atoms.
2. A composition according to claim 1 where R is a straight or branched alkyl group of 11 or 17 carbon atoms.
3. A composition according to claim 1 where the hindered amine is of the formula
4. A composition according to claim 1 where the hindered amine is present from 0.01 to 5% by weight, based on the weight of the lubricant.
5. A composition according to claim 1 where the hindered amine is present from 0.05 to 3% by weight, based on the weight of the lubricant.
6. A composition according to claim 1 where the hindered amine is present from 0.1 to 2% by weight, based on the weight of the lubricant.
7. 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 sterically hindered amine compounds of the formula where R is a straight or branched alkyl group of from 7 to 17 carbon atoms.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
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| US83438306P | 2006-07-31 | 2006-07-31 | |
| US60/834,383 | 2006-07-31 | ||
| PCT/EP2007/057552 WO2008015116A2 (en) | 2006-07-31 | 2007-07-23 | Lubricant composition |
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| Publication Number | Publication Date |
|---|---|
| CA2657382A1 CA2657382A1 (en) | 2008-02-07 |
| CA2657382C true CA2657382C (en) | 2014-09-09 |
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| CA2657382A Expired - Fee Related CA2657382C (en) | 2006-07-31 | 2007-07-23 | Lubricant compositions comprising tetramethylpiperidines |
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| EP (1) | EP2049630B1 (en) |
| JP (2) | JP5546858B2 (en) |
| KR (1) | KR101433140B1 (en) |
| CN (1) | CN101495605B (en) |
| AU (1) | AU2007280548B2 (en) |
| BR (1) | BRPI0714961B1 (en) |
| CA (1) | CA2657382C (en) |
| IL (1) | IL196250A (en) |
| MX (1) | MX2009001124A (en) |
| PL (1) | PL2049630T3 (en) |
| RU (1) | RU2462505C2 (en) |
| WO (1) | WO2008015116A2 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| MX2009001124A (en) * | 2006-07-31 | 2009-03-05 | Ciba Holding Inc | Lubricant composition. |
| US8236204B1 (en) | 2011-03-11 | 2012-08-07 | Wincom, Inc. | Corrosion inhibitor compositions comprising tetrahydrobenzotriazoles solubilized in activating solvents and methods for using same |
| US8236205B1 (en) | 2011-03-11 | 2012-08-07 | Wincom, Inc. | Corrosion inhibitor compositions comprising tetrahydrobenzotriazoles and other triazoles and methods for using same |
| US9969950B2 (en) | 2012-07-17 | 2018-05-15 | Infineum International Limited | Lubricating oil compositions containing sterically hindered amines as ashless TBN sourcces |
| WO2014028629A1 (en) * | 2012-08-14 | 2014-02-20 | Basf Se | Lubricant composition comprising hindered cyclic amines |
| US20150045261A1 (en) * | 2012-10-12 | 2015-02-12 | Basf Se | Lubricant Compositions Comprising Trimethoxyboroxine To Improve Fluoropolymer Seal Compatibility |
| JP2016501284A (en) * | 2012-11-16 | 2016-01-18 | ビーエーエスエフ ソシエタス・ヨーロピアＢａｓｆ Ｓｅ | Epoxy compound-containing lubricating oil composition for improving fluoropolymer seal compatibility |
| FR3000103B1 (en) * | 2012-12-21 | 2015-04-03 | Total Raffinage Marketing | LUBRICATING COMPOSITION BASED ON POLYGLYCEROL ETHER |
| RU2015149917A (en) | 2013-04-22 | 2017-05-26 | Басф Се | ADDITIVE FOR IMPROVEMENT OF COMPATIBILITY WITH SEALS OF LUBRICANT COMPOSITIONS WITH FLUOROPOLYMER SEALS |
| US10066186B2 (en) | 2013-04-22 | 2018-09-04 | Basf Se | Lubricating oil compositions containing a halide seal compatibility additive and a second seal compatibility additive |
| RU2528833C1 (en) * | 2013-05-15 | 2014-09-20 | Открытое акционерное общество "Нефтяная компания "Роснефть" | Gearbox oil |
| EP3000866A4 (en) | 2013-05-20 | 2017-01-18 | Idemitsu Kosan Co., Ltd | Lubricant composition |
| EP2816097A1 (en) * | 2013-06-18 | 2014-12-24 | Shell Internationale Research Maatschappij B.V. | Lubricating oil composition |
| US9309205B2 (en) | 2013-10-28 | 2016-04-12 | Wincom, Inc. | Filtration process for purifying liquid azole heteroaromatic compound-containing mixtures |
| US20160289588A1 (en) * | 2013-11-04 | 2016-10-06 | Basf Se | Lubricant Composition |
| US9562208B2 (en) * | 2014-07-02 | 2017-02-07 | Basf Se | Sulfonate esters to improve fluoropolymer seal compatibility of lubricant compositions |
| WO2016036493A1 (en) * | 2014-09-04 | 2016-03-10 | Vanderbilt Chemicals, Llc | Liquid ashless antioxidant additive for lubricating compositions |
| JP6863557B2 (en) * | 2016-12-05 | 2021-04-21 | 出光興産株式会社 | Lubricating oil composition and its manufacturing method |
Family Cites Families (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6028496A (en) * | 1983-07-25 | 1985-02-13 | Adeka Argus Chem Co Ltd | Lubricating oil composition |
| US5273669A (en) * | 1988-07-18 | 1993-12-28 | Ciba-Geigy Corporation | Lubricant composition |
| US5073278A (en) * | 1988-07-18 | 1991-12-17 | Ciba-Geigy Corporation | Lubricant composition |
| US5268113A (en) * | 1989-07-07 | 1993-12-07 | Ciba-Geigy Corporation | Lubricant composition |
| DE59002284D1 (en) * | 1989-07-07 | 1993-09-16 | Ciba Geigy Ag | LUBRICANT COMPOSITION. |
| US7592495B2 (en) * | 2000-07-11 | 2009-09-22 | King Industries | Compositions of Group II and/or Group III base oils and alkylated fused and/or polyfused aromatic compounds |
| JP2004051758A (en) * | 2002-07-19 | 2004-02-19 | Asahi Denka Kogyo Kk | Lubricating oil composition based on mineral oil having high sulfur content |
| CN1333054C (en) * | 2004-06-29 | 2007-08-22 | 中国石油化工股份有限公司 | Lubricating oil composite stabilizer and stable hydrogenation lubricating oil composition |
| MX2009001124A (en) * | 2006-07-31 | 2009-03-05 | Ciba Holding Inc | Lubricant composition. |
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2007
- 2007-07-23 MX MX2009001124A patent/MX2009001124A/en active IP Right Grant
- 2007-07-23 KR KR1020097000672A patent/KR101433140B1/en active IP Right Grant
- 2007-07-23 EP EP20070787797 patent/EP2049630B1/en not_active Not-in-force
- 2007-07-23 CN CN200780028456.7A patent/CN101495605B/en not_active Expired - Fee Related
- 2007-07-23 AU AU2007280548A patent/AU2007280548B2/en not_active Ceased
- 2007-07-23 CA CA2657382A patent/CA2657382C/en not_active Expired - Fee Related
- 2007-07-23 RU RU2009106723/04A patent/RU2462505C2/en not_active IP Right Cessation
- 2007-07-23 WO PCT/EP2007/057552 patent/WO2008015116A2/en active Application Filing
- 2007-07-23 PL PL07787797T patent/PL2049630T3/en unknown
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Also Published As
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| IL196250A (en) | 2013-10-31 |
| BRPI0714961A2 (en) | 2013-07-30 |
| MX2009001124A (en) | 2009-03-05 |
| BRPI0714961B1 (en) | 2016-11-22 |
| EP2049630A2 (en) | 2009-04-22 |
| PL2049630T3 (en) | 2015-10-30 |
| JP5546858B2 (en) | 2014-07-09 |
| EP2049630B1 (en) | 2015-04-29 |
| CA2657382A1 (en) | 2008-02-07 |
| KR101433140B1 (en) | 2014-08-22 |
| AU2007280548A1 (en) | 2008-02-07 |
| CN101495605A (en) | 2009-07-29 |
| CN101495605B (en) | 2014-03-05 |
| RU2462505C2 (en) | 2012-09-27 |
| AU2007280548B2 (en) | 2012-04-05 |
| IL196250A0 (en) | 2009-09-22 |
| KR20090033358A (en) | 2009-04-02 |
| WO2008015116A2 (en) | 2008-02-07 |
| WO2008015116A3 (en) | 2008-03-20 |
| JP2009545640A (en) | 2009-12-24 |
| RU2009106723A (en) | 2010-09-10 |
| JP2014139313A (en) | 2014-07-31 |
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