MXPA05001129A

MXPA05001129A - Engine oils comprising lead corrosion-inhibitors.

Info

Publication number: MXPA05001129A
Application number: MXPA05001129A
Authority: MX
Inventors: David Eliezer Chasan
Original assignee: Ciba Sc Holding Ag
Priority date: 2002-08-06
Filing date: 2003-07-29
Publication date: 2005-05-16
Also published as: EP1532232A1; AU2003253351A1; CA2494639A1; US20040038835A1; KR20050032104A; WO2004015043A1; AU2003253351B2; BR0313248A; CN1675341A; JP2005534782A; TW200413518A

Abstract

Formulated engine oils that comprise certain 1,2,4-triazole metal deactivators are especially non-aggressive towards lead engine parts such as bearings. The inclusion of certain 1,2,4-triazole compounds allows the co-use of corrosive additives such as sulfur-containing additives and vegetable oil-derived friction modifiers while at the same time meeting ASTM D 4485 specifications.

Description

ENGINE OILS COMPRISING LEAD CORROSION INHIBITORS The present invention relates to engine oil compositions (engine fluids) that are not aggressive to lead. The US patent specification. No. 4,734,209 describes metal deactivators for functional fluids. The US patent specification. No. 4,491,527 describes compositions useful for inhibiting the deposition of lead paint in lubricants. Engine oil specifications become stricter as performance requirements and new formulations are under development to meet these new specifications. Engine oil specifications are defined in AST D 4485. The new engine oil formulations in development, include certain adhesive chemistries. Many of these additive chemicals are corrosive to lead. It is difficult for formulators to satisfy the present engine oil specifications by employing certain beneficial additives as long as they also meet the lead corrosion specification.

From 1994 onwards, it has been required that all diesel oils meet a lead corrosion specification defined in ASTM D 4485 and as measured in accordance with ASTM D 5968 (which is carried out at 125 degrees C) or ASTM D 6594 (which takes place at 135 degrees C). The ASTM D 4485 standard specification for engine oil performance indicates a maximum tolerated lead corrosion level of 60 ppm for API CF-4 and CG-4 categories by ASTM D 5968 and 120 ppm for CH-4 category by ASTM D 6594. For example, if these formulated motor oil components that cause lead corrosion include certain detergents, anti-wear additives, friction modifiers and antioxidants. Many of these desired additive chemistries are disqualified from use because they cause motor oil formulations to fail to meet industrial specifications for lead corrosion limits. For example, desired additive chemistries that are aggressive to lead and otherwise disqualified for use in motor oils include sulfur-containing additives and certain friction modifiers derived from vegetable oil. It has been surprisingly found that engine oils formulated that comprise certain Metal deactivators 1, 2, 4-triazole are especially non-aggressive towards lead, for example for lead motor parts such as bearings. The engine oils according to this invention meet the corrosion protection performance requirements of the diesel lubricant specifications defined in AST D4485. This aspect of lead corrosion is not usually a problem in other types of lubricants, for example turbine and hydraulic oils. The engine oils of this invention are universal diesel oils. Universal oils encompass both diesel oils and automobile passenger oils. Motor oils are used in internal combustion engines, for example in motor vehicles adapted for example with Otto, diesel, two-stroke, Wankel or orbital engines. Specifically, the present invention relates to an engine oil composition that is not aggressive to lead, this composition comprises: (a) A base fluid, (b) At least one compound of the formula (I) (c) At least one oil additive that is aggressive to lead and is selected from the group consisting of antioxidants, anti-wear additives, dispersants, detergents, anti-foam additives, viscosity inorators, copper passivators, inhibitors of oxidation, pour point depressants, de-emulsifiers and friction modifiers, where Ri and R2 are the same or different and are Ci-C2oalkyl, C3-C20alkenyl, C5-Ci2cycloalkyl, C7-Ci3aralkyl or C6-Ci0aril, or Ri and R2 together with the nitrogen atom to which each one is connected can form a heterocyclic residue of 5, 6 or 7 members or Rx and R2 are a group of the formula R3X [(-R4-) 0] n (-R4) -, where X is 0, S or N, R3 is hydrogen or Ci-C2azoyl, R4 is Ci-C12alkylene, n is 0 or an integer from 1 to 6, or one of Ri and R2 is a group of the formula or R2 is a group of the formula (II) and Rx is a group of the formula - [R4] nN (R5) -A- [N (s) 2] ra where m is 0 or 1 and when m is zero , A is a group of the formula (II) and when m is 1, A is alkylene or C6-Ci0arylene and R5 is a group of the formula (II), and wherein in the absence of the component (b), the composition of engine oil exceeds approximately 100 ppm lead as measured according to the ASTM D 6594 test. R4 for example is a C-C6alkylene group, for example C2-C3alkylene. The number n is for example, 0, 1, 2, 3, 4, 5 or 6. Alkyl is straight or branched chain and is for example methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, 2-ethylhexyl , n-nonyl, n-decyl, n-dodecyl, n-tetradecyl, n-hexadecyl, n-octadecyl or n-eicosyl.

Alkenyl is straight or branched chain and is for example, prop-2-enyl, but-2-enyl, 2-methyl-prop-2-enyl, pent-2-enyl, hexa-2, -dienyl, dec-10- enyl or eicos-2-enyl. Cycloalkyl is, for example, cyclopentyl, cyclohexyl, cyclooctyl, cyclodecyl, adamantyl or cyclododecyl. Aralkyl is, for example, benzyl, 2-phenylethyl, benzhydryl or naphthylmethyl. Aryl is, for example, phenyl or naphthyl. When Ri and R2 together with the hydrogen atom to which they are connected form a heterocyclic group, the heterocyclic group, for example, is a morpholine ring, pyrrolidine, piperidine or perhydroazepine. Alkylene includes for example methylene, ethylene, 1: 2- or 1: 3 -propylene, 1: 4 -butylene, 1: 6 -hexylene, 1: 8 -octylene, 1: 10-decylene and 1: 12 -dodecylene.

Arylene includes, for example, phenylene and naphthylene. Specific compounds of the present formula (I) include: 1- (or 4) - (dimethylaminomethyl) triazole; 1- (or 4) - (diethylaminomethyl) triazole; 1- (or 4) - (di-iso-propylaminomethyl) triazole; 1- (or 4) - (di-n-butylaminomethyl) triazole; 1- (or 4) - (di-n-hexilami nomethyl) triazole; 1- (or 4) - (di-isooctylaminomethyl) triazole; 1- (or 4) - (di- (2-ethylhexyl) amino-methyl) triazole; 1- (or 4) - (di-n-octylaminomethyl) triazole; 1- (or 4) - (di-n-decylaminomethyl) -triazole; 1- (or 4) - (di-n-dodecylaminemethyl) triazole, - 1- (or 4) - (di-n-octadecylaminomethyl) triazole; 1- (or 4) - (di-n-eicosylaminomethyl) triazole; 1- (or 4) - [di- (prop-2'-enyl) aminomethyl] triazole; 1- (or 4) - [di- (but-2'-enyl) aminomethyl] triazole; 1- (or 4) - [di- (eicos-2 '-enyl) aminomethyl] -triazole; 1- (or 4) - (di-cyclohexylaminomethyl) triazole; 1- (or 4) - (di-benzylaminomethyl) triazole; 1- (or 4) - (di-phenylaminomethyl) triazole; 1- (or 4) - (41-morpholinomethyl) triazole; 1- (or 4) - (! '- pyrrolidinomethyl) triazole; 1- (or 4) - (11-piperidinomethyl) triazole; 1- (or 4) - (11 -perhydroazepinomethyl) triazole; 1- (or 4) - (2 ', 2"-dihydroxyethyl) aminomethyl] triazole; 1- (or 4) - (dibutoxipropylaminomethyl) triazole; l- (or 4) - (dibutylthiopropyl-aminomethyl) triazole; 4) - (di-butylaminopropyl-aminomethyl) triazole;?,? - bis- (1- or 4-triazolylmethyl) laurylamine;?,? - bis- (1- or 4-triazolylmethyl) oleylamine;?,? - bis- (1- 4-triazolylmethyl) ethanolamine and N, N,? ', N' -tetra- (l- or 4-triazolylmethyl) ethylene diamine.

A representative compound of the formula (I) is, for example, 1- (di-isooctylaminomethyl) triazole, 1- (di-isooctylaminomethyl) -1,2,4-triazole, or is 1- (di- (2-ethylhexyl) aminomethyl) 1,2,4-triazole. The present compounds of the formula (I) are prepared by known methods for example as described in the U.S. patent specification. No. 4,734, 209, the description of which is hereby incorporated by reference. The base fluids according to the invention use mineral oil base fluids (Group I, II and III API), poly-alpha-olefins - PAOs (Group IV API), esters (Group V API), other synthetic fluids, natural oils which are of animal or vegetable origin, and their mixtures. The base fluids are of convenient viscosity for use in motor oil applications. The present compounds of the formula (I) are employed at concentrations of about 0.01 to about 1.0% by weight, based on the weight of the formulated motor oil. For example, the compounds of the formula (I) are present from about 0.02 to about 0.5% by weight; for example from about 0.03 to about 0.3% by weight; for example from about 0.01 to about 0.5 or from about 0.01 to about 0.3% by weight; for example from about 0.02 to about 1.0 or from about 0.02 to about 0.3% by weight; for example from about 0.03 to about 1.0 or from about 0.03 to about 0.5% by weight. Suitable antioxidants of component (c) are chosen from: 1) Alkylated monophenols, for example 2,6-di-tert-butyl-4-methylphenol, 2-butyl-, 6-di-methylphenol, 2,6-di-ter -butyl-4-ethylphenol, 2,6-di-tert-butyl-4-n-butylphenol, 2,6-di-tert-bu -yl-4-isobutylphenol, 2,5-di-cyclopentyl-4- methyl phenol, 2 - (a-methyl-cyclohexyl) -4,6-dimethyl-ylphenol, 2,6-di-octyldecyl-4-methylphenol, 2,4,6-tri-cyclohexylphenol, 2,6 -di-tert-butyl-4-methoxymethylphenol, linear or branched side-chain nonylphenols, for example 2,6-di-nonyl-4-methylphenol, 2, -dimethyl-6- (1'-methyl-undec-1 ' - il) phenol, 2,4-dimethyl-6- (11-methylheptadec-1-yl) phenol, 2,4-dimethyl-6 - (11-methyl-tridec-11-yl) phenol or mixtures thereof . 2) Alkyltiomethylphenols, for example 2,4-di-octylthiomethyl-6-tert-butylphenol, 2,4-dioctylthiomethyl-6-methylphenol, 2,4-di-octylthiomethyl-6-ethylphenol or 2,6-di-dodecylthiomethyl- 4 -nonyl phenol. 3) Hydroquinones and alkylated hydroquinones, for example 2, 6-di-tert-butyl-4-methoxyphenol, 2,5-di-ter- butylhydroquinone, 2,5-di-ether-amylhydroquinone, 2,6-diphenyl-4-octadecyloxyphenol, 2,6-di-tert-butyl-hydroquinone, 2,5-di-tert-butyl-4-hydroxyanisole, 3, 5 di-tert-butyl-4-hydroxyanisole, 3,5-di-tert-butyl-4-hydroxyphenyl stearate or bis (3,5-di-tert-butyl-4-hydroxyphenyl) adipate. 4) Tocopherols, for example alpha-, beta-, gamma- or delta-tocopherol or their mixtures (vitamin E). 5) 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. -amyl phenol) or 4,4-bis ( 2,6-dimethyl-4-hydroxyphenyl) disulfide 6) Alkylidenebisphenols, for example 2,2'-methylenebis (6-tert-butyl-4-methylphenol), 2,2'-methylenebis (6-tert-butyl -4- ethylphenol), 2,2 '-me ilenbis (4-methyl-6 - (alpha-methylcyclohexyl) -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'-ethylidebis (4,6-di-tert-butylphenol), 2,2'-ethylidebis (6-tert-butyl-4-isobutylphenol), 2,2'-methylene-bis (6 - (a-methylbenzyl) -4 -nonylphenol), 2,2'-methylene-bis (6- (alpha, alpha-dimethylbenzyl) ) -4 -nonylphenol), 4,4'-methylenebis (2,6-di-tert-butylphenol), 4,4'-methylenebis (6-tert-butyl-2-methylphenol), 1,1-bis (5-er-bu il -4-hydroxy-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-methylphenyl) -3-n-dodecyl mercaptobutane, ethylene glycol bis (3, 3-bis (3 '-tert-butyl-' -hydroxyphenyl) butyrate), bis (3-tert-butyl-4-hydroxy-5-methylphenyl) dicyclo-pentadiene, 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-hydroxyphenyl) -nolene, 2,2-bis (5-tert-butyl-1,4-hydroxy-2-methylphenyl) -4-n-dodecyl mercaptobutane or 1, 1 , 5, 5-tetra (5-tert-butyl-4-hydroxy-2-methylphenyl) -pentane 7) Compounds 0-, N- and S-benzyl, for example 3,5,3 ', 5-tetra-ter -butyl-4, 4'-dihydroxydibenzyl ether, octadecyl-4-hydroxy-3,5-dimethyl-4-benzylmercaptoaceto, tridecyl-4-hydroxy-3,5-di-tert-but-il-benzylmercap toacetate, tris (3,5-di-tert-butyl) amine, bis (4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) dithioterephthalate, bis (3, 5-di-tert-butyl-4) -hydroxybenzyl) sulfide or isooctyl 3,5-di-tert-butyl-4-hydroxy-benzylmercaptoacetate. 8) Hydroxybenzylated malonates, for example dioctadecyl 2,2-bis (3,5-di-tert-butyl-2-hydroxybenzyl) malonate, dioctadecyl 2- (3-tert-butyl-4-hydroxy-5-methylbenzyl) -malonate , di-dodecyl mercaptoethyl- 2,2-bis (3,5-di-tert-butyl-4-hydroxybenzyl) -malonate or di (4- (1,1,3,3-tetramethylbutyl) phenyl) -2,2 -bis (3, 5) -di-tert-butyl-4-hydroxybenzyl) malonate 9) Hydroxybenzyl aromatic compounds, for example 1, 3, 5 -tris (3,5-di-tert-butyl-4-hydroxybenzyl) -2, 4,6-trimethylbenzene, 1,4-bis (3,5-di-tert-butyl-4-hydroxybenzyl) -2,3,5,6-tetramethylbenzene or 2,4,6-tris (3,5-di- tert-butyl-4-hydroxybenzyl) phenol 10) Triazine compounds for example 2,4-bisoctylmercapto-6 - (3, 5-di-tert-butyl-4-hydroxyanilino) -1,3,5-triazine, 2 - octylmercapto-4,6-bis (3,5-di-tert-butyl-4-hydroxyanilino) -1,3,5-triazin, 2-yl-mercapto-4,6-bis (3, 5-di-ester) butyl-hydroxyphenoxy) -1,3,5-triazine, 2,4,6-tris (3,5-di-tert-butyl-hydroxyphenoxy) -1,2,3-triazine, 1, 3, 5 - tris (3, 5-di-tert-butyl-4-hydroxybenzyl) -isocyanurate, 1,3,5-tris (4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanurate, 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-hydroxyphenylpropionyl) hexahydro- 1, 3, 5-triazine or 1,3,5-tris (3, 5-dicyclohexyl-4-hydroxybenzyl) isocyanurate 11) Benzylphosphonates, for example dimethyl 2, 5-di-tert-butyl-4-hydroxybenzyl-f osphonate, diethyl 3, 5-di-tert-butyl-4-hydroxybenzylphosphonate, dioctadecyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate, dioctadecyl 5-tert-butyl-4-hydroxy-3-methylbenzylphosphonate or the calcium salt of monoethyl ester 3-, 5-di-tert-butyl- 4 -hidroxibencilfosfónico 12) Acylaminophenols, for example 4 -hidroxílauranilida, 4-hydroxystearanilide or octyl N- (3, 5-di-tert-butyl-4-hydroxy-phenyl) carbamate 13) Esters of beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid, beta- (5-tert-butyl) -4-hydroxy-3-methylphenyl) propionic acid, beta- (3,5-dicyclohexyl-4-hydroxyphenyl) - propionic acid, 3, 5 -di -tert-butyl -4 -hidroxifenilacetico, or beta- (5-tert-butyl) -4-hydroxyphenyl)) -3 -tiabutírico with mono- or polyhydric alcohols, eg with methanol, ethanol, n-octanol, i-octanol, octadecanol, 1, 6-hexanediol, 1, 9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris (hydroxyethyl isocyanurate,?,? '- bis (Hydroxyethyl) oxalamide, 3-thiaundecanol, 3 -tiapentadecanol, -hexandiol trimethyl, trimethylolpropane, 4-hydroxymethyl-l-phospha-2, 6, 7-trioxabicyclo (2.2.2) octane, glycerol or transesterification products based on triglycerides natural for example coconut oil, nabine oil or nabilla, sunflower oil or rapeseed oil. 14) Amides of beta- (3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid, for example, N, N'-bis (3,5-di-tert-butyl-4-hydroxyphenylpropionyl) hexamethylenediamine, N, N'-bis (3,5-di-tert-buty-4-hydroxyphenylpropionyl) trimethylenediamine or N, N'-bis (3,5-di-tert-butyl-4-hydroxy-phenylpropionyl) hydrazine 15) Acid ascorbic (vitamin C) 16) Amine-type antioxidants eg N, N1-diisopropyl-p-phenylenediamine, N, N'-di-sec-butyl-p-phenylenediamine, N, N'-bis (1,4-dimethylpentyl) -p- phenyleridiamine, N, N'-bis (l-ethyl-3-methy1-pentyl) -p-phenylenediamine, N, N'-bis (1-methyl-heptyl) -p-phenylenediamine, N, N '- dicyclohexy1-p-phenylenediamine,?,? ' -diphenyl-p-phenylene diamine,?,? -di- (naphth-2-yl) -p-phenylenediamine, N-isopropyl-N'-phenyl-p-phenyl-enediamine, N- (1,3-dimethylbutyl) -N'-phenyl-p-phenylenediamine, N - (1-methylhep-N '-phenyl-p-phenylenediamine, N-cyclohexyl-N' -phenyl-p-phenylenediamine, 4- (p-toluenesulfonamido) diphenylamine,?,? '-dimethyl-N, N' -di-sec -butyl-p-phenylenediamine, diphenylamine, N-allyldiphenylamine, 4-isopropoxy-diphenylamine, N-phenyl-naphthylamine, N- (4-tert-octylphenyl) -1-naphthylamine, N-phenyl-2-naphthylamine, octylated diphenylamine , eg p, p'-di-tert-octyldiphenyl-amine, 4-n-butylaminophenol, 4-butyrylaminophenol, 4-nonanoylaminophenol, 4- dodecanoylaminophenol, 4-octadecanoylaminophenol, di- (4-methoxyphenyl) -amine, 2,6-di-er-buyl-4-dimethylamino-methyl-phenol, 2,4'-diamino-diphenylmethane, 4,4'-diamino-diphenylmethane, N, N, N ', N' - tetramethyl -4,4'-diamino-diphenyl methane, 1,2-di- ((2-methyl-phenyl) -amino) -ethane, 1,2-di- (phenylamino) propane , (o-tolyl) biguanide, di (4- (l ', 3' ~ dimethyl: hyl-butyl) -phenyl) amine, N-phenyl-l-naphthylamine tert-octylated, a mixture of ter-butyl / ter- mono- and dialkylated octyldiphenylamines, a mixture of mono- and dialkylated nonildiphenylamines, a mixture of mono- and dialkylated dodecyldiphenylamines, a mixture of mono- and dialkylated isopropyl / isohexyldiphenylamines, mixtures of mono- and dialkylated ter-butyldiphenylamines, 2,3-dihydrate - 3,3-dimethyl-4H-1,4-benzothiazine, phenothiazine, a mixture of mono- and dialkylated ter-butyl / tert-octylphenothiazines, a mixture of mono- and dialkylated tert-octyl-phenothiazines, N-allylphenothiazine, N, N , N ', 1-tetraphenyl-1,4-diaminobut-2-ene,?,? - bis- (2,2,6,6-tetramethylpiperid) in-4-yl) hexamethylenediamine, bis- (2, 2, 6,6-tetramethylpiperidin-4-yl) sebacate, 2,2,6,6-tetramethylpiperidin -one or 2, 2, 6,6-tetramethylpiperidin-4 - ol and 17) Aliphatic or aromatic phosphites, thiodipropionic acid or thiodiacetic acid esters, or dithiocarbamic or dithiophosphoric acid salts, 2,2, 12, 12 -. 12-tetramethyl-5,9-dihydroxy-3,7,1-trithiatridecane or 2,1,15,15-tetramethyl-5,12-dihydroxy -3,7,14,14-tetra-thiahexadecane. Suitable anti-wear agents of component (c) are chosen from: 1) Dihydrocarbyl dithiophosphate metal salts wherein the metal is aluminum, lead, tin manganese, cobalt, nickel, zinc or copper, but more often zinc. The zinc salt (zinc dialkyl dithiophosphate) is represented as RO \ P-s Zn R'O wherein R and R 'independently represent C-C20alkyl, C3-C2alkylene, C5-C2cycloalkyl, C7-Ci3aralkyl or C6-Ci0aryl, for example R and R 'are independently Ci-C2alkyl and 2) Compounds containing sulfur and / or phosphorus and / or halogen, such as sulfurized olefins and vegetable oils, tritolyl phosphate, tricresyl phosphate, paraffins chlorides, alkyl and aryl di- and trisulphides, amine salts of mono- and dialkyl phosphates, amine salts of acid methylphosphonic acid, diethanolaminomethyloltriazole, di (2-ethylhexyl) -aminomethyloltriazole, derivatives of 2,5-dimercapto-1,3,4-thiadiazole, ethyl ((bisisopropyloxyphosphinothioyl) thio) propionate, triphenyl thiophosphate (triphenyl phosphorothioate), tris (alphenylphenyl) ) phosphorothioates and their ures (for example tris (isononylphenyl) phosphorothioate), diphenylmonononylphenyl phosphorothioate, isobutylphenyl diphenyl phosphorothioate, dodecylamine salt of 3-hydroxy-1,3-thiaphosphetan 3-oxide, 5,5,5-tris acid (isooctyl) 2-acetate) of trithiophosphoric acid, 2-mercaptobenzothiazole derivatives, such as l- (N, N-bis (2-ethylhexyl) amino-methyl) -2-mercapto-1H-1,3-benzothiazole or ethoxycarbonyl-5-octyldithiocarbamate. Suitable dispersants of component (c) are chosen from: 1) Mannich bases which are produced from condensation reaction of a high molecular weight phenol, an alkylene polyamine and an aldehyde such as formaldehyde 2) Succinic base dispersants which are products of reaction of an olefin polymer and a succinic acylating agent (acid, anhydride, ester or halide) additionally reacted with an organic hydroxy compound and / or an amine and 3) High molecular weight amides and esters such as reaction products of a hydrocarbyl acylating agent and an aliphatic polyhydric alcohol (such as glycerol, pentaerythritol or sorbitol). Ash-free (metal-free) polymeric materials that usually contain a high-molecular weight structure soluble in oil, linked to a polar functional group that associates with particles when dispersed, are typically used as dispersants. Main hydrocarbon structure materials commonly used are olefin polymers and copolymers, ie propylene, butylene, isobutylene, styrene; they may or may not be additional functional groups incorporated in the main structure of the polymer. Polar materials such as amines, alcohols, amides or esters, are connected to the main structure by means of a bridge. Suitable detergents of component (c) are chosen from: calcium, magnesium, barium, sodium or lithium salts of organic acids, for example sulfonates, alkylphenas, sulphided alkyl phenates, carboxylates, salicylates, phosphonates, thiophosphonates and phosphinates. The salts may be neutral or may be overbased, for example by metal hydroxides or carbonates.

Suitable anti-foam additives of component (c) are chosen from: silicone oils, polysiloxanes and polyethylene glycol ethers. Suitable viscosity index improvers of component (c) are chosen from: polyisobutylene, ethylene and propylene copolymers, polyacrylates, polymethacrylates, vinylpyrrolidone / methacrylate copolymers, polyvinylpyrrolidones, polybutenes, olefin copolymers, styrene / acrylate copolymers, styrene copolymers / isoprene, styrene / isobutadiene copolymers, isoprene / butadiene copolymers and polyethers. Suitable copper passivators of component (c) are chosen from: 1) Benzotriazoles and their derivatives, for example 4-or 5-alkylbenzotriazoles (for example tolutriazole) and its derivatives, 4, 5, 6, 7-tetrahydrobenzotriazole, 5, 51-methylene-bisbenzotriazole; Mannich bases of benzotriazole or tolutriazole, such as l- (di (2-ethylhexyl) aminomethyl) tolutriazole and 1- (di- (2-ethylhexyl) aminomethyl) -benzotriazole; alkoxyalkylbenzotriazoles, such as (nonyloxymethyl) -benzotriazole, 1- (1-butoxyethyl) -benzotriazole or 1 - (1-cyclohexyloxybutyl) -tolutriazole 2) Imidazole derivatives, for example 4,4'-methylenebis (2-undecyl-5-methyl-imidazole), bis ((N-methyl) imidazol-2-yl) carbinol octyl ether 3) Heterocyclic compounds containing sulfur, example -mercaptobenzothiazole, 2,5-dimercapto-1,3,4-thiadiazole, 2,5-dimercaptobenzothiadiazole and its derivatives or 3,5-bis (di (2-ethylhexyl) aminomethyl) -1,3,4-diazoline- 2 -one, and 4) Amino compounds, for example salicylidenepropylenediamine, salicylaminoguanidine or its salts. Suitable oxidation inhibitors of component (c) are chosen from: 1) Nonionic polyoxyalkylene polyols and their esters, polyoxyalkylene phenols, organic acids and their esters, metal salts, amine salts and anhydrides, for example alkyl and alkenyl succinic acids and their partial esters with alcohols, diols or hydroxycarboxylic acids, partial amides of alkyl and alkenylisuccinic acids, 4-nonylphenoxyacetic acid, alkoxy acids and alkoxyethoxycarboxyliands, such as dodecyloxyacetic acid, dodecyloxy (ethoxy) acetic acid and their amine salts, or N-oleoylsarcosine, sorbitan monooleate, lead naphthenate and alkenyl succinic anhydrides, for example anhydride docecylsuccinic and 2- (2-carboxyethyl) -l-dodecyl-3-methylglycerol and its salts, for example the sodium salts and triethanolamine 2) Nitrogen-containing compounds selected from: i) primary, secondary or tertiary amines, aliphatic or cycloaliphatic and amine salts of organic and inorganic acids, for example oil soluble alkyl ammonium carboxylates and also 1- (N, N-bis (2-hydroxyethyl) amino) -3- (4 -nonyl phenoxy) propan-2-ol, or ii) Heterocyclic compounds for example: imidazolines or oxazolines substuted for example 2-heptadecenyl-1- (2-hydroxyethyl) -imidazoline 3 ) Phosphorus-containing compounds, for example, phosphoric acid amine salts, partial phosphoric acid esters or partial phosphonic acid esters or zinc dialkyl lithium phosphates. 4) Sulfur-containing compounds, for example barium dinonylnaphthalene sulphonates, calcium petroleum sulfonates, aliphatic carboxylic acids substituted with alkyl thio, esters of aliphatic 2-sulfocarboxylic acids or their salts, and 5) glycerol derivatives, for example glycerol monooleate, 1 - (alkylphenoxy) -3 - (2-hydroxyethyl) glycerols, 1- (alkylphenoxy) -3- (2,3-dihydroxypropyl) glycerol or 2 - . 2-carboxyalkyl-1,3-dialkylglycerols. Suitable pour point depressants of component (c) are chosen from polymethacrylates and alkylated naphthalene derivatives. Suitable demulsifiers of component (c) are chosen from polyether polyols and dinonylnaphthalenesulfonates. Suitable friction modifiers of component (c) are chosen from fatty acids and their derivatives, for example natural fatty acid esters such as glycerol monooleate, amides, imides and amines, for example oleylamine, organomolybdenum dithiocarbamates containing sulfur, organomolybdenum dithiophosphates containing sulfur-phosphorus, organomolybdenum compounds containing sulfur-nitrogen based on dispersants, molybdenum carboxylate salts, molybdenum-amine complexes, molybdenum amine / alcohol / amide complexes, and swarm compounds of molybdenum, Teflon ™ and molybdenum disulfide. Additives that are aggressive towards lead are antioxidants, anti-wear additives, detergents, copper passivators, or friction modifiers, such as sulfur-containing antioxidants, sulfur-containing anti-wear additives, sulfur-containing copper passivators or friction modifiers derived from vegetable oil. For example, antioxidants containing sulfur, aggressive towards lead are phenothiazine antioxidants. The additives of component (c) are added in the usual amounts in each case in the range from about 0.01 to about 10.0% by weight, based on the composition of motor oil. The compounds of the formula (I) can be introduced into the engine oil in ways known per se. The compounds are easily soluble in oil. It is also possible to prepare a master batch of so-called additive (package) that can be diluted with the corresponding fluid to use concentrations at the expense in which it is required. The compounds of the formula (I) can be introduced as part of the additive package. In the absence of the present compounds of the formula (I), the engine oils comprising the components (a) and (c) do not meet or only come close to satisfying the lead corrosion specification defined in ASTM D 4485, as is measured by ASTM D 6594. These are the motor agents that comprise the components (a) and (c), in the absence of the present compounds of formula (I), have excess of about 100 ppm, at about 120 ppm, about 150 ppm, at about 180 ppm, or about 210 ppm as Measured by ASTM D 6594. The invention also relates to a method for preventing corrosion of lead parts which are in the presence of an engine oil composition comprising (a) a base fluid and (c) at least one additive of oil that is aggressive towards lead and is selected from the group consisting of antioxidants, anti-wear additives, dispersants, detergents, anti-foam additives, improved viscosity index, copper passivators, oxidation inhibitors, pour point depressants, demulsifiers and friction modifiers, this method comprises incorporating in the motor oil composition (b) at least one compound of the formula (I), wherein in the absence of the component (b), the composition of engine oil exceeds approximately 100 lead, as measured according to the ASTM D 6594 test. The following example illustrates the invention in more detail. It should not be considered as limiting the present invention in any way.

Example ASTM D 6594 Evaluation of corrosivity of diesel engine oil at 135 ° C. In this test, four specimens of copper, lead, tin and phosphorus, bronze, are immersed in a measured amount of motor oil. The oil, at 135 ° C, is blown with air for 168 hours. When the test is completed, the stressed oil is examined for corrosion and corrosion products. The presence of copper, lead and tin in the used oil is measured by ICP. A result of less than 50 ppm lead in the stressed oil is desirable. A fully formulated, non-corrosive motor oil is used as the base formulation for this example. To demonstrate the effectiveness of the invention, 1.0 weight percent of a friction modifier / corrosion inhibitor, glycerolmonooleate (GMO) and 0.5 weight percent of an extreme pressure / antiwear additive containing sulfur, diternonyltrisulfide (TPSMR 27) , are added separately to the base formulation. Both are tested in accordance with ASTM D 6594 with and without 0.2 weight percent of a compound of the formula (1): 1- (di- (2-ethylhexyl) aminomethyl) 1,2,4-triazole (Irgamet ™ 30, Ciba Specialty Chem.). The results for lead corrosion generated during the test are illustrated in the following Table.

Without IRGA ET 30 With IRGAMET 30 1) Base formulation 75ppm 2) (1) plus 1.0% GMO 358 ppm 29 ppm 3) (1) plus 0.5% TPS 117 ppm 43 ppm 27 Both GMO and TPS 27 contribute to the corrosion of the base formulation making it unsuitable for use. In each case, IRGAMET 30 reduces corrosion significantly to very acceptable levels.

Claims

CLAIMS 1. An engine oil composition that is not aggressive to lead, this composition comprises comprises: (a) a base fluid, (b) at least one compound of the formula (I) and (c) at least one oil additive which is aggressive to lead and which is selected from the group consisting of antioxidants, anti-wear additives, dispersants, detergents, anti-foam additives, viscosity index improvers, copper passivators, inhibitors. of oxidation, pour point depressants, de-emulsifiers and friction modifiers, wherein Ri and R2 are the same or different and are d-C2oalkyl; C3-C2oalkenyl, C5 -Ci2cycloalkyl, C7-Ci3aralkyl or C6-Ci0aril, or Ri and R2, together with the nitrogen atom to which each is connected can each form a 5-, 6- or 7-membered heterocyclic residue or R-? and R2 are a group of the formula R3X [(-R4 -) 0] n (-R4) -, where X is O, S or N, R3 is hydrogen or Ci-C2aalkyl, R is Ci-C12alkylene, n is 0 or an integer from 1 to 6, or one of Ri and R2 is a group of the formula or R2 is a group of the formula (II) and Rx is a group of the formula - [R4] nN (R5) -A- [N (R5) 2] where m is 0 or 1 and when m is zero, A is a group of the formula (II) and when m is 1, A is alkylene or C6-Ci0arylene and R5 is a group of the formula (II), and wherein in the absence of the component (b), the composition of Motor oil exceeds approximately 100 ppm lead as measured according to the ASTM D 6594 test. 2. A composition according to claim 1, characterized in that the compounds of the formula (I) are selected from the group consisting of: 1- (o) - (dimethylaminomethyl) -triazole; 1- (or 4) - (diethylamino methyl) -triazole; 1- (or 4) - (di-iso-propylaminomethyl) -triazole; 1- (or 4) - (di-n-butylaminomethyl) -triazole; 1- (or 4) - (di-n-hexylaminomethyl) -triazole; 1- (or 4) - (di-isooctylaminomethyl) -triazole; 1- (or 4) - (di- (2-ethylhexyl) amino-methyl) -triazole; 1- (or 4) - (di-n-octylaminomethyl) -triazole; 1- (or 4) - (di-n-decylaminomethyl) -triazole; 1- (or 4) - (di-n-dodecylaminomethyl) -triazole; 1- (or 4) - (di-n-octadecylaminomethyl) -triazole; 1- (or 4) - (di-n-eicosylaminomethyl) -triazole; 1- (or 4) - [di- (prop-2'-enyl) aminomethyl] -triazole; l- (or 4) - [di- (but-2 '- enyl) minomethyl] -triazole; 1- (or 4) - [di- (eicos-2'-enyl) aminomethyl] -triazole; 1- (or 4) - (di-cyclohexyl aminomethyl) -triazole 1- (or 4) - (di-benzylaminomethyl) triazole; 1- (or 4) - (di-phenylaminomethyl) triazole; 1- (or 4) - (41-morpholinomethyl) -triazole; 1- (or 4) - (? '- pyrro lidinomethyl) -triazole; 1- (or 4) - (1'-piperidinomethyl) -triazole; 1- (or 4) - (11 -perhydroazepinomethyl) -triazole; 1- (or 4) - (21, 2"-dihydroxyethyl) aminomethyl] -triazole; 1- (or 4) - (dibutoxipropylaminomethyl) -triazole; l- (or 4) - (dibutyl thiopropyl-aminomethyl) -triazole; - (or 4) - (di-butyl aminopropyl -aminomet i 1) -triazole;?,? - bis- (1- or 4-triazolylmethyl) laurylamine;?,? - bis- (1- or 4-triazolylmethyl) oleylamine;?,? - bis- (1- or 4-triazolylmethyl) ethanolamine and N, N,? ', N 1 -tetra- (4-triazolylmethyl) ethylene diamine 3. A composition according to claim 1, characterized because the compound of the formula (I) is 1- (di-isooctylaminomethyl) -1,2,4-triazole or 1- (di- (2-ethylhexyl) amino-methyl) -1,2,4-triazole. A composition according to claim 1, characterized in that the component (b) is present at about 0.01 to about 1.0% by weight based on the engine oil 5. A composition according to claim 1, characterized in that the component (b) it is present in about 0.02 to about 0.5 weight percent, based on the engine oil. 6. A composition according to claim 1, characterized in that the component (b) is present at about 0.03 to about 0.3 weight percent, based on the engine oil. 7. A composition according to claim 1, characterized in that the additives of component (C) are selected from the group consisting of antioxidants., anti-wear additives, detergents, copper passivators and friction modifiers. 8. A composition according to claim 1, characterized in that the additives of the component (C) are selected from the group consisting of sulfur-containing antioxidants, sulfur-containing anti-wear additives, sulfur-containing copper passivators and friction modifiers derived from sulfur. vegetable oil . 9. A composition according to claim 1, characterized in that the additives of component (C) are selected from the group consisting of phenothiazine antioxidants and friction modifiers derived from vegetable oil. 10. A method for preventing corrosion of lead parts that are in the presence of a composition of motor oil comprising (a) a base fluid and (b) at least one oil additive that is aggressive towards lead and which is selected from the group consisting of antioxidants, anti-wear additives, dispersants, detergents, anti-aging additives. foam, viscosity index improvers, copper passivators, oxidation inhibitors, pour point depressants, de-emulsifiers and pressure modifiers, this method comprises incorporating in the motor oil composition (b) at least one compound of the formula ( I) according to claim 1, wherein in the absence of component (b) the engine oil composition exceeds approximately 100 ppm lead as measured according to the ASTM D 6594 test.