FR2909681A1 - COMPOSITION OF ADDITIVES AND COMPOSITIONS OF NEW LUBRICANTS - Google Patents

Abstract

The invention relates to an additive composition comprising a triazole derivative, a nitrogen compound and a phenol compound. It also relates to a lubricant composition comprising a major amount of a base oil and a minor amount of the additives.APPLICATION: Use of the additive composition and the lubricant composition to retard the increase of viscosity in a machine.

Description

The present invention relates to compositions of additives and

  lubricants and methods for their use. More particularly, the present invention relates to an additive composition comprising (i) a triazole derivative, (ii) a nitrogen compound and (iii) a phenol compound. Lubricating oils, used in internal combustion engines and transmissions of automobiles or trucks, are subject to a demanding environment during use. This environment results in the oxidation of the oil, which is catalyzed by the presence of impurities present in the oil, and which is also favored by the high temperatures of the oil during use.

  Oxidation of lubricating oils contributes to sludge formation in oils and degradation of lubricant viscosity characteristics. Oxidation is often limited to some extent by choosing suitable antioxidant additives, which significantly improves the life of the lubricating oils. Antioxidant additives can extend the useful life of the lubricating oil, for example by reducing or preventing unacceptable increases in viscosity and / or unacceptable formation of deposits.

  In addition, protecting the metal surface of an engine against wear degradation by choosing the proper balance of antiwear agents in a lubricating composition can significantly increase the service life of the metal surface. The antiwear agents form a thin film on the metal surfaces which prevents metal-to-metal contact, resulting in a decrease in the degree of wear. A well-known and commonly used anti-wear agent is zinc dialkyldithiophosphate (ZDDP).

  However, the demanding environment to which the lubricating oils are subjected, including high temperatures and / or high pressures, causes decomposition of the ZDDP present in a lubricating oil composition.  Studies have shown that some of the exhaust catalysts can be deactivated by phosphorus, derived primarily from ZDDPs which were the major antiwear agents in passenger car engine oil formulations and diesel engine formulations. performance over the last 50 years.  As a result, it is likely that future engine oils will contain reduced amounts of phosphorus.  In addition, since ZDDP decomposes and releases zinc molecules, these zinc molecules are able to react with other performance additives present in the lubricating composition, which causes the formation of sludge and other materials in the process. particles that may have adverse effects on engine performance.  These undesirable effects of oxidation pose problems in satisfying the requirements of increasingly stringent engine performance.  Simply decreasing the amount of ZDDP is not a practical solution to the problem due to the concomitant reduction of antiwear properties.  Accordingly, it would be desirable for a lubricating oil composition to include improved additives which reduce the oxidative degradation of the lubricating oils.  It has now been discovered that a composition comprising (i) a triazole derivative substituted with an aryl group, (ii) a nitrogen compound and (iii) a phenolic compound can provide an extremely effective system capable of inhibiting oxidation.  According to the present invention there is provided an additive composition comprising (i) a triazole derivative substituted with an aryl group; (ii) a nitrogen compound represented by the formula (I): wherein R1 and R2 are each independently selected from the group consisting of at least one aryl group comprising about 6 to about 30 atoms, a hydrogen atom a halogen atom, a hydroxy group, a hydrocarbyl group, a substituted hydrocarbyl group, an amino group, an amido group, a phosphoro group and a sulfono group; and (iii) a phenolic compound.  In one aspect, there is also provided a lubricant composition comprising a major amount of a base oil and a minor amount of an additive composition comprising (i) a triazole derivative substituted with an aryl group; (ii) a nitrogen compound represented by the formula (I): embedded image wherein R 1 and R 2 are each independently selected from the group consisting of at least one aryl group comprising about 6 to about 30 atoms, a hydrogen atom, a halogen atom, a hydroxyl group, a hydrocarbyl group, a substituted hydrocarbyl group, an amino group, an amido group, a phosphoro group and a sulfono group; and (iii) a phenolic compound.  In addition, there is provided a method for reducing oxidative degradation of a lubricant composition, said method comprising the step of providing a machine with a lubricant composition comprising a major amount of a base oil and a small amount of lubricant. quantity of an additive composition comprising (i) a triazole derivative substituted with an aryl group; (ii) a nitrogen compound represented by the formula (I): wherein R1 and R2 are each independently selected from the group consisting of an aryl group comprising about 6 to about 30 atoms, a hydrogen atom, a halogen atom, a hydroxy group, a hydrocarbyl group, a substituted hydrocarbyl group, an amino group, an amido group, a phosphoro group and a group sulfono; and (iii) a phenolic compound.  In addition, there is provided a method for operating a machine, said method comprising introducing into the machine a lubricant composition comprising a major amount of a base oil; and a minor amount of an additive composition comprising (i) a triazole derivative substituted with an aryl group; (ii) a nitrogen compound represented by the formula (I): wherein R1 and R2 are each independently selected from the group consisting of at least one aryl group comprising from about 6 to about 30 atoms, an atom of hydrogen, halogen, hydroxy, hydrocarbyl, substituted hydrocarbyl, amino, amido, phosphoro and sulfono; and (iii) a phenolic compound.  In addition, there is provided a method for lubricating at least one moving part of a machine, said method comprising contacting said at least one moving part with a lubricant composition comprising a major amount of a base oil; and a minor amount of an additive composition comprising (i) a triazole derivative substituted with an aryl moiety; (ii) a nitrogen compound represented by the formula (I); Wherein R 1 and R 2 are each independently selected from the group consisting of at least one aryl group comprising about 6 to about 30 atoms, a hydrogen atom, a halogen atom, a hydroxy group, a group hydrocarbyl, a substituted hydrocarbyl group, an amino group, an amido group, a phosphoro group and a sulfono group; and (iii) a phenolic compound.  Additional objects and advantages of the present invention will become apparent hereinafter and / or may be established by the practice of the present invention.  The objects and advantages of the present invention will be realized and attained by means of the underlined elements and combinations in particular.  It should be understood that the foregoing general description and the following detailed description are illustrative and explanatory only and are not limiting of the present invention.  The present invention generally relates to a lubricant composition comprising a major amount of a base oil; and a minor amount of an additive composition comprising (i) a triazole derivative substituted with an aryl group; (ii) a nitrogen compound represented by the formula (I): wherein R1 and R2 are each independently selected from the group consisting of at least one aryl group comprising from about 6 to about 30 atoms, one atom hydrogen, halogen, hydroxy, hydrocarbyl, substituted hydrocarbyl, amino, amido, phosphoro and sulfo; and (iii) a phenolic compound.  As used in the present invention, it is understood that the term "dominant amount" refers to an amount greater than or equal to 50% by weight, for example from about 80 to about 98% by weight based on the total weight of the composition.  Further, as used in the present invention, it is understood that the term "small amount" refers to less than 50% by weight based on the total weight of the composition.  As used in the present invention, the term "aromatic" or "aryl", unless otherwise specified, refers to the conventional, substituted or substituted non-aliphatic hydrocarbyl or heterocyclic moieties within this class, for example a cyclic hydrocarbyl substituent. or polyunsaturated heterocyclic, usually aromatic, which may comprise a single ring or multiple rings (up to three rings) which are fused to each other or covalently bound.  Conventional aromatic hydrocarbyl groups include phenyl, naphthyl, biphenylenyl, phenanthrenyl, phenalenyl and similar groups.  These groups are optionally substituted with one or more hydrocarbyl substituents.  Also included groups are aryl groups substituted with other aryl groups, for example the biphenyl group.  The heterocyclic aryl or aromatic groups are unsaturated cyclic groups containing carbon atoms in the ring and further containing one or more heteroatoms, which are usually oxygen, nitrogen, sulfur and / or phosphorus, such as pyridyl, thienyl, furyl, thiazolyl, pyranyl, pyrrolyl, pyrazolyl, imidazolyl, pyrazinyl, thiazolyl and similar groups.  These groups are optionally substituted with one or more substituents such as hydroxy substituents, optionally substituted lower alkyl, optionally substituted lower alkoxy, amino, amido, ester groups and carbonyl groups (eg, aldehyde or ketone groups).  As used in the present invention, the term "alkaryl", unless otherwise specified, refers to an alkyl group substituted with the conventional or non-substituted conventional non-aliphatic hydrocarbyl or heterocyclic moieties described above.  Typical aryl groups include phenyl, naphthyl, benzyl and similar groups.  These groups are optionally substituted with one or more substituents such as hydroxy, optionally substituted alkyl, optionally substituted alkoxy, amino, amido, ester groups, and carbonyl groups (eg, aldehyde or keto groups).  As used in the present invention, the terms "hydrocarbon" and "hydrocarbyl" or the term "hydrocarbon based" indicate that the described moiety has a predominantly hydrocarbon character in the context of the present invention.  These groups include groups that are of a purely hydrocarbon nature, which means that they contain only carbon and hydrogen.  They may also include moieties containing substituents or atoms that do not alter the predominantly hydrocarbon character of the moiety.  These substituents may include halo, alkoxy, nitro, and the like.  These groups may also contain heteroatoms.  Suitable heteroatoms will be apparent to those skilled in the art and include, for example, sulfur, nitrogen, oxygen and phosphorus.  As a result, although remaining predominantly hydrocarbon in the context of the present invention, these groups may contain atoms other than carbon atoms, present in a chain or ring otherwise constituted by carbon atoms.  A triazole derivative suitable for use in the compositions of the present invention may be any triazole substituted with an aryl group.  In certain embodiments, the triazole derivative is an aryl-substituted 1,2,3-triazole derivative.  In other embodiments, the triazole derivative is an aryl-substituted 1,2,4-triazole derivative.  In another embodiment, the triazole derivative is not an alkyl-bis-3-amino-1,2,4-triazole.  By way of example, the triazole derivative may be substituted with a substituted or unsubstituted aryl group comprising a single ring or multiple rings, for example, covalently linked rings.  Non-limiting examples of substituted aromatic groups comprising covalently linked rings include biphenyl, 1,1'-binaphthyl, p, p'-bitolyl, biphenylenyl and similar groups.  As another example, the aryl group may comprise fused multiple nuclei.  Non-limiting examples of aryl groups comprising fused multiple nuclei include naphthyl, anthryl, pyrenyl, phenanthrenyl, phenalenyl and similar groups.  As a further example, the aryl moiety may comprise a single ring covalently linked to the triazole.  Non-limiting examples of aryl groups comprising a single ring covalently linked to triazole include the phenyl group and similar groups.  As another example, the aryl group may comprise a single ring fused with the triazole.  Non-limiting examples of aryl groups comprising a single ring fused with triazole include benzotriazole and tolyltriazole moieties.  An example of a commercially available triazole derivative which can be conveniently used in the present invention is benzotriazole, which is a slightly dirty white substance having a melting point in the range of 95%. at 99 ° C., a flash point of 170 ° C. and a water solubility of 25 g / l at 20 ° C.  The triazole derivative can be combined / reacted / mixed with other additives to increase its solubility in a composition.  In one embodiment, the triazole derivative may be represented by the formula (II) below: ## STR2 ## wherein R 3 is selected from the group consisting of a hydrogen atom and a group wherein R4 is selected from the group consisting of hydrogen, alkyl of from about 1 to about 24 carbon atoms, and substituted hydrocarbyl.  In another embodiment, the R3 and R4 groups of the triazole derivative represented by the formula (II) may each independently comprise from about 1 to about 16 carbon atoms.  The triazole derivative may be present in the lubricant compositions and additive compositions disclosed in any effective amount, which may be readily determined by those skilled in the art.  In one embodiment, the lubricating composition of the present invention may comprise about 0.05% by weight to about 0.5% by weight and, for example, about 0.1% by weight to about 0.3% by weight. weight of the triazole derivative, relative to the total weight of the lubricating composition.  In another embodiment, the additive composition of the present invention may comprise about 0.48% by weight to about 5% by weight of the triazole derivative, based on the total weight of the additive composition.  The described composition may also include a nitrogen compound for various uses.  There is no particular limitation on the type of nitrogen compound that can be used in the described composition of the present invention.  In general, a nitrogen compound which can be suitably used in the present invention can be represented by the following formula (I): ## STR2 ## wherein R 1 and R 2 are each independently selected from the group consisting of an aryl group comprising about 6 to about 30 atoms, a hydrogen atom, a halogen atom, a hydroxy group, a hydrocarbyl group, a substituted hydrocarbyl group, an amino group, an amido group, a phosphoro group and a group sulphono.  For example, R1 and R2 may each independently comprise an aryl group of from about 6 to about 30 carbon atoms.  Nonlimiting examples of aryl groups which may represent R 1 and R 2 include phenyl, benzyl, naphthyl and alkaryl groups.  As another example, R 1 and R 2 may each independently comprise an alkaryl group, such as an alkylphenyl or alkylnaphthyl group, wherein the alkyl group comprises from about 4 to about 30 carbon atoms and, for example, about 4 to about 12 carbon atoms.  As a further example, R1 and R2 may each independently comprise a substituted or unsubstituted aryl group.  Non-limiting examples of substituents for the aryl group may include an alkyl group comprising about 1 to about 20 carbon atoms, hydroxyl, carboxyl and nitro groups.  As another example, R 1 and R 2 may each independently represent a benzyl, phenyl or alkyl-substituted naphthyl group.  Other non-limiting examples of suitable nitrogen compounds include phenylamine; diphenylamine; triphenylamine; various phenylamines, diphenylamines and alkylated triphenylamines; N, N'-bis (4-aminophenyl) alkylamine; 3-hydroxydiphenylamine; N-phenyl-1,2-phenylenediamine; N-phenyl-1,4-phenylenediamine; dibutyldiphenylamine; dioctyldiphenylamine; dinonyldiphenylamine; phenyl-alphanaphthylamine; phenyl-beta-naphthylamine; diheptyldiphenylamine; and p-oriented styrenic diphenylamine.  Additional nonlimiting examples of suitable nitrogen compounds and processes for their preparation include those in U.S. Patent No. 6,218,576, the disclosure of which is incorporated by reference in the present invention.  The nitrogen compounds used in the present invention may comprise a structure other than that shown above in formula (I) which represents a single nitrogen atom in the molecule.  Thus, the nitrogenous compound may comprise a different structure, provided that said at least one nitrogen atom carries at least one aryl group attached to it, for example as in the case of various diamines comprising a carbon atom 2909681. secondary nitrogen and an aryl group attached to one of the nitrogen atoms.  The nitrogen compounds used in the present invention may have antioxidant properties in the described compositions when used alone or in combination as described in the present invention.  Nitrogen compounds used in the present invention must be soluble in a final lubricant composition.  The amount of nitrogen compounds in the lubricating compositions may vary depending on specific needs and specific applications.  In one embodiment, the lubricating composition of the present invention may comprise from about 0.2% by weight to about 1.2% by weight and, for example, from about 0.4% by weight to about 1.0%. by weight of the nitrogenous compound, relative to the total weight of the lubricating composition.  In another embodiment, the additive compositions of the present invention may comprise about 2% by weight to about 12% by weight of the nitrogen compound, based on the total weight of the additive composition.  A phenolic compound which can be suitably used in the compositions of the present invention can be any phenol, provided that it is soluble in a lubricant composition.  For example, the phenol compound may be substituted for one or both of the ortho positions.  Examples of such phenol compounds include 2-tert-butylphenol, 2-ethyl-6-methylphenol, 2,6-di-tert-butylphenol, 2,6-di-tert-butyl-4- methylphenol, 2,2'-methylenebis-4,6-di-tert-butylphenol, 4,4'-methylene-bis (2,6-di-tert-butylphenol), 2,2 '-propylidene-bis- (6-tert-butyl-4-methylphenol) and mixtures thereof.  As another example, the phenol compound may be an esterified reaction product of a phenol and an unsaturated carboxylic acid having at least one double bond.  In one embodiment, the phenolic compound can be represented by the formula (III) below R7 wherein R5 and R6 are each independently selected from the group consisting of hydrogen, an alkyl group comprising from about 1 to about 24 carbon atoms, and a cyclic group comprising about 3 to about 12 carbon atoms, and R7 is selected from the group consisting of hydrogen, alkyl, aryl, alkaryl, and (CH2) nOOOR8, wherein represents an integer from 1 to 4 inclusive and R8 represents an alkyl group comprising from about 1 to about 18 carbon atoms.  The cyclic group may include polycyclic ring systems, such as bicyclic groups and tricyclic groups.  In another embodiment, the phenol compound may be an oligomer.  In a further embodiment, the phenol compound may be an esterified reaction product of 2,6-di-tert-butylphenol and acrylic acid.  An example of a commercially available phenol compound which can be suitably used in the present invention is 3,5-di-tert-butyl-4-hydroxyphenol propionate, which is a clear yellow to amber liquid having a viscosity of 120 mm 2 / s at 40 ° C. and a density of 0.96 g / cm 2 at 20 ° C.  Another example of a commercially available phenol compound which can be suitably used in the present invention is a high molecular weight oligomer of a butyl reaction product of p-cresol and dicyclopentadiene. which consists of a light powder or yellowish flakes with a melting point of 105 C.  An example of such an oligomer is represented by the formula (IV) below: ## EQU1 ## where n represents any integer greater than 10 such as, for example, an integer greater than about 100 or in which other examples, an integer greater than about 1000.  The phenol compound can be present in the lubricant compositions and additive compositions described in any effective amount, which can be readily determined by those skilled in the art.  In one embodiment, the lubricating composition of the present invention may comprise about 0.05% by weight to about 1.2% by weight and, for example, about 0.1% by weight to about 0.8% by weight. of the phenolic compound, relative to the total weight of the lubricating composition.  In another embodiment, the additive composition of the present invention may comprise about 0.5% by weight to about 12% by weight of the phenolic compound, based on the total weight of the additive composition.  The compositions of the present invention may optionally contain additives, such as phosphorus-containing compounds, dispersants, ash-containing detergents, ashless detergents, overbased detergents, pour point depressants, modifiers, and the like. viscosity indexes, ash-containing friction modifiers, ashless friction modifiers, nitrogen-containing friction modifiers, nitrogen-free friction modifiers, esterified friction modifiers, extreme pressure agents, antirust additives, antioxidants, corrosion inhibitors, antifoam agents, titanium compounds, titanium complexes, soluble organic molybdenum compounds, soluble organic molybdenum complexes, boron-containing compounds, boron and their associations.  In one aspect, the phosphorus-containing compounds, for example, zinc dialkyldithiophosphates, may be present in the lubricant composition in an amount sufficient to provide from about 100 to about 1000 ppm by weight of total phosphorus in the lubricant composition.  In another aspect, the phosphorus-containing compounds may be present in an amount sufficient to provide from about 600 to about 800 million parts by weight of total phosphorus of the lubricant composition.  In a further aspect, the compositions may comprise various amounts of at least one titanium-containing compound, depending on the needs and requirements of the application.  Base oils suitable for use in the formulation of the disclosed compositions may be selected from any of synthetic or mineral oils or mixtures thereof.  Mineral oils include animal oils and vegetable oils (eg, castor oil, lard oil) as well as other mineral lubricating oils such as liquid petroleum oils and mineral lubricating oils treated with petroleum oils. a solvent or treated with an acid, paraffinic type, naphthenic type or mixed paraffinic-naphthenic type.  Oils derived from coal or shale are also suitable.  In addition, oils derived from a gas-liquid process are also suitable.  The base oil may be present in a major amount, it being understood that the term "dominant amount" refers to an amount greater than or equal to 50%, eg, about 80 to about 98% by weight of the lubricant composition.  The base oil usually has a viscosity, for example, from about 2 to about 150 cSt and, by way of further example, from about 5 to about 15 cSt at 100 C.  Thus, the base oils can usually have a viscosity in the range of about SAE to about SAE 250 and, more usually, in the range of about SAE 20W to about SAE 50.  Suitable automotive oils also include mixed grades such as 15W-40, 20W-50, 75W-140, 80W-90, 85W-140, 85W-90, and similar grades.  Non-limiting examples of synthetic oils include hydrocarbon oils such as polymerized and interpolymerized olefins (eg polybutylenes, polypropylenes, propylene-isobutylene copolymers and similar polymers); polyalphaolefins such as poly- (1-hexenes), poly (1-octenes), poly (1-decenes) and similar polymers, and mixtures thereof; alkylbenzenes (e.g., dodecylbenzenes, tetradecylbenzenes, di-nonylbenzenes, di- (2-ethylhexyl) benzenes and the like); polyphenyls (e.g., biphenyls, terphenyl, alkylpolyphenyls and the like); alkylated diphenyl ethers and alkylated diphenyl sulfides and their derivatives, analogs and homologs and similar compounds.  Alkylene oxide polymers and interpolymers and derivatives thereof wherein the terminal hydroxy groups have been modified by esterification, etherification or the like are another class of known synthetic oils that can be used.  These oils are exemplified by the oils prepared by the polymerization of ethylene oxide or propylene oxide, the alkyl and aryl ethers of these polyoxyalkylene polymers (for example, polyisopropylene glycol methyl ether having a weight of average molecular weight of about 1000, polyethylene glycol diphenyl ether having a molecular weight of about 500 to 1000, polypropylene glycol diethyl ether having a molecular weight of about 1000 to 1500 and similar ethers); or their mono- and polycarboxylic esters, for example the acetic acid esters, the C 3 to C 8 mixed fatty acid esters or the C 3 oxy acid diester of tetraethylene glycol.  Another class of synthetic oils that can be used include dicarboxylic acid esters (eg, phthalic acid, succinic acid, alkyl succinic acids, alkenyl succinic acids, maleic acid, azelaic acid, suberic acid, sebacic acid, fumaric acid, acid adipic acid, linoleic acid dimer, malonic acid, alkyl malonic acids, alkenyl malonic acids and the like) with various alcohols (eg butyl alcohol, hexyl alcohol, dodecyl alcohol, 2-ethylhexyl alcohol, ethylene glycol, diethylene glycol monoether, propylene glycol and similar alcohols).  Specific examples of these esters include dibutyl adipate, di (2-ethylhexyl) sebacate, di-n-hexyl fumarate, dioctyl sebacate, diisooctyl azelate, diisodecyl azelate, dioctyl phthalate, didecyl phthalate, dieicosyl sebacate, linoleic acid dimer 2-ethylhexyl diester, the complex ester formed by reacting one mole of sebacic acid with two moles of tetraethylene glycol and two moles of 2-ethylhexanoic acid, and similar esters.  Esters useful as synthetic oils also include those prepared from C5 to C18 monocarboxylic acids and polyols and polyol ethers, such as neopentyl glycol, trimethylolpropane, pentaerythritol, dipentaerythritol, tripentaerythritol and the like. similar compounds.  Accordingly, the base oil that can be used to prepare the compositions described in the present invention can be selected from any of the base oils of Groups I to IV specified in the Base Oil Interchangeability Guidelines. American Petroleum Institute (API).  These groups of base oils are as follows: Group I contains less than 90% saturated compounds and / or more than 0.03% sulfur and a viscosity number greater than or equal to 80 and less than 120; Group II contains 90% or more of saturated compounds and less than or equal to 0.03% sulfur and a viscosity number greater than or equal to 80 and less than 120; Group III contains 90% or more saturated compounds, 0.03% sulfur or less, and a viscosity number greater than or equal to 120; Group IV consists of polyalphaolefins (PAO); and Group V includes all other base oils not included in Group I, II, III or IV.  The test methods used in the definition of the above-mentioned groups are ASTM D2007 for saturated compounds; ASTM D2270 method for viscosity index; and one of ASTM methods D2622, 4294, 4927 and 3120 for sulfur.  Group IV base oils, i.e. polyalphaolefins (PAOs), comprise hydrogenated oligomers of an alphaolefin, the most important oligomerization processes being free radical processes, Ziegler catalysis and catalysis. cationic Friedel-Crafts.  The polyalphaolefins usually have viscosities in the range of 2 to 100 cSt at 2909681, for example 4 to 8 cSt at 100 C.  They may be, for example, branched-chain or straight-chain alphaolefin oligomers having from about 2 to about 30 carbon atoms, non-limiting examples of which include poly-1-butenes, and poly-1-decene.  Of these, and mixtures thereof, which relate to the remainder of the above base oil, a "Group I base oil" also includes a Group I base oil with which one or more base oils of one or more Other groups may be mixed, provided that the resulting mixture has characteristics corresponding to those specified above for Group I base oils.  Examples of base oils include Group I base oils and Group II base oil blends with a Group I bright stock high viscosity base lubricating oil.  Base oils that can be suitably used in the present invention can be prepared using a variety of different processes including, but not limited to, distillation, solvent refining, hydrogen treatment, oligomerization esterification and regeneration.  The base oil can be an oil derived from hydrocarbons synthesized by the Fischer-Tropsch process.  Hydrocarbons synthesized by the Fischer-Tropsch process can be prepared from a synthesis gas containing H 2 and CO using a Fischer-Tropsch catalyst.  These hydrocarbons usually require additional processing in order to be useful as the base oil.  For example, the hydrocarbons can be hydroisomerized using the methods described in U.S. Patent No. 6,103,099 or 6,180,575; Polypropenes, polyisobutenes, poly-1-hexenes, poly-1-octenes homopolymers, interpolymers included.  In this referenced 2909681 hydrocracked and hydroisomerized using the methods described in U.S. Patent No. 4,943,672 or 6,096,940; dewaxed using the methods described in U.S. Patent No. 5,882,505; Or hydroisomerized and dewaxed using the methods described in U.S. Patent No. 6,013,171; 6,080,301; or 6,165,949.  Unrefined oils and refined oils and regenerated, mineral or synthetic oils (as well as mixtures of two or more of any of these oils) of the type described above may be used in based.  Unrefined oils are those obtained directly from a mineral or synthetic source without further purification treatment.  For example, a shale oil obtained directly from pyrogenation operations, a petroleum oil obtained directly from primary distillation or an ester oil obtained directly by an esterification process and used without further processing would be an unrefined oil. .  Refined oils are similar to unrefined oils except that they have been further processed in one or more purification steps to improve one or more properties.  Most of these purification techniques are known to those skilled in the art, examples being solvent extraction, secondary distillation, acid or base extraction, filtration, percolation, and techniques. Similar.  The regenerated oils are obtained by methods similar to those used to obtain refined oils applied to refined oils that have already been used in service.  These regenerated oils are also known as reprocessed or reprocessed oils and are often further processed by techniques for the removal of spent additives, contaminants and oil degradation products.  In various embodiments, there is disclosed a method for retarding the occurrence of an increase in viscosity in a lubricant composition.  As used in the present invention, it is understood that the term "retarding the onset of a viscosity increase" refers to the delay in the onset of an increase in the viscosity of a lubricant composition due to the oxidation process, as compared to a composition which is devoid of the compositions of the present invention, comprising a triazole derivative substituted with an aryl group, a nitrogen compound and a phenolic compound, as described in the present invention.  The method for delaying the onset of viscosity increase in a lubricant composition may comprise the step of providing a machine with a lubricant composition comprising a major amount of a base oil; and a small amount of an additive comprising (i) a triazole derivative substituted with an aryl group; (ii) a nitrogen compound represented by the formula (I): wherein R1 and R2 are each independently selected from the group consisting of at least one aryl group comprising about 6 to about 30 atoms, hydrogen, halogen, hydroxy, hydrocarbyl, substituted hydrocarbyl, amino, amido, phosphoro and sulfono; and (iii) a phenolic compound.  In various embodiments, there is also described a method for lubricating at least one moving part of a machine.  As used in the present invention, it is understood that the term "at least one moving part of a machine" refers to at least a portion of a machine which can be set in motion, comprising a gear, a piston, a bearing, a rod, a spring, a camshaft, a crankshaft and the like.  The method for lubricating at least one moving part of a machine comprising contacting said at least one moving part with a lubricant composition comprising a major amount of a base oil and a minor amount of the additives described.  In other embodiments, there is also disclosed a method for operating a machine, comprising introducing into the machine a lubricant composition comprising a major amount of a base oil and a small amount of the additive composition described.  The machine in the processes described may be selected from the group consisting of internal combustion engines with spark ignition and compression ignition.  In addition, said at least one moving part can be chosen between a gear, a piston, a bearing, a rod, a spring, a camshaft, a crankshaft, etc.  The lubricant composition can be any composition that is effective for lubricating a machine.  In one aspect, the composition is selected from the group consisting of oils for passenger car engines, oils for medium speed diesel engines and oils for high efficiency diesel engines.  EXAMPLES The following examples illustrate the present invention and its advantageous properties.  In this example, and also elsewhere in the present invention, all parts and percentages are by weight unless otherwise indicated.  The compositions according to the present invention have been formulated with an aryl substituted triazole derivative, a nitrogen compound, a phenolic compound and a base composition, as indicated on the following. Tables 1 and 2.  The triazole derivative used in Examples of Composition 1 and 2 was a commercially available tolyltriazole (Cobratec TT-100, PMC Specialties Group, Cincinnati, Ohio).  The nitrogenous compound was an alkylated diphenylamine (Hi-TEC 7190, Afton Chemical Corporation, Richmond, VA) and the phenolic compound was a commercially available transesterified phenol (Ethanox 4716, Albemarle Corporation, Richmond, VA).  A comparative example was formulated without a triazole derivative, as shown in Table 3, using the same nitrogen compound, phenolic compound and base composition as in Composition Examples 1 and 2.  TABLE 1 Example of composition 1 with an antioxidant system CONSTITUENT% by weight Triazole 0.2 Arylamine 0.8 Phenolic antioxidant n 1 0.1 ZDDP 0.08 Composition of base remaining TABLE 2 - Example of composition 2 with antioxidant system COMPONENT% by weight Triazole 0.2 Arylamine 0.4 Phenolic antioxidant n 2 0.2 ZDDP 0.08 Base composition rest 36.5 TEOST MHT-4 (mg) 31.1 TEOST MHT-4 (mg) 5 10 TABLE 3 Comparative Example of Composition 3 CONSTITUENT% by Weight Triazole-Arylamine 0.8 Phenolic Antioxidants No. 1 0.1 ZDDP 0.05 Base Composition The Rest The Base Composition of Examples of Compositions at 3 included the ingredients in the intervals of

  concentrations indicated for base composition 2 of Table 4 below. The base composition was formulated with a GF-5 base oil indicated by the International Lubricants Standardization and Approval Committee (ILSAC), which in this example was a SAE grade engine oil, type 5W-30. All values are in percent by weight. TABLE 4 Base 1 Base 2 Examples of base compositions (% by weight) (% by weight) Dispersing system 0.15-15 1-10 Metal detergents 0.1-15 0.2-8 Corrosion inhibitors 0-5 0 -2 Dihydrocarbyl-dithiophosphate metal 0.1-6 0.1-4 Defoaming agents 0-5 0.001-0.15 Friction modifiers 0-5 0-2 Additional anti-wear agents 0-1.0 0-0.8 Lowering agents pour point 0.01-5 0.01-1.5 Viscosity modifier 0.01-10 0.25-7 Base oil balance rest Thermo-oxidation test of engine oil (TEOST MHT-4) was carried out on the examples of compositions 1 and 2 and the example of comparative composition 3. The TEOST MHT-4 test is a reference test in 48 TEOST MHT-4 (mg) 2909681 25 Lubricants industry for evaluation of oxidation characteristics and formation of carbon deposits of lubricants. The test is designed to simulate the formation of high temperature deposits in the area of the piston rings of modern engines. The test utilizes a patented apparatus (U.S. Patent No. 5,401,661 and U.S. Patent No. 5,287,731) with the MHT-4 protocol which is a relatively recent modification of this test. A smaller amount of deposit indicates a better limitation of oxidation, which delays the onset of viscosity increase in a lubricant composition. The results demonstrate the advantage of using the described composition to delay the onset of viscosity increase in a lubricant composition. As indicated by the preceding example, the composition example 1 comprising the described antioxidant system presented a numerical evaluation value of the 36.5 mg TEOST MHT-4 test. Similarly, the composition example 2 comprising the described antioxidant system presented a numerical evaluation value of the 31.1 mg TEOST MHT-4 test. By comparison, the composition example 3 which did not include the described composition showed a much higher numerical evaluation value of the TEOST MHT-4 test, equal to 48 mg. Thus, it can be seen that the described composition surprisingly and significantly reduces the deposits on the pistons, which delays the onset of the increase in viscosity in a lubricant composition.

It is believed that the examples are presented for purposes of illustration only and are not intended to limit the scope of the present invention. As will be understood by those skilled in the art, the particular ingredients used and the concentrations of the ingredients may differ from those used in the examples. For example, prophetic examples are contemplated which use ingredients at concentrations outside the ranges of base composition 2, for example in the ranges given for base composition 1 of Table 4 above.

It will be appreciated that, in the manner used in the present invention, the singular forms "a", "a", "the" and "the" include plural references unless expressly and unequivocally limited to a reference. Thus, for example, the reference to "an antioxidant" includes the reference to two or more different antioxidants. As used in the present invention, the term "includes" and its grammatical variants are intended to be non-limiting, so that the mention of elements in a list is not made to the exclusion of other elements. similar that can be used in place of, or added to, the enumerated elements. For the purposes of the present invention, unless otherwise indicated, it is to be understood that all numerical values expressing quantities, percentages or proportions and the other numerical values used in the present invention are modified in all cases by the term " about". Accordingly, unless otherwise indicated, the numerical parameters indicated in the present invention are approximations which may vary depending on the desired properties sought to be achieved in the present invention. In any case, and not as an attempt to limit the application of the doctrine of equivalents to the scope of the present invention, each numerical parameter must be considered at least in light of the number of significant digits indicated and by applying usual rounding techniques. It goes without saying that the present invention has been described for explanatory purposes, but in no way limiting, and that many modifications can be made without departing from its scope.

Claims (30)

  An additive composition, characterized in that it comprises: (i) a triazole derivative substituted with an aryl group; (ii) a nitrogen compound represented by the formula (I): wherein R1 and R2 are each independently selected from the group consisting of at least one aryl group having 6 to 30 atoms, an atom of hydrogen, halogen, hydroxy, hydrocarbyl, substituted hydrocarbyl, amino, amido, phosphoro and sulfono; and (iii) a phenolic compound. 20   2. Additive composition according to claim 1, characterized in that the triazole derivative is substituted with a substituted aryl group, comprising multiple rings.   3. Additive composition according to Claim 1, characterized in that the triazole derivative is substituted with a substituted aryl group comprising a single ring.   4. Additive composition according to claim 1, characterized in that the triazole derivative is represented by the formula (II): wherein R3 is selected from the group consisting of hydrogen and a group alkyl having 1 to 24 carbon atoms and wherein R4 is selected from the group consisting of hydrogen, alkyl of 1 to 24 carbon atoms, and substituted hydrocarbyl.   5. Additive composition according to claim 1, characterized in that the triazole derivative is not an alkyl-bis-3-amino-1,2,4-triazole.   6. Additive composition according to claim 1, characterized in that the phenolic compound comprises an esterified reaction product of 2,6-di-tert-butylphenol and an unsaturated carboxylic acid comprising at least one double bond and 3 to 24 carbon atoms.   An additive composition according to claim 1, characterized in that the phenolic compound is represented by the formula (III): R7 (III) wherein R5 and R6 are each independently selected from the group consisting of a hydrogen atom an alkyl group having 1 to 24 carbon atoms and a cyclic group having 3 to 12 carbon atoms and R7 is selected from the group consisting of hydrogen, alkyl, aryl, alkaryl and (CH2) n- COOR5, wherein n represents an integer from 1 to 4 inclusive and R8 represents an alkyl group having 1 to 18 carbon atoms. 25 30 2909681 29   8. Additive composition according to claim 1, characterized in that the phenolic compound is 3,5-di-tert-butyl-4-hydroxyphenol propionate.   9. Additive composition according to claim 1, characterized in that the triazole derivative is present in an amount ranging from 0.48% by weight to 5% by weight.   10. Additive composition according to claim 1, characterized in that the nitrogen compound is present in an amount in the range of 2% by weight to 12% by weight.   An additive composition according to claim 1, characterized in that the phenolic compound is present in an amount ranging from 0.5 wt% to 12 wt%.   An additive composition according to claim 1, characterized in that it further comprises at least one additive selected from the group consisting of phosphorus-containing compounds, dispersants, ash-containing detergents, ashless detergents , overbased detergents, pour point depressants, viscosity index improvers, ash containing friction modifiers, ashless friction modifiers, nitrogen friction modifiers, friction modifiers without nitrogen, esterified friction modifiers, extreme pressure agents, rust inhibitors, additional antioxidants, corrosion inhibitors, defoamers, titanium compounds, titanium complexes, soluble organic molybdenum compounds, organic soluble molybdenum compounds, boron-containing compounds and complexes containing re.   A lubricant composition, characterized in that it comprises: a major amount of a base oil and a minor amount of an additive composition comprising (i) a triazole derivative substituted with an aryl group ; (Ii) a nitrogen compound represented by the formula (I): wherein R1 and R2 are each independently selected from the group consisting of at least one aryl group having 6 to 30 atoms, a hydrogen atom, a halogen atom, a hydroxy group, a hydrocarbyl group, a substituted hydrocarbyl group, an amino group, an amido group, a phosphoro group and a sulfono group; and (iii) a phenolic compound. 20   14. Lubricant composition according to claim 13, characterized in that the triazole derivative is present in an amount in the range of 0.05% by weight to 0.5% by weight.   Lubricant composition according to claim 13, characterized in that the triazole derivative is present in an amount in the range of 0.1% by weight to 0.3% by weight.   Lubricant composition according to Claim 13, characterized in that the nitrogen compound is present in the range of 0.2% by weight to 1.2% by weight.   Lubricant composition according to claim 13, characterized in that the nitrogen compound is present in an amount ranging from 0.4% by weight to 1.0% by weight. (1) 2909681 31   Lubricant composition according to claim 13, characterized in that the phenolic compound is present in an amount ranging from 0.05 wt. To 1.2 wt. 5   19. Lubricant composition according to claim 13, characterized in that the phenolic compound is present in an amount ranging from 0.1 wt.% To 12 wt.   20. Lubricant composition according to claim 13, characterized in that it further comprises at least one additive selected from the group consisting of phosphorus-containing compounds, dispersants, ash-containing detergents, ashless detergents, overbased detergents, pour point depressants, viscosity index improvers, ash-containing friction modifiers, ashless friction modifiers, nitrogen-containing friction modifiers, friction modifiers without abrasives; nitrogen, esterified friction modifiers, extreme pressure agents, rust inhibitors, additional antioxidants, corrosion inhibitors, antifoaming agents, titanium compounds, titanium complexes, soluble organic molybdenum compounds, soluble organic molybdenum complexes, boron-containing compounds and boron.   21. Lubricant composition according to claim 13, characterized in that it further comprises at least one compound containing titanium. 30   22. Lubricant composition according to claim 13, characterized in that it further comprises a phosphorus-containing compound in an amount in the range of 100 to 1000 millionths of total phosphorus in the lubricant composition.   23. Lubricant composition according to claim 22, characterized in that the phosphorus-containing compound is present at a concentration in the range of 600 to 800 millionths of total phosphorus in the lubricant composition.   24. Lubricant composition according to claim 13, characterized in that it is selected from the group consisting of a motor vehicle oil, a medium speed diesel engine oil and a high efficiency diesel engine oil.   25. A process for retarding the occurrence of an increase in viscosity in a lubricant composition, characterized in that it comprises the step of: providing a machine with a lubricant composition comprising a major amount of an oil basic ; and a minor amount of an additive composition comprising: (i) a triazole derivative substituted with an aryl group; (ii) a nitrogen compound represented by the formula (I): wherein R 1 and R 2 are each independently selected from the group consisting of at least one aryl group having 6 to 30 atoms, a group consisting of hydrogen, halogen, hydroxy, hydrocarbyl, substituted hydrocarbyl, amino, amido, phosphoro and sulfono; and (iii) a phenolic compound.   26. A process according to claim 25, characterized in that the machine is selected from the group consisting of spark ignition internal combustion engines and compression ignition internal combustion engines.   27. A method for lubricating at least one moving part of a machine, characterized in that it comprises: bringing said at least one moving part into contact with a lubricant composition comprising a dominant amount of a base oil. ; and a minor amount of an additive composition comprising: (i) a triazole derivative substituted with an aryl group; (ii) a nitrogen compound represented by the formula (I): wherein R1 and R2 are each independently selected from the group consisting of at least one aryl group having 6 to 20 atoms, an atom of hydrogen, halogen, hydroxy, hydrocarbyl, substituted hydrocarbyl, amino, amido, phosphoro and sulfono; and (iii) a phenolic compound.   28. The method of claim 27, characterized in that the machine is selected from the group consisting of spark ignition internal combustion engines and compression ignition internal combustion engines.   29. A method of operating a machine, characterized by comprising: introducing into the machine a lubricant composition comprising a major amount of a base oil; and a minor amount of an additive composition comprising: (i) a triazole derivative substituted with an aryl moiety; (ii) a nitrogen compound represented by the formula (I): wherein R 1 and R 2 are each independently selected from the group consisting of at least one aryl group having 6 to 30 atoms a hydrogen atom, a halogen atom, a hydroxy group, a hydrocarbyl group, a substituted hydrocarbyl group, an amino group, an amido group, a phosphoro group and a sulfono group; and (iii) a phenolic compound.   30. A method according to claim 29, characterized in that the machine is selected from the group consisting of spark ignition internal combustion engines and compression ignition internal combustion engines.