MXPA98009520A - Biodegradable lubricant composition of triglycerides and soluble copper in ace - Google Patents

Abstract

The present invention relates to a lubricant composition comprising a triglyceride oil lubricant and an oil-soluble copper antioxidant compound. The oil soluble copper compounds are antioxidants especially effective for triglycerides. The lubricant composition can include soluble zinc compounds that reduce wear and / or soluble antimony compounds that reduce wear and can function as antioxidant adjuvants that reduce the amount of oil soluble copper required. The preferred zinc and antimony compounds are zinc anti-wear / antioxidant dithiophosphate, and anti-rumidium antimicryldithiocarbamate antioxidant adjuvants.

Description

BIODEGRADABLE LUBRICANT COMPOSITION OF TRIGLYCERIDES AND SOLUBLE COPPER IN OIL DESCRIPTION OF THE INVENTION The present invention relates to biodegradable lubricant compositions made from vegetable oil triglycerides and oil soluble copper compounds. Lubricating compositions can be used for the lubrication of engines, transmissions, gearboxes and for hydraulic applications. The specified compounds of optional oil-soluble antimony can reduce the amount of copper needed to impart oxidation resistance. Vegetable oil triglycerides have been available for use in food and cooking products. Many of these vegetable oils contain natural antioxidants such as phospholipids and sterols that prevent them. oxidation during storage. Triglycerides are considered the product of esterification of glycerol with 3 carboxylic acid molecules. The amount of unsaturation in carboxylic acids affects the susceptibility of triglyceride to oxidation. Oxidation can include reactions that bind two or more triglycerides together through reactions of atoms near unsaturation. These reactions can form a material with higher molecular weight that can become insoluble and discolored, for example, mud. Oxidation can also result in cleavage of the ester linkage or other internal cleavage of the triglycerides. Triglyceride fragments of the cleavage, having lower molecular weight, are more volatile. The carboxylic acid groups produced from the triglyceride turn the acidic lubricant. Aldehyde groups can also be generated. The groups . carboxylic acids have attraction to oxidized metals and can solubilize them in oil promoting the removal of metal from some surfaces. Due to oxidation problems with triglycerides, most commercial lubricants are formulated from petroleum distillates that have lower amounts of unsaturation rendering them resistant to oxidation. Petroleum distillates need additives to reduce wear, reduce oxidation, lower the pour point and change the viscosity index (to adjust the viscosity at high or low temperature) etc. Petroleum distillates are resistant to biodegradation and the additives used to adjust their characteristics (often containing metals and reactive compounds) additionally detract from the biodegradability of the lubricant used. Synthetic ester lubricants that do not have unsaturation or have low unsaturation in carbon-to-carbon bonds are used in premium engine oils because of their desirable properties. However, the acids and alcohols used to make synthetic ester generally derive from petroleum distillates and, therefore, are not from a renewable source. In addition, they have a higher cost and are less biodegradable than natural triglycerides. U.S. Patent No. 867,890 discloses the use of soluble copper compounds to prevent oxidation in mineral oil lubricants with an ashless dispersant and dihydrocarbyldithiophosphate. In said patent, effective amounts of copper were described as from about 5 to about 500 parts per million. The use of vegetable oil triglycerides in lubricating oils has been limited due to their susceptibility to oxidative degradation. ' Oil-soluble copper compounds are identified that impart resistance to oxidation to vegetable oil triglycerides making them suitable for use in a variety of lubricating compositions including those that demand uses at higher temperatures such as motor oil. Triglyceride oils formed from high percentages of oleic acid tend to be better stabilized by the oil-soluble copper. A synergism between the oil-soluble copper compounds and the oil-soluble antimony compounds results in effective antioxidant protection at lower soluble copper contents. The present invention was carried out with the support of the government in accordance with Contract No. 93-COOP-1-9542 issued by the United States Department of Agriculture and funded by the United States Department of Defense. The government has certain rights in the invention. Triglycerides stabilized by copper in the present invention are one or more triglycerides of the formula wherein R ', R2 and R3 are aliphatic hydrocarbyl groups containing between about 7 and about 23 carbon atoms in which at least about 20, 30, 40, 50 or 60 percent of the R groups of the triglycerides are monounsaturated and, more conveniently, in those between about 2 to about 90 mole percent of the groups R ', R2, R3 based on the total number of all those triglyceride groups, are the aliphatic portion of the oleic acid. These triglycerides are available from a variety of plants or their seeds and are commonly referred to as vegetable oils. The term "hydrocarbyl group" as used herein, denotes a radical having a carbon atom directly attached to the rest of the molecule. The aliphatic hydrocarbyl groups include the following: (1) the aliphatic hydrocarbon groups are preferred; that is, alkyl groups such as heptyl, nonyl, undecyl, tridecyl, heptadecyl; alkenyl groups containing a single double bond, such as, heptenyl, nonenyl, undecyl, tridecyl, heptadecyl, heneicosenyl; alkenyl groups containing 2 or 3 double bonds, such as 8, 11-heptadecadienyl and 8,11,14-heptadecadienyl. All isomers of these are included, although straight chain groups are preferred. (2) Substituted aliphatic hydrocarbon groups; that is, groups containing non-hydrocarbon substituents which, in the context of the present invention, do not modify the predominantly hydrocarbon character of the group. Those skilled in the art will appreciate the substituents that are suitable; examples are hydroxy, carbalkoxy, (especially lower carbalkoxy) and alkoxy (especially lower alkoxy), the term, "lower" denotes groups containing no more than 7 carbon atoms. (3) Heterogroups; that is, groups which, while possessing predominantly aliphatic hydrocarbon character, within the context of the present invention, contain atoms other than carbon present in a chain or ring composed otherwise of aliphatic carbon atoms. Suitable heteroatoms will be apparent to those skilled in the art and include, for example, oxygen, nitrogen and sulfur. Generally, the fatty acid portions (hydrocarbyl group R ', R2 or R3 plus a carboxyl group) are such that the R', R2 and R3 groups of the triglyceride are at least 30, 40, 50 or 60 percent, preferably at least 70 percent and more preferably at least 80 mole percent monounsaturated. Normal sunflower oil has an oleic acid content of 25-40 percent. By genetically modifying sunflower seeds, a sunflower oil can be obtained in which the oleic content is from about 60 to about 90 mole percent of the triglyceride acids. U.S. Patent Nos. 4,627,192 and 4,743,402 are hereby incorporated by reference for their descriptions directed toward the preparation of sunflower oil with high oleic content. The oils of genetically modified plants are preferred for applications where the temperature used exceeds 100 ° C, 250 ° C or 175 ° C, such as internal combustion engines. For example, a triglyceride composed exclusively of portions of oleic acid has an oleic acid content of 100%, and, therefore, a monounsaturated content of 100% A triglyceride consisting of portions of acids that are 70% oleic acid monounsaturated), 10% stearic acid (saturated), 5% palmitic acid (saturated), 7% linoleic acid (di-unsaturated) and 8% hexadecanoic acid (monounsaturated) has a monounsaturated content of 78% Triglycerides that have a useful Improved in this invention are exemplified by vegetable oils that are genetically modified so as to contain a higher than normal oleic acid content, ie a high proportion of the R1 groups, R2 and R3 are heptadecyl groups and a high proportion of the R1 COO-R2COO- and R COO- that are adhered to the groups 1, 2, 3-propanotriilo -CH2CHCH2- are the residue of an oleic acid molecule. Preferred triglyceride oils are genetically modified high oleic acid triglyceride oils (at least 60 percent). The genetically modified high oleic acid vegetable oils used within the present invention are high oleic acid safflower oil, high oleic acid corn oil, high oleic acid rapeseed oil, high sunflower oil. of oleic acid, soybean oil with high oleic acid, cottonseed oil with high content of oleic acid, peanut oil with high oleic acid, oil of lesquerella with high oleic acid, oil of "meadowfoam" and palm oil with high oleic content Vegetable oil with a high content of oleic acid is sunflower oil with a high content of oleic acid obtained from the Helianthus species. This product is available from SVO Enterprises, Eastlake, Ohio under the trade name sunflower oil with high Sunyl oleic content. Sunyl 80 is a triglyceride with a high oleic acid content in which the acidic portions comprise 80 percent oleic acid. Another vegetable oil with high content of oleic acid is rapeseed oil with high oleic acid obtained from Brassica ca pestris or Brassica napus, also available from SVO Enterprises registered as rapeseed oil with high content of RS oleic acid, RS 80 means an oil of rapeseed in which the acidic portions comprise 80 percent oleic acid. Corn oil with a high content of oleic acid and combinations of sunflower oils with a high content of oleic acid and corn with a high content of oleic acid are also preferred.

It should be noted that olive oil is included or can be excluded as vegetable oil in different embodiments of the present invention. The oleic acid content of olive oil typically ranges between 65-85 percent. However, this content is not obtained by genetic modification, but occurs naturally. Castor oil can also be included or can be excluded as vegetable oil for this application. It should also be noted that the genetically modified vegetable oils have high oleic acid contents at the expense of the di- and tri- unsaturated acids, such as linoleic acid. A normal sunflower oil has between 20-40 percent portions of oleic acid and between 50-70 percent portions of linoleic acid (di-unsaturated). This gives a content of 90 percent portions of mono- and di-unsaturated acid (20 + 70) or (40 + 50). The genetically modified vegetable oils generate a vegetable oil with a low content of di- or tri-unsaturated portions. The genetically modified oils of the present invention have an oleic acid portion: linoleic acid serving ratio of about 2 to about 90. A content of 60 percent oleic acid portions and a content of linoleic acid fractions of 30 per cent. One percent of a triglyceride oil gives an oleic: linoleic acid ratio of 2. A triglyceride oil composed of a portion of oleic acid of 80 percent and a portion of linoleic acid of 10 percent gives a ratio of 8. An oil of triglycerides composed of a portion of oleic acid of 9 percent and a portion of linoleic acid of 1 percent gives a ratio of 90. The ratio for normal sunflower oil is 0.5 (oleic acid portion of 30 percent). one hundred and one portion of linoleic acid 60 percent). The triglycerides described above have many desirable lubricating properties compared to commercial mineral oil lubricating base materials (hydrocarbon). The moisture level of triglycerides is approximately 200 ° C and the flash point is approximately 300 ° C (both determinations according to AOCS Ce 9a-48 p ASTM D1310). In a lubricating oil, this results in low organic emissions to the environment and a reduced fire hazard. The flash points of basic hydrocarbon oils are, as a rule, lower. Triglyceride oils are polar in nature and, therefore, differ from non-polar hydrocarbons. This explains the excellent ability of triglycerides to be adsorbed on metal surfaces as thin adherent films. The adherent nature of the film ensures lubrication while the thin nature allows the parts to be designed with less intervening space for the lubricant. A study of the operation of planing surfaces placed in close relation to each other, considering the pressure and temperature as fundamental factors affecting the lubrication, shows that the properties of film formation of triglycerides are especially advantageous in hydraulic systems. Also, the water can not force out an adherent triglyceride oil film from a metal surface as easily as a hydrocarbon film. The structure of the triglyceride molecule is generally more stable against the mechanical and thermal stresses that exist in hydraulic systems than the linear structure of mineral oils. In addition, the ability of the polar triglyceride molecule to adhere generally to metal surfaces improves the lubricating properties of these triglycerides. The only property of these triglycerides that would prevent their intended use for hydraulic purposes is their tendency to oxidize easily. Vegetable based oils have substantial benefits compared to petroleum-based mineral oils as lubricant base materials. These benefits include: 1) Renewable - the basic materials are renewable resources of the agricultural market of the United States. 2) Biodegradable - The base fluids are completely biodegradable due to their ability to cleave in the bond of esters and to oxidize near the carbon-carbon double bond. 3) Non-toxic - Base fluids can be ingested. This benefit together with biodegradability, means that fluids are a less significant environmental hazard in the face of uncontrolled spills. 4) Safety - Vegetable oils have very high flash points, on average, more than 290 ° C (570 ° F) reducing the risk of fire of the lubricant. 5) Reduced Motor Emissions - Due to the low volatility and high boiling points of triglyceride based oils, less lubricant ends up in discharge emissions and as particulate material. 6) High Viscosity Index (HVI) - vegetable oils have temperature properties - convenient viscosity with viscosity index (Vis) greater than 200 which results in better control of oil viscosity at high engine temperatures and reduces the need for expensive VI improver additives. A high viscosity index means that the oil reduces its density less when heated. Therefore, an oil of lower viscosity at room temperature can be used. 7) Improved Fuel Economy - improvements in fuel economy result from reduced friction of triglyceride oils. The HVIs of the triglyceride oils allow the use of less viscous base supplies to meet the higher temperature requirements in the areas of the top ring and the piston groove. This reduces fuel consumption. 8) In-situ Lubricant Films - Thermal or oxidative degradation results in fatty acid constituents that can adhere to the surface and improve the anti-wear properties. 9) Unique protection against Pollutants and the Corrosion - The chemical structures of the fatty acids in vegetable oils with high oleic acid content provide inimitable protection against natural corrosion, inherent detergency and solubility properties. The detergent and solubility properties help keep the mud and sediment-free parts moving. Conveniently, the above-described vegetable oils and / or the genetically modified vegetable oils are at least about 20, 30, 40, 50 and 60% by volume of a lubricant composition, more conveniently, such as when used as a motor lubricant. , from about 40 to about 95 or 99% by volume and preferably about 50 or 60 to about 90 or 95% by volume of the lubricant. Other base lubricating fluids such as petroleum distillate products, oils isomerized or subjected to hydrocracking, such as those synthesized from the fractionation of hydrocarbons, polyalphaolefins (PAOs) or synthetic ester oils may comprise up to 30, 40 , 50, 60 or 70% by volume, more conveniently between about 1 or 3 and about 25% vol. of the formulated lubricant composition. These can be added for the purpose of imparting certain properties or they can be carriers for other additives used in the lubricant composition. The formulated lubricant composition can further contain up to 20% by volume, more conveniently between about 5 and about 15% by volume of commercial lubricant additives. These include metal-containing antioxidants, anti-wear additives, detergents, inhibitors, ashless dispersants, antioxidants antimony adjuvants and pour point depressants, such as vinyl acetate copolymers with fumaric acid esters of oil alcohols. of coconut The lubricant can also contain up to 35% by volume of modifiers. viscosity index, such as copolymers of olefins, polymethacrylates, etc. The lubricant compositions may contain, and generally contain, other traditional lubricating additives, such as anti-corrosive inhibitors, such as, lecithin, sorbitan monooleate, dodecyl succinic anhydride or ethoxylated alkylphenols. The copper antioxidant may be mixed in the oil as any suitable oil-soluble copper compound. By soluble in oil it is meant that the compound is soluble under normal mixing conditions in the oil or in a package of additives for the lubricant composition. The copper compound may be in cuprous or cupric form. The copper compound can be copper dihydrocarbyl thio- or dithiophosphates. Similar zinc thio and dithiophosphates are well known and copper thio and dithiophosphate compounds are made by corresponding reactions where one mole of cuprous or cupric oxide can be reacted with one or two moles of dithiophosphoric acid. Alternatively, copper can be added as the copper salt of a synthetic or natural carboxylic acid. Examples include saturated fatty acids C3 to Cis, such as stearic or palmitic acid, but include unsaturated and aromatic acids, such as oleic acid or branched carboxylic acids, such as naphthenic acids of molecular weight, from 200 to 500 Synthetic carboxylic acids are preferred for the improved handling and solubility properties of the resulting copper carboxylates. Preferred examples include copper 2-ethylhexanoate, copper neodecanoate, copper stearate, copper propionate, copper naphthalate and copper oleate or mixtures thereof. The copper compound can also be oil-soluble copper dithiocarbamates of the general formula (RR'NCSS) n Cu where n is 1 or 2 and R and R 'are the same or different hydrocarbyl radicals containing from 1 to 18 and preferably from 2 to 12 carbon atoms including radicals such as alkenyl, alkyl, aralkyl and cycloaliphatic radicals. Alkyl groups of 2 to 8 carbon atoms are preferred. Acetyl copper sulfonates, phenates and acetonates can also be used. In a preferred embodiment, the organic portion of the oil-soluble copper compound is free of atoms other than carbon, hydrogen and oxygen. When used in combination with zinc dialkyl dithiophosphates, the amount of copper in the oil is important to obtain the combination of antioxidant and anti-wear properties necessary for long-lived lubricants.

Conveniently, the lubricant composition contains from about 50 to about 3000 ppm Cu, more conveniently, from about 50 to about 2000 ppm, preferably from about 100 or 150 to about 800 ppm or 1200 ppm and (especially when antimony is present) preferably between about 100 or 150 and about 500, 600, 700 or 800 ppm based on the weight of the lubricant composition. The oil-soluble antimony compounds in the lubricant composition can act as an adjuvant antioxidant which reduces the amount of oil-soluble copper typically used between about 1000 ppm and 2000 ppm in the lubricant at about 500 ppm with the same antioxidant protection. An effective antimony compound is dialkyldithiocarbamate antimony such as that registered under the name Vanlube 73 of R. T. Vanderbilt having the formula where R and R 'are hydrocarbyl radicals as described below with 1 to 18 carbon atoms, more conveniently 2 to 12 carbon atoms. More conveniently, the hydrocarbyl radicals are alkyl or alkenyl radicals. Antimony dialkylphosphorodithioates such as that registered under the Vanlube 622 or 648 designation also of R. T. Vanderbilt can be effective. These are similar to the zinc dihydrocarbildi thiophosphates that have the formula wherein R and R can be the same or different hydrocarbyl radicals containing from 1 to 18, preferably from 2 to 12 carbon atoms as described for the zinc compound. Suitably, the hydrocarbyl radicals are alkyl, alkenyl, aryl, aralkyl, alkaryl or cycloaliphatic radicals. Conveniently, antimony concentrations in the lubricant are from about 100 to about 4000 ppm, more conveniently from about 100 to about 2000 ppm, preferably from about 100 or 200 to about 800 or 1000 ppm of antimony based on the lubricant composition. Commercial manufacture of a preffered antimony compound recommends between about 0.1 and about 1% by weight (600 ppm antimony) and for anti-wear and / or extreme pressure uses between 0.1 and about 5% by weight in lubricating compositions . It has also been found that soluble antimony compounds function as anti-wear agents. This reduces the need for zinc dithiophosphates which contribute to the depletion of phosphorus in catalytic converters. The antidote additives of zinc dihydrocarbyl dithiophosphate (wear inhibitors) are conveniently used in the compositions and can be prepared according to known techniques by first forming a dithiophosphoric acid, generally by reaction of an alcohol or a phenol with P2SS and then neutralizing the di-phosphoric acid with a suitable zinc compound. Mixtures of alcohols including mixtures of primary and secondary alcohols can be used. The secondary alcohols generally impart improved anti-wear properties, with primary alcohols that provide improved thermal stability properties. The mixtures of the two are especially useful. In general, any basic or neutral zinc compound could be used although oxides, hydroxides and carbonates are used more frequently. Commercial additives frequently contain an excess of zinc due to the use of an excess of the basic zinc compound in the neutralization reaction. The dihydrocarbyl zinc dithiophosphates useful in the present invention are oil soluble salts of dihydrocarbyl esters of dithiophosphoric acids and can be represented by the following formula: wherein R and R 'may be the same or different hydrocarbyl radicals containing from 1 to 18, preferably from 2 to 12 carbon atoms and include radicals such as alkyl, alkenyl, aryl, aralkyl, alkaryl and cycloaliphatic radicals. Especially preferred as R and R 'groups are alkyl groups of 2 to 8 carbon atoms. Thus, the radicals can be, for example, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl, amyl, n-hexyl, n-heptyl, n-octyl, decyl, Dodecyl, octadecyl, 2-ethylhexyl, phenyl, butylphenyl, cyclohexyl, methylcyclopentyl, propenyl, butenyl etc. In order to obtain solubility in oil, the total amount of carbon atoms (ie, R and R ') in the dithiophosphoric acid will generally be about 5 or more. The zinc dithiotophates are conveniently used in amounts which result in from about 100 to about 3000 ppm of zinc in the lubricant composition, more conveniently from about 500 to about 2500 ppm of zinc. The use of oil-soluble antimony can reduce the need for oil-soluble zinc. In the oils of the prior art, other antioxidants in addition to zinc dialkyldithiophosphate are sometimes needed to improve the oxidative stability of the oil. These supplemental antioxidants are typically in the oil in amounts of about 0.5 to about 2.5% by weight. Supplementary antioxidants may be included in this composition and include phenols, hindered phenols, bis-phenols and sulfur phenols, catechol, alkylated catechols and sulfided alkyl catechols, diphenylamine and alkyl diphenylamines phenyl-1-naphthylamine and its alkylated derivatives, alkyl borates and aryl borates, alkyl phosphites and alkyl phosphates, aryl phosphites and aryl phosphates, O, O, S-trialkyl dithiophosphates, 0.0, S-triaryl dithiophosphates and O, O, S-trisubstituted dithiophosphates optionally containing alkyl and aryl groups, metal salts of dithioacids, phosphites, sulfides, hydrazides and triazoles.

However, the inclusion of small amounts of copper generally eliminates the need for these supplemental antioxidants. It would be within the scope of the invention that a supplemental antioxidant be included especially for oils that operate under conditions in which the presence of such supplemental antioxidants may be beneficial. The use of soluble copper in oil allows to partially or completely replace the supplementary antioxidants. Frequently, it allows lubricating compositions having the desired antioxidant properties to be obtained without additional supplemental antioxidant or with lower concentrations than normal, for example with less than 0.5% by weight and frequently, less than about 0.3% by weight of the supplemental antioxidant. The dispersion of the lubricant composition can be improved by ashless dispersant compounds for traditional lubricating oils such as derivatives of carboxylic acids substituted with long chain hydrocarbons in which the hydrocarbon groups contain from 50 to 400 carbon atoms. These, in general, are an ashless dispersant containing nitrogen with an oil solubilising group of relatively high molecular weight aliphatic hydrocarbons adhered thereto or an ester of a succinic acid / anhydride with a high molecular weight aliphatic hydrocarbon adhered thereto and derived from monohydric and polyhydric alcohols, phenols and naphthols. Nitrogen-containing dispersant additives are those known in the art as sediment dispersants for motor crankcase oils. These dispersants include mineral salts soluble in oil, amides, imides, oxazolines and esters of mono- and dicarboxylic acids (and where the corresponding acid anhydrides exist) of various amines and nitrogen-containing materials with amino-nitrogen or heterocyclic nitrogen) and at least one amido or hydroxy group capable of forming a salt, amide, imide, oxazoline or an ester. Other dispersants with nitrogen content that can be employed in the present invention include those in which a polyamine with nitrogen content is directly adhered to the long chain aliphatic hydrocarbon as shown in U.S. Patent Nos. 3,275,554 and 3,565,804, which are incorporated herein by reference, wherein the halogen group in the halogenated hydrocarbon is displaced by various alkylene polyamines. In U.S. Patent 4,867,890 which is incorporated herein by reference, further details are described as to the ashless dispersants.

This invention conveniently utilizes a detergent inhibiting additive which is free, preferably of phosphorus and zinc, and comprises at least one composition based on excess in metals and / or at least one carboxy dispersant composition, diarylamine, sulphide composition and an agent of the passivity of metals. The purpose of the detergent inhibitor additive is to provide cleaning of the mechanical parts, anti-wear and protection against extreme pressure, performance against oxidation and protection against corrosion. Excess based salts of organic acid metals are well known to those skilled in the art and generally include metal salts in which the amount of metal present therein exceeds the stoichiometric amount. Said salts are said to have conversion levels in excess of 100% (ie, they comprise more than 100% of the theoretical amount of metal necessary to convert the acid into its "neutral" or "normal" salt). It is often said that these salts have metal ratios in excess of one (ie, the ratio of the equivalents of metal to equivalents of organic acid present in the salt is greater than that necessary to provide the normal or neutral salt that required only a stoichiometric ratio of 1: 1). They are commonly called overbased salts, hyperbased or superbased and are generally salts of organic sulfur acids, organic phosphorus acids, carboxylic acids, phenols or mixtures of two or more of any of these. A worker with knowledge in the matter could realize that the mixtures of those salts based on excess can also be used. The term "metal ratio" is used in the prior art and in the present, to designate the ratio of the total chemical equivalents of the metal in the salt based on excess to the chemical equivalent of the metal in the salt that would be expected to result in the reaction between the organic acid to be based on excess and the metal compound basically reactant according to the known chemical reactivity and the stoichiometry of the two reactants. Therefore, in a normal or neutral salt, the ratio of metals is one and in an overbased salt the ratio of metals is greater than 1. The excess-based salts used have, in general, metals ratios of at least approximately 3: 1. Typically, the salts have ratios of at least about 12: 1. In general, they have metal ratios that do not exceed approximately 40: 1. Typically, salts having ratios of about 12: 1 to about 20: 1 are employed. The reactive metal compounds basically used to make these overbased salts are generally an alkaline earth metal or alkaline compound (ie, Group IA, IIA, and IIB metals excluding the francium and radium and typically excluding rubidium, cesium, and beryllium). ) although other basic reaction metal compounds can be used. The compounds of Ca, Ba, Mg, Na and Li, such as their hydroxides and lower alkanoxide alkoxides are generally used as base metal compounds in the preparation of these overbased salts although others may be used as shown in prior art that is incorporated herein by reference. Excess-based salts containing a mixture of ions of two or more of these metals can be employed in the present invention. Excess-based salts may be of oil-soluble organic sulfur acids such as sulfonic, sulfamic, thiosulfonic, sulfinic, sulfuric acid of partial esters, sulfuric and thiosulfuric. In general, they are salts of carbocyclic or aliphatic sulfonic acids. U.S. Patent No. 5,427,700 discloses various overbased salts of organic acid metals in more patent detail which is incorporated herein by reference. Agents of the passivity of metals such as tolitriazole or an oil-soluble derivative of a dimercaptothiadiazole are present, conveniently in the lubricant composition. The dimercaptothiazoles which can be used as starting material for the preparation of the oil-soluble derivatives containing the dimercaptothiadiazole nucleus have the following structural formulas and the following names: 2,5-dimercapto-1,3,4-thiadiazole 3,5-dimercapto-1,2,4-thiadiazole 3,4-dimercapto-1, 2,5-thiadiazole 4, 5-dimercapto-1, 2,3-thiadiazole N- -C-SH II C-SH Of these, the one that is most readily available, and the one preferred for the purpose of the present invention, is 2,5-dimercapto-1,3,4-thiadiazole. This compound will sometimes be referred to later in this DMTD. However, it should be understood that any of the other dimercaptothiadiazoles can be substituted for all or a portion of the DMTD. The DMTD is conveniently prepared by the reaction of one mole of hydrazine, or a hydrazine salt, with two moles of a carbon disulfide in an alkaline medium and then acidification; Derivatives of DMTD have been described in the art, and any of those compounds can be included. The preparation of some derivatives of DMTD is described in E.K. Fields "Industrial and Engineering Chemistry", 49, p. 1361-4 (September 1957). For the preparation of the oil-soluble DMTD derivatives, it is possible to use DMTD already prepared or to prepare the DMTD in situ and, subsequently, to add the material to be reacted with the DMTD. Further details regarding various metal passivity agents and their preparation are described in U.S. Patent 5,427,700 which is incorporated herein by reference. The present invention also optionally uses viscosity modifying compositions that include viscosity index modifiers to provide sufficient viscosity at elevated temperatures. The modifier compositions include a nitrogen-containing ester of a carboxy-containing interpolymer, said interpolymer having a reduced specific viscosity of between about 0.05 and about 2, said ester being substantially free of titratable acidity and being characterized by the presence within the its polymer structure of at least one of each of three pending polar groups: (A) a carboxylic ester group with relatively high molecular weight with at least 8 aliphatic carbon atoms in the ester radical, (B) a carboxylic ester group with relatively low molecular weight having no more than 7 aliphatic carbon atoms in the ester radical, and (C) a carbonylpolyamino group derived from a polyamine compound having a primary or secondary amino group in which the molar ratio of (A) : (B): (C) is (60-90): (10-30): (2-15). An essential element of a preferred viscosity modifying additive is that the ester is a combined ester, ie one in which there is the combined presence of a high molecular weight ester group and a low molecular weight ester group, especially in the relationship indicated above. This combined presence is critical for the viscosity properties of the combined ester, from the point of view of its viscosity modifying characteristics and from the point of view of its thickening effect on the lubricant compositions in which it is used as an additive. With reference to the size of the ester groups, it should be noted that an ester radical is represented by the formula -C (O) (OR) Y that the number of carbon atoms in an ester radical is the combined total of the carbon atoms of the carbonyl group and the carbon atoms of the ester group, that is, the group (OR). In U.S. Patent No. 5,427,700, which is incorporated herein by reference, viscosity modifying additives are described in more detail. The lubricant composition may comprise a synthetic oil based on esters. The synthetic oil based on esters comprises the reaction of a monocarboxylic acid of the formula Rld -COOH or a polycarboxylic acid, such as the dicarboxylic acid of the formula with an alcohol of the formula R 1 R (OH) m in which R 16 is a hydrocarbyl group containing between about 5 and about 12 carbon atoms, R17 is hydrogen or a hydrocarbyl group containing between about 4 and about 50 carbon atoms, R18 is a hydrocarbyl group containing between 1 and about 18 carbon atoms, m is an integer from 0 to about 6 and n is an integer of 1 to about 6. Useful monocarboxylic acids are the isomeric carboxylic acids of pentanoic, hexanoic, octanoic, nonanoic, decanoic, undecanoic and dodecanoic acids. When R] 7 is hydrogen, the useful dicarboxylic acids are succinic acid, maleic acid, azelaic acid, suberic acid, sebacic acid, fumaric acid, adipic acid. When R17 is a hydrocarbyl group containing between 4 and about 50 carbon atoms, the useful dicarboxylic acids are the succinic alkyl acids and the succinic alkenyl acids. The alcohols which can be used are methyl alcohol, ethyl alcohol, butyl alcohol, isomeric pentyl alcohols, isomeric hexyl alcohols, dodecyl alcohol, 2-ethylhexyl alcohol, ethylenic alcohol, diethylene glycol propylene glycol. neopentyl glycol, pentaerythritol, dipentaerythritol, etc. The specific examples of these esters include dibutyl adipate, di (2-ethylhexyl) sebacate, di-n-hexyl fumarate, dioctyl sebacate, diisooctyl azelate, diisodecyl azelate, dioctyl phthalate , didecylphthalate, diethylester sebacate, the 2-ethylhexyl diester of linoleic acid dimer, the complex ester formed by the reaction of one mole of sebacic acid with two moles of tetraethylene glycol and two moles of 2-ethylhexanoic acid, the ester formed by reacting one mole of adipic acid with two moles of a 9-carbon alcohol derived from the oxo process of a dimer of l-butene and the like .. E plos A microreactor of accelerated oxidation stability was developed by the Tribology Group of the Department of Chemical Engineering of the Pennsylvania State University to analyze the volatility and oxidative stability of oils.The test employs a metallic block with an ac depth of 0.95 ± 0.35 mm where the oil sample is analyzed. It is very similar to a thermogravimetric constant temperature analysis except that the amount of insoluble sediment (deposit) is determined separately. The apparatus is described in more detail in an article by J. M. Pérez and other "Diesel Deposit-Microanalysis Formation Trends Methods" SAE newspaper number 910750 (1991). In general, a 30-minute test at 225 ° C is equivalent to approximately 3000-6000 miles of use in a vehicle engine and a 60-minute test would be equivalent to approximately 12,000 miles (6,000-20,000) depending on the design of the engine and load factors in the application. Any liquid in the specimen can be evaluated by gel impregnation chromatography to obtain information regarding changes in the molecular weight distribution of the liquid as a function of the test conditions. Low molecular weight products contribute to evaporation losses and higher molecular weight products may eventually form sediments. Table 1 shows the stability tests for accelerated oxidation in 10 vegetable oils. Maritime cabbage oil has, obviously, some or some natural antioxidants. The generally high amounts of deposit formed in the 30 minute tests indicate that the oils are not acceptable for engine oil base material without major modification.

Table 2 shows the effect of a copper additive in the accelerated oxidative stability test of natural oils. The test times were prolonged for 30 minutes as shown in Table 1 a. periods of 1 to 3 hours indicating that a significant oxidation resistance was imparted by the oil-soluble copper compound. The amount of copper is given in ppm Cu which indicates the amount of copper associated with the oil-soluble copper compound. All results were acceptable in the 1 hour trials indicating that the stabilized lubricant compositions have an acceptable oxidation resistance for use in vehicle engines (approximately one equivalent to 12,000 miles). Vegetable oils with a high content of oleic acid (sunflower, rapeseed, soybean, very oleaginous maize and corn) provided a superior oxidation resistance with copper than castor oil (which has a high percentage of ricinoleic acid, a monounsaturated hydroxy acid ). This indicates a certain synergy between the soluble copper compounds and the triglycerides of aliphatic or olefinic carboxylic acids, especially of oleic acid. Note that in Table 1, the castor oil without added antioxidants had superior oxidation resistance to all oil oils other than marine colony. Table 2 illustrates the fact that vegetable oil with 2000 ppm of the soluble copper compound has sufficient oxidative stability for use in vehicle engines. Table 3 shows that the soluble copper compound provides superior stability to oxidation compared to conventional stabilizer packages (used in mineral oils as commercial additives for anti-wear oxidation, dispersants, etc.) engine oil package labeling (Eng Pack ) and a package of additives in SG service quality (SG Pack). Also included in this table is a patented additive containing chlorine (additive with Cl), a Ketjen lubricating polymer from AKZO Chemical Corp., and K-2300, another additive for commercial lubricating oils. The Eng. Pack, SG Pack, the additive with Cl content and the Ketjen Lube additives had marginal yield as antioxidants at 30 min. and unacceptable performance at 60 min. The oil-soluble copper provided results greater than 30 and 60 minutes regardless of whether it was used alone or in combination with other additives. The K-2300 of 5% per vol. seems to decrease oxidative stability. The zinc dithiophosphate (ZDP), which in the mineral oil acts as an antioxidant / anti-wear additive, provides some antioxidant protection with sunflower oil with high oleic content with or without additive with Cl and / or Ketjen lubricant. However, the ZDP slightly decreases oxidative stability when used with copper. As can be seen in the last four examples of oils in the table, the patented additive with Cl content decreases the oxidative stability when used with the SG Pack with or without copper although it provided some oxidative stability without these components as observed in the examples 4-8. This illustrates the complexity of formulating a lubricant composition. Table 4 illustrates accelerated oxidation stability assays _ in copper-free vegetable oils stabilized with conventional antioxidants and oils for mineral oil-based engines (10W30 and 10 40). A 10 -30 vegetable oil lubricant used in effect for 2400 miles in a 1986 Oldsmobile V6 is included. That composition was included to show that the formulated oil would work in a car engine and would have residual oxidative stability after such use. The use of oil-soluble copper in subsequent lubricating oil formulations provides additional oxidative stability beyond that demonstrated here. The information regarding the oils for engines based on mineral oils is provided as comparison values of what has been commercially acceptable and feasible in oxidative stability.

Comparison of the first two examples using an antioxidant without copper shows that an air environment causes more undesirable sediments than a nitrogen environment. The third example shows that the antioxidant without copper content results in excessive sediments in 60 minutes. Mineral oils of multiple weights (10W30 and 10 40) show that 10 30 undergoes an excessive evaporation while 10 40 suffers a sediment formation. Vegetable oils in backboards stabilized with oil soluble copper have a convenient low sediment formation and low evaporation compared to these commercial mineral oil compositions. Table 5 illustrates the oxidation stability of oil-stabilized oil compositions containing oil-soluble copper containing antioxidants. The first 5 examples show that the stabilizing effect of 2000 ppm of copper decreases only after 3 hours (eg, to about 180210min.) In the oxidation acceleration test. It has been observed that the oil-soluble copper increases the wear (reduced anti-wear properties) of the sunflower oil, which is why in the next 5 examples a more wear-resistant oil composition is shown with 1% by volume of zinc dithiophosphate (ZDP). Examples of margarine, sunflower and corn with copper oils show that vegetable oils with a high content of oleic acid (maritime col and sunflower) are better stabilized against oxidation than normal corn oil. Four sunflower samples with 2000, 1500, 1000 and 200 ppm copper show that 1000 to 2000 ppm of copper are suitable for good oxidative stability in a 60 minute test. In Table 5 the compositions with copper and antimony have, in general. oxidative stability equivalent to the sample with copper alone. These compositions with copper and antimony can function with 500-600 ppm only of copper and 500-600 ppm of antimony and exhibit equivalent oxidative stability to the compositions with 2000 ppm of copper. Therefore, antimony allows copper to be effective at a lower concentration. The total ppm of metals can therefore be decreased. Antimony was added as antimony dialkyldithiocarbamate. The use of the antioxidant antimony adjuvant avoids problems of the dispersion of 2000 ppm of oil-soluble copper and minimizes the increasing harmful effect of the wear of the copper soluble in the oil. Table 6 shows that many conventional antioxidants do not impart oxidative stability even at 175 ° C (ie, 50 ° C less than in previous tests). The tests in Table 6 were carried out at 175 ° C since most of the antioxidants are very volatile at 225 ° C and, in general, they were known to be less effective than soluble copper. These antioxidants would be appropriate for some of the applications of hydraulic fluids at low temperatures. The Tribology Group of the Department of Chemical Engineering of the Pennsylvania State University also conducted a four-ball wear test as shown in Figure 1. In it, the balls (E) are 52-100 bearings. steel balls of 1.27 cm in diameter, the side arm (C) keeps the ball container (D) fixed, (B) is the level of lubricant in the ball container (D), the three bottom balls are fixed, the thermocouple (A) measures the temperature, the heating block (F) controls the temperature, and the upper end ball rotates by a force provided by the shaft (G). The assay method includes a standard assay method and a sequential assay method. The sequential test method was complemented by a modified abrasive wear test that determined the load required to cause abrasive wear with the lubricant in particular. The wear on the balls characteristic of the lubricants in the sequential test is shown in Figure 2. Typical mineral oil wear with additives is described by the upper curve marked with an A. The addition of an extreme pressure additive to the mineral oil results in a curve similar to that marked with a B. A good Anti-wear additive can result in a curve similar to C where there is no increase in wear or there is very little increase in wear (sign of wear) after the test in (30 minutes in this example). The bottom line D is the elastic deformation line Hertz that represents the contact area formed by elastic deformation of the balls due to contact pressure before starting the test. The delta wear value of Table 7 represents the difference in wear signals before and after each segment of the three sequence test. Table 7 illustrates the wear properties of vegetable oils and mineral oil with different additives. Comparing lubricants 1 and 2 it is obvious that vegetable oil inherently has better wear resistance both during settling and during periods 1 and 2 in steady state. Comparing lubricant 1 with 2 and 3 shows that copper soluble in oil decreases the inherent wear resistance of vegetable oil. The lubricant 5 of sunflower oil with 1% by vol. of zinc dithiophosphate (ZDP) shows that a little zinc dithiophosphate (ZDP) is needed only to give the sunflower oil a wear resistance equivalent to or better than that of a SAE 10W30 mineral oil (lubricant 11). Lubricants 6 and, 7 show that 1% per vol. ZDP provides good wear resistance (as good as SAE 10W 30 lubricant 11). Lubricants 8 and 9 show that the LB-400 extreme wear additive is not as effective in providing wear resistance as the ZDP and that the amounts of LB-400 change its effectiveness. The LB-400 is a phosphate ester available from Rhone-Poulenc as an anti-wear additive. Lubricant 10 shows that an oxidation-resistant oil-soluble copper containing vegetable lubricant with an effective amount of an anti-wear additive can perform similarly or better than a mineral oil product with respect to settling and wear. As shown in accelerated oxidation tests, zinc dithiophosphate (ZDP) decreases the oxidation resistance of vegetable oils stabilized with oil-soluble copper. As shown above, copper soluble in oil increases wear while the ZDP decreases wear (provides protection against wear). The combination of soluble copper and ZDP offers viable packages for low wear and low oxidation. As previously stated, antimony compounds can also be used as an antioxidant adjuvant with copper and zinc compounds. The oil-soluble antimony can replace some or all of the oil-soluble zinc, for example, (ZPD).

In many transport applications, for example, the piston ring and inner sleeve, transmission, gearbox, hydraulic pumps; lubricants are required to have, in addition to good friction and wear reduction properties, extreme pressure (extreme temperature) properties to prevent abrasive wear, galling and catastrophic wear faults. The friction and wear studies described above can be complemented by an evaluation test of abrasive wear increasing the load until abrasive wear occurs. Typically, commercial mineral-based engine oils have an abrasive load of 80 kgf or less. The vegetable oil compositions can be formulated to have abrasive filings in excess of 100 kgf. The copper soluble in oil reduces the abrasive load. The fatty acids in vegetable oils do not increase the abrasive load, although they reduce friction. Table 8 shows that vegetable oils have inherently as much resistance to abrasive wear due to lack of lubricant or more than mineral base materials (petroleum distillates). The abrasive load is the load in kg in the four-ball wear analyzer (shown in Figure 1) required to cause abrasive wear (defined as delta wear (?) exceeding 20 mm). This test is carried out by increasing the load on the four-ball wear analyzer until abrasive wear occurs. The test evaluates how well the lubricant composition can protect the metal parts when the high pressure makes the lubricant film thinner and thinner. This property is important in piston rings and inner liners, transmissions, gearboxes and hydraulic pumps. In an abrasive wear resistance test, wear versus load is plotted and in general three linear regions are seen. In the first region, wear increases linearly as the load increases. The lubricant and the additives are controlling the wear. At a determinable load, the lubricant and additives lose control of wear and wear increases at a higher speed developing a wear signal that becomes large enough to withstand the load. In the following, the wear continues at an intermediate speed between the first two speeds until the failure of the parts occurs. Table 9 illustrates the viscosity and metal content of two different lubricants for vegetable oil engines and a commercial 10W-30 (petroleum distillate) mineral oil.

Table 1 Stability Tests for Accelerated Oxidation of Natural Oils (Oxidation Tests of 40 uL) TEMPERATURE 225 ° C Micro-oxidation in low carbon steel, 40uL sample, open system 30 min Sediment sample (% by liquid evaporation weight) (% by weight) (% by weight) Sunflower Oil 63 24 13 High oleic Sunflower Oil 52 33 15 Semolina Oil of Castor 45 48: Rapeseed Oil of High Oleic 31 14 Soybean Oil for Salad 68 23 Soybean Oil 67 24 High Oleic Corn Oil 58 30 12 Corn Oil 59 31 10 Maritime Colony Oil 10 83 Lesquerefla Oil 63 30 Table 2 Effect of! Copper Additive in Accelerated Oxidative Stability Tests of Natural Oils TEMPERATURE 225nC Micro-oxidation in low carbon steel, sample ce 40uL, open system cp ? cwits d? Soy for N / A N / A 60 10 N / A N / A Salad + 2000 ppm Cu High Corn Oil 17 6 37 10 Olfpco + 2000 ppm Cu Corn Oil 10 60 10 N / A N / A Conventional + 2000 ppm Cu N / D means that the test results are not available Table 3 Accelerated Oxidation Stability Test of Sunflower Oil Formulations with Different Additives TEMPERATURE 225 ° C Ba or carbon steel sample of 40 uL, open system [continued Table CO Table 3 (Continued) Stability Test for Accelerated Oxidation of Sunflower Oil Formulations with Different Additives TEMPERATURE 225 ° C ___ Low carbon steel, 40 uL sample, open system Sample 60 mip. 120 min liquid sediment evap. liquid sediment evap. j High Oleicum Sunflower Oil 63 * 24 * 13 * N / A N / A N / D + 2000 ppm Cu 95 2.5 90.5 1% per vol. of ¿DP. 15 75 10 N / A N / A N / A W3 + 2000 ppm Cu + 1% per vol. of 2.5 90 7.5 11 82 ZDP High Oleic Sunflower Oil + 47 35 N / D N / A N / D 1.5% per vcl. of Additive with Cl + 2000 ppm Cu 1.5 97 1.5 4.5 89.5 + 1% per vol. of ZDP 11 76 13 N / A N / A N / D + 2000 ppm Cu + 1% per vol of 86 33 52 14 ZDP minute test instead of 60 min.

Table 4 Accelerated Oxidation Tests on Copper-Free Vegetable Oil Stabilized with Conventional Antioxidants and Mineral Oil-Based Engine Oils TEMPERATURE 225 ° C Low carbon steel, dry gas flow = 20 cm3 / min., 40μl sample cp [continuation Table 4 | Mineral oil 10VV-30 30 min. air -0.2 47.5 52.5 Mineral oil 10VV-3Ó 60 min. air 1.5 O, O 71, 9 Mineral oil 10W-30 120 min. air 8.7 6.0 85.3 Mineral oil 10VV-4Q 30 min. air 0.5 86 13.5 Mineral oil 10VV-4Q 60 min. air 5.9 74.4 19.7 Mineral oil 10VV-4Q 120 min. air 17.0 50.9 32, 1 cp N) Table 5 Stability Tests for Accelerated Oxidation in Copper Stabilized Vegetable Oils TEMPERATURE 225QC Cp co Table 5 (continued) Stability Tests for Oxidation.Acerated in Stabilized Vegetable Oils with Copper TEMPERATURE 225 ° C SAMPLE CONDITION% BY LIQUID WEIGHT EVAPORATION SEDIMENT TEST Sunflower Oil + 2000 ppm Cu + 1% 30 min. air 1, 5 104 per vol. of ZDP (1, 4) (97.7) (0.9) Sunflower Oil + 2000 ppm Cu + 1 y (60 min air 2.6 92.5 8 per vol ZDP (2.5) (89.7) (7.8) cp Sunflower oil + 2000 pPm of Cu + 1% 120 min. air 1 1, 2 72 6.8 per vol. of ZDP (12.4) (80.0) (7.6) Sunflower Oil + 2000 ppm Cu + 1% 180 min. air 27.9 61.5 15.6 per vol. of ZDP (26.6) (58.6) (14.9) Sunflower Oil + 2000 ppm Cu + 1% 210 min. air 56,3 25.2 17.5 per vo. of ZPD (56.9) (25.5) (17.7) Maritime Col + Cu 60 min. air 5.1 70 24.9 [Table 5 (continued) | Cp cp The numbers in parentheses are corrected to 100% Table 6 Accelerated Oxidation Tests in Copper-free Vegetable Oil Stabilized with Conventional Aptioxidants TEMPERATURE 175 ° C Low carbon steel, 50 mm with dry air 20 cm3 / m? P, 40 μl sample cp Table 7 Comparison of Oil Wear Properties Four-Ball Wear Test Data-steel-on-steel, 40 kg load at 75 ° C, in air, 600 rpm cp cp co ? The wear is shown in parentheses in this table? Wear for "settled" is the difference between the final wear signal and the Hertz diameter that represents the eiast.ca conformation of the balls to the 40 kg load. Wear for stable wear is the difference in the wear signal observed in the Stable state test of 30 mm Diameter Hertz in a load of 40 kg with 52-100 steel balls is 0.30 mm Table 8 Extreme Pressure Properties of Some Lubricants Based on Natural Oils LUBRICANT LOADING ABRASIVE WEAR, kg Mineral Base Mate / 828 40 r Sunflower Oil 50 Corn Oil 50 Sunflower Oil + 2000 ppm Cu 40 Sunflower Oil + adií Cl + 5% K-2300 < 60 Maize 10VA / 30 for fuel E-85 > 110 cp U3 Sunflower! 0W30 110 Sunflower 10W30 + 2000ppm Cu > 100 SAE 10W30 commercial < 80 Sunflower or Corn and Sunflower oil blend + 500- 160 600 ppm Cu + 500 ppm Sb, 1700 ppm Zn zinc dithiophosphate Table 9 Typical Properties of Formulated Oils or * TNB is the neutralizing power of the medium. It is monitored to ensure that the medium is not turning acidic. An acid medium can corrode the metal components. N / A means that the values are not available.

Although according to the patent statutes the best preferred embodiment and embodiment has been established, the scope of the invention is not limited thereto, but is limited by the scope of the appended claims.

Claims (24)

1. CLAIMS 1. A lubricant composition characterized in that it comprises; a) a lubricant comprising at least 20 percent by volume based on the volume of said lubricating composition of at least one vegetable oil triglyceride of the formula wherein R1, R and R are independently, aliphatic hydrocarbyl groups of 7 to 23 carbon atoms, said hydrocarbyl groups of said at least one triglyceride being at least 20. molar monosaturated, and b) from about 50 to about 3000 ppm copper based on the weight of the lubricant composition, said copper being in oil soluble form.
2. 2. The lubricating composition according to claim 1, characterized in that it additionally comprises from about 500 to about 2500 ppm of zinc, said zinc being in oil soluble form.
3. 3. The lubricant composition according to claim 1, characterized in that at least 60 mol% of R1, R2 and R3 combined of said at least one triglyceride are the alkene portion of oleic acid. Four . The lubricant composition according to claim 2, characterized in that said vegetable oil triglyceride includes an oil of a genetically modified plant comprising sunflower, safflower, corn, soybean, rapeseed, marinated cabbage, lesquerella, peanut, cottonseed, cañuela, "raeadowfoam" or combinations thereof. 5. The lubricant composition according to claim 1, characterized in that said copper is added in the form of a copper carboxylate. 6. The lubricating composition according to claim 5, characterized in that the majority of the carboxylate of said copper carboxylate is free of atoms other than carbon, oxygen and hydrogen. The lubricating composition according to claim 1, characterized in that it further comprises between about 100 and about 4000 ppm of antimony based on the weight of said lubricating composition, wherein said antimony is in an oil soluble form. 8. The lubricating composition according to claim 7, characterized in that said copper is present from about 100 to about 800 ppm based on the weight of said lubricating composition. The lubricant composition according to claim 8, characterized in that said antimony is added as antimony dialkyldithiocarbamate. The lubricant composition according to claim 8, characterized in that it additionally comprises from about 500 to about 2500 ppm of zinc based on the weight of said lubricating composition, said zinc being in an oil soluble form. 11. The lubricant composition according to claim 9, characterized in that it additionally comprises between about 500 and about 2500 ppm of zinc, said zinc being in oil soluble form and being added in the form of zinc dithiophosphate. 12. The lubricant composition according to claim 9, characterized in that it further comprises a tolutriazole compound. The lubricant composition according to claim 8, characterized in that at least 60% per mole of R1, R2 and R3 combined of said at least one triglyceride are the alkene portion of oleic acid. 14. The lubricating composition according to claim 13 characterized in that said vegetable oil triglyceride includes an oil from a genetically engineered plant comprising sunflower, safflower, corn, soybean, rapeseed, cañuela, maritime col, peanut, cottonseed, lesquerella or " pissed foam "or combinations thereof. 15. The lubricant composition according to claim 11, characterized in that at least 60% per mole of R, R "and R3 combined are the alkene portion of oleic acid 16. The lubricant composition according to claim 15, characterized because said vegetable oil triglyceride includes an oil from a genetically engineered plant comprising sunflower, safflower, corn, soybeans, peanuts, rape seed, lesquerella or "meadowfoam" or combinations thereof. 17. A lubricating composition according to claim 5, characterized in that said vegetable oil triglyceride is between about 40 and about 99 percent by volume of said lubricant. 18. The lubricating composition according to claim 8, characterized in that said vegetable oil triglyceride is between about 40 and about 99 percent by volume of said lubricant. 19. The lubricating composition according to claim 13, characterized in that said vegetable oil triglyceride is between about 40 and about 99 percent by volume of said lubricant. 20. A lubricating oil composition derived from the mixture in any order of the components characterized in that they comprise: a) a lubricant that includes at least 20 percent by volume based on the volume of said lubricating oil composition of at least a vegetable oil triglyceride of the formula wherein R ', R2 and R3 are independently, aliphatic hydrocarbyl groups of 7 to 23 carbon atoms, said hydrocarbyl groups of said at least one triglyceride being at least 20% per mono-unsaturated mole, and b) from about 50 to about 3000 ppm of copper based on the weight of the lubricant composition, said cobra being in an oil soluble form. 21. The lubricating oil composition according to claim 20, characterized in that it also includes between about 100 and about 4000 ppm of antimony. 22. The lubricating oil composition according to claim 20, characterized in that said vegetable oil triglyceride is between about 40 and about 99 percent by volume of said composition 23. The lubricating oil composition according to claim 22 , characterized in that at least 60% per mole of R ', R2 and R3 combined of said at least one triglyceride are oleic acid minus C02H: 24. The lubricating oil composition according to claim 23, characterized in that it also includes between about 100 and about 4000 ppm of antimony in an oil soluble form.