USE OF MOLYBDENUM COMPLEXES IN LUBRICATING OIL COMPOSITIONS FOR DIESEL ENGINES

Abstract: The use of (a) one or more trinuclear molybdenum compounds; and/or (b) one or more molybdenum dithiocarbamate and/or dithiophosphate compounds other than those defined in (a), in a diesel engine lubricating oil composition to control soot induced viscosity increase of the composition. The molybdenum compounds are also useful in controlling wear in the diesel engine and extending the drain interval of lubricating oil compositions.

Description: USE OF MOLYBDENUM COMPLEXES IN LUBRICATING OIL COMPOSITIONS FOR DIESEL ENGINES The present invention relates to use of molybdenum compounds in diesel engine lubricating oil compositions; more specifically, the invention provides for soot induced viscosity increase of lubricating oil compositions and soot induced wear in an engine to be controlled. Molybdenum disulfide is a well-known lubricant. Unfortunately, its use as an additive in oils of lubricating viscosity is limited by its insolubility in oil. Consequently, oil-soluble molybdenum sulfur-containing compounds have been proposed and investigated for use as lubricating oil additives. Commercially available dinuclear molybdenum sulfide lubricating oil additives are well-known in the art. For example, Mo 2 O 2 S 2 (dtc) 2 , where dtc represents diorganodithiocarbamate ligands that are connected to the dinuclear molybdenum sulfide core, can be added to a fresh oil of lubricating viscosity in order to enhance the oil's friction-reducing properties. Trinuclear molybdenum compounds are also disclosed in International Application No. WO 98/26030. High soot loadings in lubricating oils for diesel engine are deleterious to the oil's performance. The soot can lead to significant viscosity increase of the lubricating oil, and wear in the engine. Control of soot induced viscosity increase is necessary to pass diesel lube engine tests, such as the Mack T-8, Mercedes Benz OM441LA, XUD11 BTE and Cummins Mi l. Furthermore, the trend towards longer engine oil drain intervals has become a major concern for producers of lubricating oils for heavy duty diesel engines. Currently the engine oil drain intervals are in the range of from 40,000 to 60, 000 km, but drain intervals of 100, 000 km or more are expected to be required in the future. Conventionally, soot induced viscosity increases may be controlled by addition of excessive amounts of dispersant to lubricants. The amounts can be as much as 5 mass % (active ingredient) of dispersant. Such an approach is economically costly, leads to low temperature performance debits due to the oil thickening effect of the dispersant, and corrosion problems. Although this can be compensated by the use of lighter mineral oils such as 100 neutral oil, this can in turn lead to undesirable increase in oil volatility and liability to oxidise. Alternatively, synthetic oils may be used but these tend to be more costly. Additionally, no recognisable benefit in wear performance is obtained from increasing the amount of dispersant. WO 87/04454 discloses that certain transition metals may be utilised in an oil-soluble form in a diesel lubricant composition to substantially reduce soot related viscosity increase and the viscosity rate increase. Manganese or titanium salts of specific acids are disclosed as the preferred transitions metal compounds, with no exemplication of molybdenum compounds being provided. WO 97/47709 discloses a highly functionalised graft copolymer, which, when incorporated into a lubricant, allows the lubricant to disperse soot produced as by-product of a diesel engine without adversely affecting the viscosity of the lubricant. However, there still remains a need for alternative methods for controlling soot induced viscosity increase and wear in diesel engine lubricating oils. Further there is a need for diesel engine lubricating oils that can combine such viscosity performance with acceptable low temperature viscometric performance, such as cold cranking simulation performance, through the use of heavier mineral oil base stocks, such 150 or 200 neutral oils. This invention is concerned with the use of specific molybdenum compounds to meet the above mentioned needs. Accordingly a first aspect of the present invention is the use of (a) one or more trinuclear molybdenum compounds, and/or (b) one or more molybdenum dithiocarbamate and/or dithiophosphate compounds other than those defined in (a), in a diesel engine lubricating oil composition to control soot induced viscosity increase of the lubricating oil composition. . second aspect of the present invention is the use of (a) one or more trinuclear molybdenum compounds, and/or (b) one or more molybdenum dithiocarbamate and/or dithiophosphate compounds other than those defined in (a), in a diesel engine lubricating oil composition to control soot induced wear of the engine. A third aspect of the present invention is the use of (a) one or more trinuclear molybdenum compounds, and/or (b) one or more molybdenum dithiocarbamate and/or dithiophosphate compounds other than those defined in (a), in a diesel engine lubricating oil composition to extend the drain interval of the lubricating oil composition. BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 shows the percentage loss of various additives in oil solutions containing different levels of carbon black. Percent carbon black (% CB) is shown on the x axis and percent change of additive (%Δ) on the y axis. Figure 2 shows the concentration dependence of wear response of trinculear molybdenum compounds in sooted basestock. Weight % Mo 3 S 7 (dtc) 4 in sooted basestock is shown on the x axis and Four-Ball wear scar (mm) on the y axis. DESCRIPTION OF THE INVENTION The molydenum compounds of the present invention are particularly effective in lubricating oil compositions when present in an amount from 1 to 2000 ppm, preferably from 5 to 1000 ppm, advantageously 10 to 750 ppm, such as 20 to 750 ppm, more preferably from 30 to 500 ppm, and most preferably 40 to 250 ppm, as mass of elemental molybdenum based on the mass of the lubricating oil composition. The molybdenum compounds of the present invention preferably have a concentration by weight in the lubricating oil composition of from 50 to about 50,000 ppm based on the weight of the lubricating oil for diesel engines. Suitable molybdenum compounds may be of any nuclearity; preferably they are dinuclear and trinuclear molybdenum compounds. Examples of dinuclear molybdenum compounds may be represented by the formula Mo 2 O x S y (dtc) 2 or Mo 2 O x S y (ddp) 2 where x and y are each 0, 1, 2, 3 or 4, provided that x+y is 4, and dtc is diorganodithiocarbamate and ddp is diorganodithiophosphate. Specific examples include molybdenum dithiocarbamate and dithiophosphate compounds available from Vanderbilt and Asahi Denka, such as MOLYVAN 822, SAKURALUBE 155, SAKURALUBE 100 and SAKURALUBE 165 (all TRADEMARKS). Trinuclear molybdenum compounds, sometimes referred to as molybdenum trimers or trimers, of the present invention comprise one or more cores containing molybdenum and sulfur atoms. Also within the scope of the invention are cores where the sulfur atoms are substituted by oxygen and/or selenium atoms. Preferably the cores consist of molybdenum and sulfur atoms. Examples of trinuclear molybdenum compounds are selected from compounds having the formula Mo 3 S k L n Q z wherein the L are independently selected ligands having organo groups with a sufficient number of carbon atoms to render the compound soluble or dispersible in the oil, n is from 1 to 4, k varies from 4 through 10, Q is selected from the group of any neutral electron donating compounds. One skilled in the art can readily determine which compounds can be used as Q since Q is present to fill any vacant coordination sites on the molybdenum compound. For example, Q may be selected from water, amines, alcohols, phosphines, and ethers, and z ranges from 0 to 5 and includes non-stoichiometric values. Preferably at least 21 total carbon atoms should be present among all the ligands' organo groups, such as at least 25, at least 30, or at least 35 carbon atoms. The ligands may be independently selected from the group of X - R and and mixtures thereof, wherein X, X X 2 , and Y are independently selected from the group of oxygen and sulfur, and wherein R R 2 , and R are independently selected from hydrogen and organo groups that may be the same or different. Preferably the organo groups are hydrocarbyl groups such as alkyl (e.g., in which the carbon atom attached to the remainder of the ligand is primary or secondary), aryl, substituted aryl and ether groups. More preferably, each ligand has the same hydrocarbyl group (e.g., alkyl, aryl, etc.). Preferably the trinuclear molybdenum compounds have ligands selected from diorganodithiocarbamate and diorganodithiophosphate; more preferably the trinuclear molybdenum compounds have diorganodithiocarbamate ligands. Specific examples of preferred trinuclear molybdenum compounds are Mo 3 S 7 (dtc) 4 , Mo 3 S 4 (dtc) 4 , or mixtures thereof. Importantly, the organo groups of the ligands have a sufficient number of carbon atoms to render the compound soluble or dispersible in the oil. For example, the number of carbon atoms in each group will generally range between 1 to 100, preferably from 1 to 30, and more preferably between 4 to 20. Preferred ligands include dialkyldithiophosphate, alkylxanthate, and dialkyldithiocarbamate, and of these dialkyldithiocarbamate is the most preferred. The number of carbon atoms mentioned above are also applicable to the diorganodithiocarbamate and diorganodithiophosphate ligands of other molybdenum compounds, such as dinuclear molybdenum compounds. Organic ligands containing two or more of the above functionalities are also capable of serving as ligands and binding to one or more of the cores. The compounds of the present invention require selection of ligands having the appropriate charge to balance the core's charge. Two or more trinuclear cores interconnected by means of one or more ligands are within the scope of the invention. Without wishing to be bound by any theory, it is believed that two or more trinuclear cores may be bound or interconnected by means of one or more ligands and the ligands may be multidentate. Such structures fall within the scope of this invention. This includes the case of a multidentate ligand having multiple connections to a single core. It is believed that oxygen and/or selenium may be substituted for sulfur in the core(s). Compounds having the formula Mo 3 S L n Q z have cationic cores surrounded by anionic ligands where the cores are represented by the structures below: and/or and have net charges of +4. Consequently, in order to solubilize these cores the total charge among all the ligands must be -4. Four monoanionic ligands are preferred. Preferably, the molybdenum compound utilised herein will have a Mo 3 S 7 core Applicants believe, though not wishing to be bound, that the instant molybdenum compounds can effectively modify soot surfaces and form stable films on soot surfaces thereby reducing the soot-soot interactions resulting in resistance to soot scraping and improved wear performance thereby controlling viscosity increase. It is believed that the molybdenum compounds form molecules that interfere with soot agglomeration and alter film chemistry to reduce abrasive wear. It is further believed that the large alkyl groups of the adsorbed molybdenum compounds prevent further soot agglomeration while softening hard soot surfaces. The molybdenum compounds may further decompose under engine operating conditions to form antiwear films at the points of contact of engine surfaces. The term "hydrocarbyl" denotes a substituent having carbon atoms directly attached to the remainder of the ligand and is predominantly hydrocarbyl in character within the context of this invention. Such substituents include the following: 1. Hydrocarbon substituents, that is, aliphatic (for example alkyl or alkenyl), alicyclic (for example cycloalkyl or cycloalkenyl) substituents, aromatic-, aliphatic- and alicyclic-substituted aromatic nuclei and the like, as well as cyclic substituents wherein the ring is completed through another portion of the ligand (that is, any two indicated substituents may together form an alicyclic group). 2. Substituted hydrocarbon substituents, that is, those containing non- hydrocarbon groups which, in the context of this invention, do not alter the predominantly hydrocarbyl character of the substituent. Those skilled in the art will be aware of suitable groups (e.g., halo, especially chloro and fluoro, amino, alkoxyl, mercapto, alkylmercapto, nitro, nitroso, sulfoxy, etc.) 3. Hetero substituents, that is, substituents which, while predominantly hydrocarbon in character within the context of this invention, contain atoms other than carbon present in a chain or ring otherwise composed of carbon atoms. Oil-soluble or -dispersible trinuclear molybdenum compounds can be prepared by reacting in the appropriate liquid(s)/solvent(s) a molybdenum source such as (NH 4 ) Mo 3 S 13 .n(H 2 O),where n varies between 0 and 2 and includes non-stoichiometric values, with a suitable ligand source such as a tetralkylthiuram disulfide. Other oil-soluble or dispersible trinuclear molybdenum compounds can be formed during a reaction in the appropriate solvent(s) of a molybdenum source such as of (NH 4 ) 2 Mo 3 S 13 .n(H 2 O), a ligand source such as tetralkylthiuram disulfide, dialkyldithiocarbamate, or dialkyldithiophosphate and, where required, a sulfur abstracting agent such as cyanide ions, sulfite ions, or substituted phosphines. Alternatively, a trinuclear molybdenum-sulfur halide salt such as [M ] 2 [Mo 3 S 7 A 6 ], where M is a counter ion, and A is a halogen such as Cl, Br, or I, may be reacted with a ligand source such as a dialkyldithiocarbamate or dialkyldithiophosphate in the appropriate liquid(s)/solvent(s) to form an oil-soluble or -dispersible trinuclear molybdenum compound. The appropriate liquid/solvent may be for example aqueous or organic. In general, the compounds prepared as outlined above can be purified by well known techniques such as chromatography and the like; however, it may not be necessary to purify the compounds. Crude mixtures that contain substantial amounts of the compound have been found to be effective. In relation to all aspects of the present invention, the molybdenum compounds may be oil- soluble or oil-dispersible. A compound's oil solubility or dispersibility may be influenced by the number of carbon atoms in the ligands' organo groups. Preferably, the ligand source chosen has a sufficient number of carbon atoms in its organo groups to render the compound soluble or dispersible in the lubricating composition. Preferably, in relation to all aspects of the present invention the molybdenum compound, e.g., whether dinuclear or trinuclear, is a molybdenum dithiocarbamate compound; more preferably the molybdenum compound is a trinuclear molybdenum dithiocarbamate compound, such as Mo 3 S 7 (dtc) 4 . The terms "oil-soluble" or "oil-dispersible" used herein do not necessarily indicate that the compounds or additives are soluble, dissolvable, miscible, or capable of being suspended in the oil in all proportions. These do mean, however, that they are, for instance, soluble or stably dispersible in oil to an extent sufficient to exert their intended effect in the environment in which the oil is employed. Moreover, the additional incorporation of other additives may also permit incorporation of higher levels of a particular additive, if desired. In relation to all aspects of the present invention the molybdenum dithiocarbamate and dithiophosphate compounds are useful in lubricating oil compositions for use in low speed, high torque operating diesel engines, such as light duty and heavy duty diesel engines. Preferably lubricating oil compositions used in such engines are prone to soot build-up, and this is particularly the case where the lubricating oil used is a mineral oil. In relation to all aspects of the present invention lubricating oil compositions may contain soot or may be free from soot. Thus the present invention contemplates that the molybdenum compounds of the present invention can be added either prior to or post soot formation in the lubricating oil composition. Preferably the or each molybdenum compound is added prior to soot formation in order to reduce the amount of dispersant required and thereby achieve acceptable low temperature performance. Soot in lubricating oil compositions typically results from lubricating oils being subjected to operating conditions such as exposure to high shear forces, high temperature, a hostile chemical or physical environment, or similar conditions. The molybdenum compounds of the present invention are useful in controlling, that is retarding or preventing, soot induced viscosity increase, and soot induced wear. The molybdenum compounds are particularly effective in being able to absorb onto carbon black or engine soot. Other known lubricant additives may be compatible with the invention and can be present in the lubricating oil being treated. These include for example friction-reducing agents, dispersants, single or mixed metal detergents, pour point depressants, viscosity improvers, antioxidants, surfactants, and antiwear agents. They can be present in amounts commonly utilized in the art. For example, beneficial lubricant additives containing phosphorous and/or sulfur compounds such as ZDDP may be contained in the lubricating oils of the present invention. Co-Additives The lubricating oil composition of the present invention can be used in the formulation of crankcase lubricating oils (i.e. heavy duty diesel motor oils and passenger car diesel oils) for spark-ignited and compression-ignited engines. The additives listed below are typically used in such amounts so as to provide their normal attendant functions. Typical amounts of individual components are also set forth below. All the values listed are stated as mass percent active ingredient in the total lubricating oil composition. The use of dispersants, such as ashless dispersants, as co-additives has been referred to hereinbefore and will be further discussed hereinafter. The individual additives may be incorporated into a base stock in any convenient way. Thus, each of the components can be added directly to the base stock by dispersing or dissolving it in the base stock at the desired level of concentration. Such blending may occur at ambient temperature or at an elevated temperature. Preferably, all the additives except for the viscosity modifier and the pour point depressant are blended into a concentrate or additive, package, described herein as the additive package, that is subsequently blended into base stock to make finished lubricant. Use of such concentrates is conventional. The concentrate will typically be formulated to contain the additive(s) in proper amounts to provide the desired concentration in the final formulation when the concentrate is combined with a predetermined amount of base lubricant. The concentrate is conveniently made in accordance with the method described in US 4,938,890. That patent describes making a pre-mix of ashless dispersant and metal detergents that is pre- blended at a temperature of at least about 200°C. Thereafter, the pre-mix is cooled to at least 85° C and the additional components are added. The final crankcase lubricating oil formulation may employ from 2 to 20 mass % and preferably 5 to 10 mass %, more preferably 7 to 8 mass % of the concentrate or additive package with the remainder being base stock. The ashless dispersant may comprise an oil soluble polymeric hydrocarbon backbone having functional groups that are capable of associating with particles to be dispersed. Typically, the dispersants comprise amine, alcohol, amide, or ester polar moieties attached to the polymer backbone often via a bridging group. The ashless dispersant may be, for example, selected from oil soluble salts, esters, amino-esters, amides, imides, and oxazolines of long chain hydrocarbon substituted mono and dicarboxylic acids or their anhydrides; thiocarboxylate derivatives of long chain hydrocarbons; long chain aliphatic hydrocarbons having a polyamine attached directly thereto; and Mannich condensation products formed by condensing a long chain substituted phenol with formaldehyde and polyalkylene polyamine. The viscosity modifier (VM) functions to impart high and low temperature operability to a lubricating oil. The VM used may have that sole function, or may be multifunctional. Multifuctional viscosity modifiers that also function as dispersants are also known. Suitable viscosity modifiers are polyisobutylene, copolymers of ethylene and propylene and higher alpha- olefins, polymethacrylates, polyalkylmethacrylates, methacrylate copolymers, copolymers of an unsaturated dicarboxylic acid and a vinyl compound, inter polymers of styrene and acrylic esters, and partially hydrogenated copolymers of styrene/isoprene, styrene/butadiene, and isoprenebutadiene, as well as the partially hydrogenated homopolymers of butadiene and isoprene and isoprene/divinylbenzene. Metal-containing or ash-forming detergents function both as detergents to reduce or remove deposits and as acid neutralizers or rust inhibitors, thereby reducing wear and corrosion and extending engine life. Detergents generally comprise a polar head with long hydrophobic tail, with the polar head comprising a metal salt of an acid organic compound. The salts may contain a substantially stoichiometric amount of the metal in which they are usually described as normal or neutral salts, and would typically have a total base number (TBN), as may be measured by ASTM D-2896 of from 0 to 80. It is possible to include large amounts of a metal base by reacting an excess of a metal compound such as an oxide or hydroxide with an acid gas such as carbon dioxide, The resulting overbased detergent comprises neutralized detergent as the outer layer of a metal base (e.g., carbonate) micelle. Such overbased detergents may have a TBN of 150 or greater, and typically from 250 to 450 or more. Detergents that may be used include oil-soluble neutral and overbased sulfonates, phenates, sulfurized phenates, thiophosphonates, salicylates, and naphthenates and other oil-soluble carboxylates of a metal, particularly the alkali or alkaline earth metals, e,g., sodium, potassium, lithium, calcium, and magesium. The most commonly used metals are calcium and magnesium, which may both be present in detergents used in a lubricant, and mixtures of calcium and/or magnesium with sodium. Particularly convenient metal detergents are neutral and overbased calcium sulfonates having TBN of from 20 to 450 TBN, and neutral and overbased calcium phenates and sulfurized phenates having TBN of from 50 to 450. Dihydrocarbyl dithiophosphate metal salts are frequently used as anti-wear and antioxidant agents. The metal may be an alkali or alkaline earth metal, or aluminum, lead, tin, molybdenum, manganese, nickel or copper. The zinc salts are most commonly used in lubricating oil in amounts of 0.1 to 10, preferably 0.2 to 2 wt. %, based upon the total weight of the lubricating oil composition, They may be prepared in accordance with known techniques by first forming a dihydrocarbyl dithiophosphoric acid (DDPA), usually by reaction of one or more alcohol or a phenol with P 2 S 5 and then neutralizing the formed DDPA with a zinc compound. For example, a dithiophosphoric acid may be made by reacting mixtures of primary and secondary alcohols. Alternatively, multiple dithiophosphoric acids can be prepared where the hydrocarbyl groups on one are entirely secondary in character and the hydrocarbyl groups on the others are entirely primary in character. To make the zinc salt any basic or neutral zinc compound could be used but the oxides, hydroxides and carbonates are most generally employed. Commercial additives frequently contain an excess of zinc due to use of an excess of the basic zinc compound in the neutralization reaction. Oxidation inhibitors or antioxidants reduce the tendency of base stocks to deteriorate in service which deterioration can be evidenced by the products of oxidation such as sludge and varnishlike deposits on the metal surfaces and by viscosity growth. Such oxidation inhibitors include hindered phenols, secondary aromatic amines, alkaline earth metal salts of alkylphenolthioesters having preferably C5 to C2 alkyl side chains, calcium nonylphenol sulfide, ashless oil soluble phenates and sulfurized phenates, phosphosulfurized or sulfurized hydrocarbons, phosphorous esters, metal thiocarbamates, oil soluble copper compound as described in US 4,867,890, and other molybdenum containing compounds. Friction modifiers may be included to improve fuel economy. Oil-soluble alkoxylated mono- and di-amines are well known to improve boundary layer lubrication. The amines may be used as such or in the form of an adduct or reaction product with a boron compound such as boric oxide, boron halide, metaborate, boric acid or a mono-, di- or tri-alkyl borate. Other friction modifiers are known. Among these are esters formed by reacting carboxylic acids and anhydrides with alkanols. Other conventional friction modifiers generally consist of a polar terminal group (e.g. carboxyl or hydroxyl) covalently bonded to an oleophilic hydrocarbon chain. Esters of carboxylic acids and anhydrides with alkanols are described in US 4,702,850. Examples of other conventional friction modifiers are described by M. Belzer in the "Jounal of Tribology" (1992), Vol. 114, pp. 675-682 and M. Belzer and S. Jahanmir in "Lubricating Science" (1988), Vol. 1, pp. 3-26. One such example is organo-metallic molybdenum. Rust inhibitors selected from the group consisting of noninic polyoxyalkylene polyols and esters thereof, polyoxyalkylene phenols, and anionic alkyl sulfonic acids may be used. Copper and lead bearing corrosion inhibitors may be used. Typically such compounds are the thiadiaole polysulfides containing from 5 to 50 carbon atoms, their derivatives and polymers thereof. Derivatives of 1,3,4 thiadiazoles such as those described in U.S, Patent Nos. 2,71 ,125; 2,719,126; and 3,087,932; are typical. Other similar materials are described in U.S. Patent Nos. 3,821,236; 3,904,537; 4,097,387; 4,107,059; 4,136,043; 4,188,299; and 4,193,882. Other additives are the thio and polythio sulfenamides of thiadiazoles such as those described in UK Patent Specification No. 1,560,830. Benzotriazoles derivatives also fall within this class of additives. When these compounds are included in the lubricating oil composition they are preferably present in an amount not exceeding, 0.2 wt. % active ingredient. A small amount of a demulsifying component may be used. A preferred demulsifying component is described in EP 330,522. It is obtained by reacting an alkylene oxide with an adduct obtained by reacting a bis-epoxide vith a polyhydric alcohol, The demulsifier should be used at a level not exceeding 0.1 mass % active ingredient. A treat rate of 0.001 to 0.05 mass % active ingredient is convenient. Pour point depressants, otherwise known as lube oil flow improvers, lower the minimum temperature at which the fluid will flow or can be poured. Such additives are well known. Typical of those additives which improve the low temperature fluidity of the fluid are C8 and Ci8 dialkyl fumarate/vinyl acetate copolymers, polyalkylmethacrylates and the like. Foam control can be provided by many compounds including an antifoamant of the polysiloxane type, for example, silicone oil or polydimethyl siloxane. Some of the above-mentioned additives can provide a multiplicity of effects; this approach is well-known and does not require further elaboration. Preferably the molybdenum compounds of the present invention are useful in combination with one or more of the co-additives described above in the amounts described in the Table above. The present invention also provides a diesel engine lubricating oil composition which controls soot induced viscosity increase of the lubricating oil composition and which provides acceptable low temperature viscometrics of the oil without using low viscosity mineral oil or synthetic oil. The lubricating oil compositions may comprise lower than conventional amounts, for example less than 4 mass % (based on active ingredient) of dispersant. Preferably, the amount of dispersant is less than 3.5 mass %, such as less than 3 mass %, or less than 2 mass %, based on the mass of the lubricating oil composition. Such diesel engine lubricating oil compositions are particularly useful in lubricating heavy duty diesel engines. The diesel engine tests, such as the Mack T-8, XUD11 BTE and Cummins Mi l may be passable, preferably be passed, with the lubricating oil compositions of the present invention. It will be understood that various components of the composition, essential as well as optional and customary, may react under the conditions of formulation, storage, or use, and that the product obtained or obtainable as a result of such reaction is within the scope of the present invention. The lubricating oil may be selected from any lubricating oil suitable for use in diesel engines, such as those derived from animal, vegetable or synthetic oils. For example, any one of Group I, Group II, Group III, Group IV, Group V or a mixture thereof. The lubricating oil conveniently 2 1 has a viscosity of about 2 to 50 mm /s at 100 °C, preferably 2 to 20 mm /s, more preferably 2.5 to 12 mm Is, such as 2.5 to 9 mm Is, or 3 to 7 mm Is, at 100 °C. Preferably the lubricating oil comprises, preferably is, mineral oil. Concentrates of the molybdenum compounds, and optionally other additives, afford a convenient means of supply to the lubricating oils for diesel engines. Thus, the molybdenum compounds of the present invention can be utilized in a suitable oleaginous carrier to provide a convenient means of handling the compounds before their use. Oils of lubricating viscosity, such as vegetable oil, mineral oil, animal oil, synthetic oil, or diesel oil itself can be used as a carrier as well as aliphatic, naphthenic, and aromatic hydrocarbons. These concentrates may contain about 1 to about 90 weight percent of the molybdenum compound based on the weight of the concentrate, preferably from about 1 to about 70 weight percent and more preferably from about 20 to about 70 weight percent. It is also believed that the present invention prevents soot formation in the catalytic converter and/or combustion chamber. This is an added advantage and will keep the engine running more smoothly. In this instant, it is believed that the molybdenum acts as a combustion catalyst and reduces the formation of soot. In today's engines, oil bleed into the combustion chamber is continuous and needs to be burnt off. This process is referred to as "on-board refining." Since the molybdenum compounds, especially the trinuclear molybdenum compounds, of the instant invention are attracted to soot, any soot that does form will immediately adsorb the molybdenum compound which should help it combust and prevent soot formation. The invention will be more fully understood by reference to the following examples illustrating various modifications of the invention which should not be construed as limiting the scope thereof. As used herein, ddp represents dialkyldithiophosphate and dtc represents dialkyldithiocarbamate. Examples: Example 1 deals with the adsorption/binding behaviour of trinuclear molybdenum compounds with soot. Examples 2 and 3 deal with the wear benefit as well as its resistance to soot scraping using a conventional four-ball wear test. Example 1 : The adsorption of lube components onto soot surface is thought to be critical for soot-viscosity control, friction and wear. Dispersants are good in soot-handling because they can adhere to the soot surface and thereby interfere with soot particle agglomeration. The partitioning equilibria for various additives on carbon black (CB) and on real engine soot were quantitatively measured. Differential IR combined with a filtration technique were used to quantify the additive loss in oil solution mixed with carbon black or engine soot. Fixed amounts of carbon black were blended in pure basestock (lubricating oil) with 1 percent weight of the additive of interest. Before doping carbon black into the oil, the IR spectrum was taken for each additive solution as a reference point. Another IR was then taken of the filtered oil. A comparison of the IR spectra before and after the filtration was analyzed to quantify the amount of additive absorbed on the soot surface. Figure 1 shows the percentage loss of common additives in solution containing different levels of carbon black (CB). The data shows that the loss of additive in oil depends on the amount of the trapping material. The concentration dependence of adsorption loss for most additives follows the Langmuir isotherm and the additive content within oil is in equilibrium between trapping sites on soot surface and the additive concentration in solution. As shown in Figure 1 , trinuclear molybdenum compounds show a high tendency to bind with CB. This binding is much stronger than with ZDDP additives or phenolics and is almost equivalent to the binding strength of CB with dispersant. A study of temperature dependence of the equilibrium constant provides the binding enthalpy for trinuclear molybdenum compound Mo 3 S 7 (dtc) 4 . The binding enthalpy was determined to be approximately 5 Kcal/mole. The dispersant used was a polyisobutenyl succinimide and the detergent used was a calcium sulfurised phenate having a TBN of about 150. Example 2: This example illustrates that Mo 3 S 7 (dtc) 4 layers adsorbed on the soot surface show anti-wear benefit toward soot scraping. The wear performance of Mo 3 S 7 (dtc) 4 in basestock was evaluated with the four-ball wear test. The test conditions (60 Kg load, 1200 rpm speed, 45 minute at 100°C) were similar to the ASTM D4172 method. Figure 2 shows the wear response of different concentration levels of trinuclear molybdenum compound in sooted MCT30 (a diesel engine basestock) with a fixed 2.8 percent weight soot level. The sooted basestock was obtained by running a diesel GM6.2L engine with MCT30 alone (no additives). The 1 percent weight of Mo 3 S 7 (dtc) 4 in oil corresponds to a concentration of 1250ppm of [Mo]. As shown in Figure 2, a beneficial wear response in lubricating oil containing soot is observed when 0.2 percent weight of trinuclear molybdenum compound is added. The response rapidly plateaus at higher concentrations. However, since molybdenum is lost during engine operation, higher concentrations of Mo are accepted. Example 3: This example illustrates that Mo 3 S 7 (dtc) 4 films minimize soot abrasion. Under boundary conditions, rubbing surfaces become extremely reactive due to mechanical activity. Likewise, friction can initiate and accelerate chemical reactions that otherwise would not initiate at all or would take place at much higher temperatures. One possible mechanism involves the emission of low energy electrons from surfaces during friction. There is strong evidence that a non- metallic oxide layer is responsible for electron emission. These emitted electrons interact with anti-wear additive to generate negative ions or other anion-radical reactive intermediates, which are critical in anti-wear film formation. Trinuclear molybdenum compounds have a high tendency to adsorb on negatively charged metal surfaces and subsequently provide an effective way to deliver the formation of MoS 2 . Trinuclear molybdenum compounds such as Mo 3 S 7 (dtc) 4 consist of two types of ligands, three attached to individual molybdenum atoms and the other loosely attached to the trinuclear molybdenum core. (The general structure can be presented Mo 3 S 7 (dtc) 3 (dtc'). This fourth dtc ligand (dtc 1 ) shows a high tendency to depart from the metal core and to leave an electrophilic complex which is highly susceptible for anion formation on the metal surface. Table I lists the wear response. of several samples in sooted MCT30 (all in 2.8 percent weight soot level): (A) basestock alone, (B) 1 percent Mo 3 S 7 (dtc) 4 , and (C) 0.5 percent Mo 3 S 7 (dtc) 4 . In the presence of the trinuclear molybdenum compound, soot-induced wear is substantially reduced. This can be seen by the wear scar, which is reduced from 1.36mm to 0.79mm. The reduction is apparently caused by the formation of a stable friction/anti-wear film on the soot surface. Soot particles were separated from the oil solution by centrifugation with a speed of 16, OOOrpm. After separation, the wear data for the top solutions are also improved from the base case. This is due to the remaining trinuclear molybdenum compounds within the oil solution which can still provide anti-wear benefit. The wear response of dried out sooted precipitate from the centrifuge put back into MCT30 basestock with the appropriate amount of 2.8 percent weight soot. This indicates that there is a modification of the soot that presumably smoothes the surface for wear reduction. As shown in Table 1, a definite improvement against the base case (0.89mm vs 1.36mm wear scar) is observed. It is concluded that the modified soot after re-dispersion is less harmful than the fresh soot in the base case without modification. In case (C), after centrifugation, the wear scar of the sample redispersed into the basestock turns out to be much worse than the base case. It is believed that the reason that poor wear data is obtained for the 0.5 percent Mo 3 S 7 (dtc) 4 sample reintroduced into the basestock is that the soot was thoroughly washed with pentane to remove the trinuclear molybdenum compound on the surface which caused wear to increase. The removal of trinuclear molybdenum compounds from soot surfaces with excessive pentane as well as the agglomeration process of the soot particles makes it difficult to redisperse the soot back into solution. TABLE I Four-ball wear results in sooted MCT30 before and after centrifugal separation of soot

Claims: CLAIMS 1. Use of (a) one or more trinuclear molybdenum compounds, and/or (b) one or more molybdenum dithiocarbamate and/or dithiophosphate compounds other than those defined in (a), in a diesel engine lubricating oil composition to control soot induced viscosity increase of the lubricating oil composition. 2. Use of (a) one or more trinuclear molybdenum compounds, and/or (b) one or more molybdenum dithiocarbamate and/or dithiophosphate compounds other than those defined in (a), in a diesel engine lubricating oil composition to control soot induced wear of the engine. 3. Use of (a) one or more trinuclear molybdenum compounds, and/or (b) one or more molybdenum dithiocarbamate and/or dithiophosphate compounds other than those defined in (a), in a diesel engine lubricating oil composition to extend the drain interval of the lubricating oil composition. 4. The use as claimed in any one of claims 1 to 3, wherein the molybdenum compound is present in an amount from 1 to 2000 ppm as mass of elemental molybdenum based on the mass of the lubricating oil composition. 5. The use as claimed in any one of claims 1 to 4, wherein the molybdenum compound defined in (b) is a molybdenum dithiocarbamate compound. 6. The use as claimed in claim 5, wherein the molybdenum dithiocarbamate is of general formula Mo 2 O x S y (dtc) 2 where x and y are each 0, 1, 2, 3, or 4, provided that x + y is 4, and dtc is diorganodithiocarbamate ligand. 7. The use as claimed in any one of claims 1 to 4 wherein the molybdenum compound is a trinuclear molybdenum compound. 8. The use as claimed in claim 7, wherein the trinuclear molybdenum compound comprises one or more cores containing molybdenum and sulfur atoms. 9. The use as claimed in either claim 7 or claim 8, wherein the trinuclear molybdenum compound has the formula Mo 3 S k L n Q z wherein L are independently selected ligands having organo groups with a sufficient number of carbon atoms to render the compound soluble or dispersible in the oil, n is from 1 to 4, k varies from 4 through 10, Q is a neutral electron donating compound selected from the group consisting of water, amines, alcohols, phosphines and ethers, and z ranges from 0 to 5 and includes non-stoichiometric values. 10. The use as claimed in any one of claims 7 to 9, wherein L is diorganodithiocarbamate. 11. The use as claimed in any one of claims 7 to 10, wherein the molybdenum compound is selected from Mo 3 S 7 (dtc) 4 , Mo 3 S 4 (dtc) 4 and mixtures thereof, wherein dtc is diorganodithiocarbamate . 12. The use as claimed in any one of claims 7 to 11, wherein the trinuclear molybdenum compound comprises one or more cores selected from and 13. The use as claimed in any one of claims 10 to 12, wherein the diorganodithiocarbamate ligand is represented by the formula: where R { and R 2 are independently selected from hydrogen and organo groups. 14. The use as claimed in claim 13, wherein R t and R 2 are alkyl groups and the number of carbon atoms in each alkyl group ranges from 1 to 30. 15. The use as claimed in any one of claims 9 to 14, wherein the molybdenum compound forms a monolayer on the surfaces of soot. 16. The use as claimed in any one of the preceding claims, wherein the lubricating oil composition contains soot. 17. The use as claimed in any of the preceding claims, wherein the lubricating oil composition in the diesel engine is prone to soot build-up. 18. The use as claimed in any of the preceding claims, wherein the lubricating oil composition comprises mineral oil. 19. A diesel engine lubricating oil composition useful in controlling soot induced viscosity increase of the composition and/or controlling the low temperature viscometric properties of the composition wherein the composition comprises a major amount of oil of lubricating viscosity, and admixed therewith, a minor amount of: (i) one or more molybdenum compounds defined in any one of claims 1 to 14; and (ii) one or more dispersants present in an amount less than 4 mass % based on the mass of the lubricating oil composition. 20. The composition of claim 19 wherein the lubricating oil comprises mineral oil. 21. Use of a diesel engine lubricating oil composition defined in either claim 19 or claim 20 to control soot induced viscosity increase of the composition and/or control the low temperature viscometric properties of the composition. 22. A method for improving the performance of a sooted diesel oil and controlling soot induced viscosity increase and wear and extending diesel engine oil drain intervals comprising adding to a major amount of a diesel oil a minor amount of a composition comprising a least one compound having the formula Mo 3 S k L n Q z and mixtures thereof wherein the L are independently selected ligands having organo groups with a sufficient number of carbon atoms to render the compound soluble or dispersible in the oil, n is from 1 to 4, k varies from 4 through 10, Q is a neutral electron donating compound selected from the group consisting of water, amines, alcohols, phosphines and ethers, and z ranges from 0 to 5 and includes non-stoichiometric values.

Inventors: FANG HOWARD LIH, MCCONNACHIE JONATHAN, STIEFEL EDWARD IRA, FANG, HOWARD, LIH, MCCONNACHIE, JONATHAN, STIEFEL, EDWARD, IRA
Applicants: EXXON CHEMICAL LTD, EXXON CHEMICAL PATENTS INC, FANG HOWARD LIH, MCCONNACHIE JONATHAN, STIEFEL EDWARD IRA, EXXON CHEMICAL LIMITED, EXXON CHEMICAL PATENTS INC., FANG, HOWARD, LIH, MCCONNACHIE, JONATHAN, STIEFEL, EDWARD, IRA
Application year: 1998
Main classification: C10M135
IPC codes: C10M135, C10M137, C10M159