Lubricating compositions and additives therefor

Abstract: In accordance with this invention, there is provided a lubricating composition comprising a major amount of an oil of lubricating viscosity and a minor amount of an additive having the formula Mo₂L₄ wherein L is a ligand selected from xanthates and mixtures thereof and, in particular, xanthates having a sufficient number of carbon atoms to render the additive soluble in the oil. In general, the xanthate ligand, L, will have from about 1 to 30 carbon atoms.

Description: This invention relates to improved lubricating compositions. Molybdenum disulfide is a known lubricant additive. Unfortunately, it has certain known disadvantages which are associated with the fact that it is insoluble in lubricating oils. Therefore, oil soluble molybdenum sulfide containing compounds have been proposed and investigated as lubricant additives. For example, in U.S. Patent 2,951,040, an oil soluble molybdic xanthate is disclosed as being useful in lubricating compositions. Apparently, the molybdic xanthate decomposes under conditions of use to form an oil insoluble molybdenum sulfide on the metal surfaces being lubricated. U.S. Patent 4,013,571 discloses the use of certain thiosulfenyl xanthates in ashless lubricant compositions. U.S. Patent 4,259,254 discloses the use of xanthate containing molybdenum compounds in lubricating oil compositions. U.S. Patent 4,369,119 discloses an antioxidant additive for lubricating oils which is prepared by reacting an acidic molybdenum compound with a basic nitrogen compound and a sulfur compound and combining that product with an organic sulfur compound. In this regard, see also U.S. Patent 4,395,343 and U.S. Patent 4,402,840. U.S. Patent 4,474,673 discloses antifriction additives for lubricating oils which are prepared by reacting a sulfurized organic compound having an active hydrogen or potentially active hydrogen with molybdenum halide. U.S. Patent 4,497,719 discloses the use of metal salts of thiadiazole, such as molybdenum salts of thiadiazole as antiwear lube additives. The foregoing patents are listed as representative of the many known molybdenum sulfur containing lubricant additives. As is known in the art, some lubricant additives function as antiwear agents, some as antifriction agents and some as extreme pressure agents. Indeed, some additives may satisfy more than one of these functions. For example, metal dialkyl dithiophosphates represent a class of additives which are known to exhibit antioxidant and antiwear properties. The most commonly used additives of this class are the zinc dialkyl dithiophosphates. These compounds provide excellent oxidation resistance and exhibit superior antiwear properties. Unfortunately, they do not have the most desirable lubricity. Therefore, lubricating compositions containing these compounds also require the inclusion of antifriction agents. This leads to other problems in formulating effective lubricant compositions. Additionally, extreme care must be exercised in combining various additives to assure both compatibility and effectiveness. For example, some antifriction agents affect the metal surfaces differently than the antiwear agents. If each type of additive is present in a lubricant composition, each may compete for the surface of the metal parts which are subject to lubrication. This can lead to a lubricant that is less effective than expected based on the properties of the individual additive components. Thus, there still remains a need for improved lubricating oil additives that can be used with standard lubricating oils and that are compatible with other conventional components of the lubricating oil compositions. In accordance with this invention, there is provided a lubricating composition comprising a major amount of an oil of lubricating viscosity and a minor amount of an additive having the formula Mo₂L₄ wherein L is a ligand selected from xanthates and mixtures thereof having a sufficient number of carbon atoms to render the additive soluble in the oil. In general, the xanthate ligand, L, will have from 1 to 30 carbon atoms. The lubricant compositions according to this invention have excellent antiwear, antioxidant and friction reducing properties. The lubricant compositions of the present invention also are compatible with other standard additives used in formulating commercial lubricating compositions. The lubricating composition of the present invention includes a major amount of an oil of lubricating viscosity. This oil may be selected from naturally occurring mineral oils or from synthetic oils. The oils may range in viscosity from light distillate mineral oils to heavy lubricating oils such as gas engine oil, mineral lubricating oil, motor vehicle oil and heavy duty diesel oil. In general, the viscosity of the oil will range from 5 x 10⁻⁶ to 26 x 10⁻⁶ m²/s (5 centistokes to 26 centistokes) and especially in the range of 10 x 10⁻⁶ to 18 x 10⁻⁶ m²/s (10 centistokes to 18 centistokes) at 100°C. The additive may have the formula Mo₂(ROCS₂)₄ wherein R is selected from alkyl groups, aralky groups, alkoxylalkyl groups and the like. When R is an alkyl group, the number of carbon atoms in the alkyl group will generally range between 1 to 30 and, preferably, between 2 to 12. The additives of the present invention may be prepared by generally known techniques. For example an alkali metal xanthate may be reacted with dimolybdenum tetra-acetate to produce the Mo₂L₄ compound. (See Webb, T. R. et al, Inorg. Chim. Acta., 49 , 107, 1981.) The above described Mo₂L₄ complexes are effective as additives in lubricating compositions when they are used in amounts generally ranging from 0.01 to 10 wt.% based on the weight of the lubricating oil, preferably from 0.1 to 10 wt.%, and more preferably in concentrations ranging from 0.1 to 1.0 wt.%. Concentrates of the additive of the present invention in a suitable diluent hydrocarbon carrier provide a convenient means of handling the additives before their use. Aromatic hydrocarbons, especially toluene and xylene, are examples of suitable hydrocarbon diluents for additive concentrates. These concentrates may contain 1 to 90 wt.% of the additive based on the weight of diluent, although it is preferred to maintain the additive concentration between 20 and 70 wt.%. If desired, other known lubricant additives can be used for blending in the lubricant compositions of this invention. These include ashless dispersants detergents, pour point depressants, viscosity improvers and the like. These can be combined in proportions known in the art. The invention will be more fully understood by reference to the following preparative procedures examples and comparative examples illustrating various modifications of the invention, which should not be construed as limiting the scope thereof. Procedure for Preparation of Mo₂(Octylxanthate)₄ 0.98 grams (4.0 mmol) of potassium oxtylxanthate was dissolved in 25 ml of degassed methanol and added to 0.43 grams (1.0 mmol) of dimolybdenum tetra-acetate dissolved in 75 ml of degassed methanol. After stirring for approximately 1 hour, bright red crystals of Mo₂(xanthate)₄ were isolated from the dilute green solution by filtration. These crystals were washed with degassed methanol three times (20 ml each time) and vacuum dried to yield 0.94 grams (93%) of Mo₂(octylxanthate)₄. Examples 1 to 3 These examples illustrate the antiwear properties of a lubricating composition containing a dimolybdenum tetraxanthates in accordance with the invention. In these examples, the additive prepared by the procedure outlined above was evaluated for wear protection using the Four-Ball Wear Test procedure (ASTM Test D2266). In Example 1, the sample tested consisted of Solvent 150 Neutral (S150) lubricating oil and 0.5 wt.% of the Mo₂L₄ additive. In Examples 2 and 3, the sample consisted of a commercially available motor oil which did not contain zinc dithiophosphate (ZDDP) and, instead, contained 0.5 wt.% of the Mo₂L₄ additive. The results of these tests are given in Table 1. Comparative Examples 1 to 4 In Comparative Example 1, the Four-Ball Wear Test procedure was conducted using Solvent 150 Neutral. In Comparative Example 2, the test was repeated using Solvent 150 Neutral containing 1.4 wt.% of zinc dithiodiphosphate (ZDDP). In Comparative Example 3, the test was again repeated, in this instance using a commercially available motor oil which did not contain any zinc dithiophosphate (ZDDP). And finally, another Comparative Example, 4, was conducted, in this instance using a commercially formulated motor oil containing 1.4 wt.% zinc dithiodiphosphate (ZDDP). The results are also given in Table 1. Example 4 A differential scanning calorimetry (DSC) test was conducted on a lubricating oil containing the additive of this invention. In this DSC test, a sample of the oil is heated in air at a programmed rate; e.g., 5°C/minute and the sample temperature rise relative to an inert reference was measured. The temperature at which an exothermic reaction (the oxidation onset temperature) is a measure of oxidative stability of the sample. In this Example 4, the sample consisted of S150N and 0.5 wt.% of the Mo₂L₄ additive prepared as outlined above. The results of this test are shown in Table 2 below. A lube oil stability test was also conducted. This test involves measuring the kinematic viscosity of the sample at 40°C, heating the sample at 172°C for 46 hours while passing air through the sample (flow rate -1 liter/min.) and remeasuring the kinematic viscosity at 40°C. The percent increase in the viscosity is an indication of oxidation. The results of this test are also shown in Table 2. Comparative Examples 5 and 6 For comparative purposes, the DSC test and the lube stability test were conducted on samples of S150N (Comp. Ex. 5) and a fully formulated commercial motor oil (Comp. Ex. 6). The results of this test are also given in Table 2 below. Example 7 This example illustrates the friction reducing properties of the lubricating compositions of this invention. For the purpose of this example, friction measurements were performed in a ball on cylinder friction tester using S150N base oil containing 0.5 wt.% of Mo₂L₄ where L is octylxanthate. This test employs a 12.5 mm diameter stationary ball and a rotating cylinder 43.9 mm in diameter. Both components were made from AISI 52100 steel. The steel balls were used in the heat treated condition with a Vickers hardness of 840, the cylinders used in the normalized condition with a Vickers hardness of 215. The cylinder rotates inside a cup containing sufficient quantity of lubricant such that 2 mm of the cylinder bottom is submerged. The lubricant is carried to the ball contact by the rotation of the cylinder. A normal force of 9.8N was applied to the ball through dead weights, the cylinder rotated at 0.25 RPM to ensure boundary lubrication conditions prevailed. The friction force was continuously monitored through a load transducer by measuring the tangential force on the ball. Friction coefficients attain steady state values after 7 to 10 turns of the cylinder. It is well known that stearic acid is an excellent friction modifier. Under the conditions stated above, the minimum friction coefficient obtained with stearic acid in hexadecane is 0.077. With 0.5 wt.% Mo₂L₄, the friction coefficient is 0.037, exceptionally low friction under boundary lubrication conditions. Commercial friction modifiers in these ball on cylinder tests exhibit friction coefficients ranging from 0.12 to 0.14. S150N without any additives has a friction coefficient under these conditions of 0.30.

Claims: A lubricating composition comprising: a major amount of an oil of lubricating viscosity; and a minor amount of an additive having the formula Mo₂L₄, where L is a ligand selected from a xanthate and mixtures of xanthates containing organo groups having a sufficient number of carbon atoms to render the additive soluble in the oil. The composition of claim 1, wherein the number of carbon atoms in each organo group is from about 1 to about 30. The composition of claim 1 or 2, wherein the organo groups are selected from alkyl, aralkyl and alkoxylalkyl ether groups. The composition of claim 3, wherein the organo groups are alkyl groups. The composition of any preceding claim wherein the amount of the additive is in the range of from 0.01 to 10 weight percent based on the weight of oil. The composition of claim 5, wherein the amount of the additive is in the range of from 0.1 to 1.0 weight percent based on the weight of the oil. The composition of any preceding claim, wherein the oil of lubricating viscosity is selected from natural oils, synthetic oils and mixtures thereof having viscosities in the range of from 5 x 10⁻⁶ to 26 x 10⁻⁶ m²/s (5 to 26 centistokes) at 100°C. An additive concentrate for blending with lubricating oils to provide a lubricating composition having antiwear, antioxidant and friction reducing properties comprising: a hydrocarbon diluent and from 1 to 90 weight percent of an additive, based on the weight of diluent, the additive having the formula Mo₂L₄ wherein L is a ligand selected from xanthate and mixtures thereof and wherein the ligand, L, has organo groups having from 1 to 30 carbon atoms. The concentrate of claim 8, wherein the diluent is an aromatic hydrocarbon and the additive ranges between 20 to 70 weight percent, based on the weight of diluent.

Inventors: BELTZER MORTON, COYLE CATHERINE LOUISE, FRANCIS JAMES NELSON, GREANEY MARK ALAN, STIEFEL EDWARD IRA, BELTZER, MORTON, COYLE, CATHERINE LOUISE, FRANCIS, JAMES NELSON, GREANEY, MARK ALAN, STIEFEL, EDWARD IRA
Applicants: EXXON RESEARCH ENGINEERING CO, EXXON RESEARCH AND ENGINEERING COMPANY
Application year: 1990
Main classification: C10M135
IPC codes: C10N30, C10N10, C10M135, C10N20, C10M159