Lubricating Oil Containing a Nickel Alkoxyalkylxanthate, a Dixanthogen, and Zinc Dialkyldithiophosphate

1. Field of the Invention

This invention relates to a lubricating oil composition having improved antiwear performance due to the presence of a metal alkoxyalkylxanthate, a dixanthogen, and a metal thiophosphate.

2. Description of Related Art

Engine lubricating oils require the presence of additives to protect the engine from wear. For almost forty years, the principal antiwear additive for engine lubricating oils has been zinc dialkyldithiophosphate (ZDDP). However, ZDDP must be used in concentrations of 1.4 wt.% or greater to be effective. Since phosphates may result in the deactivation of emission control catalysts used in automotive exhaust systems, a reduction in the amount of phosphorus-containing additives (such as ZDDP) in the oil would be desirable. In addition, ZDDP alone does not provide the enhanced antiwear protection necessary in oils used to lubricate today's small, high performance engines.

The use of metal xanthates in lubricating oil is also known. For example, U.S. Pat. No. 2,335,017 discloses the addition of a metal-containing sulfur compound and a tertiary aliphatic ether or a phenol to a lubricating oil to improve the oil's detergent and anticorrosion properties. Several classes of metallic sulfur compounds are disclosed as being suitable, including metal xanthates of the formula ##STR1## wherein M is a metal and R is an aliphatic or aromatic radical which may contain further substituted atoms or groups such as--0 (alkyl). However, there is no mention of a metal thiophosphate being present nor of any improvement in the antiwear performance of the oil.

In addition, certain metal alkoxyalkylxanthates are known. For example, the reaction of nickel methoxyethylxanthate with other compounds has been studied (see Inoro. Chem. Vol. 18, no. 12, pp. 3612-15 (1979)) as has the decomposition of potassium methoxyethylxanthate (see J. Oro. Chem., Vol. 44, no. 10, pp. 1664-9 (1979)). Also, sodium ethoxyethylxanthate and potassium ethoxyethylxanthate are known (see European Patent Application 131,374 and U.S. Pat. No. 3,965,137, respectively). However, there is no mention of using these compounds in a lubricating oil.

Dixanthogens have also been used in lubricating oil compositions (see, for example, U.S. Pat. Nos. 2,681,316; 2,691,632; 2,694,682; and 2,925,386, the disclosures of which are incorporated herein by reference).

However, none of these publications suggest that the antiwear performance of a lubricating oil can be synergistically enhanced when certain metal xanthates, a dixanthogen, and a metal thiophosphate are present therein.

This invention concerns a lubricating oil containing antiwear reducing amounts of certain metal xanthates, a dixanthogen, and a metal thiophosphate. More specifically, we have discovered that the antiwear performance of a lubricating oil is synergistically enhanced when the oil contains a minor amount of an additive system containing a metal alkoxyalkylxanthate, a dixanthogen, and a metal thiophosphate. Nickel ethoxyethylxanthate, diethoxyethyl dixanthogen, and zinc dialkyldithiophosphate are particularly preferred additives.

FIG. 1 is a plot of average cam lobe wear versus time for five different oil formulations.

In one embodiment, this invention concerns a lubricating oil composition comprising

(a) a lubricating oil basestock,

(b) a metal alkoxyalkylxanthate,

(c) a dixanthogen, and

(d) a metal thiophosphate

In another embodiment, this invention concerns a method for reducing the wear of an internal combustion engine by lubricating the engine with an oil containing an oil soluble additive system which comprises a metal alkoxyalkylxanthate, a dixanthogen, and a metal thiophosphate.

In general, the lubricating oil will comprise a major amount of a lubricating oil basestock (or base oil) and a minor amount of an additive system which contains a metal alkoxyalkylxanthate, a dixanthogen, and a metal thiophosphate. If desired, other conventional lubricating oil additives may be present in the oil as well.

The lubricating oil basestock can be derived from natural lubricating oils, synthetic lubricating oils, or mixtures thereof. In general, the lubricating oil basestock will have a kinematic viscosity ranging from about 5 to about 10,000 cSt at 40.degree. C., although typical applications will require an oil having a viscosity ranging from about 10 to about 1,000 cSt at 40.degree. C.

Natural lubricating oils include animal oils, vegetable oils (e.g., castor oil and lard oil), petroleum oils, mineral oils, and oils derived from coal or shale.

Synthetic oils include hydrocarbon oils and halo-substituted hydrocarbon oils such as polymerized and interpolymerized olefins [e.g. polybutylenes, polypropylenes, propylene-isobutylene copolymers, chlorinated polybutylenes, poly(1-hexenes), poly(1-octenes), poly(1-deoenes), etc., and mixtures thereof]; alkylbenzenes [e.g. dodecylbenzenes, tetradecylbenzenes, dinonylbenzenes, di(2-ethylhexyl)benzene, etc.]; polyphenyls (e.g. biphenyls, terphenyls, alkylated polyphenyls, etc.); alkylated diphenyl ethers, alkylated diphenyl sulfides, as well as their derivatives, analogs, and homologs thereof; and the like.

Synthetic lubricating oils also include alkylene oxide polymers, interpolymers, copolymers, and derivatives thereof wherein the terminal hydroxyl groups have been modified by esterification, etherification, etc. This class of synthetic oils is exemplified by polyoxyalkylene polymers prepared by polymerization of ethylene oxide or propylene oxide; the alkyl and aryl ethers of these polyoxyalkylene polymers (e.g., methyl-polyisopropylene glycol ether having an average molecular weight of 1000, diphenyl ether of polyethylene glycol having a molecular weight of 500-1000, diethyl ether of polypropylene glycol having a molecular weight of 1000-1500); and mono- and polycarboxylic esters thereof (e.g., the acetic acid esters, mixed C.sub.3 -C.sub.8 fatty acid esters, and C.sub.13 oxo acid diester of tetraethylene glycol).

Another suitable class of synthetic lubricating oils comprises the esters of dicarboxylic acids (e.g., phthalic acid, succinic acid, alkyl succinic acids and alkenyl succinic acids, maleic acid, azelaic acid, suberic acid, sebasic acid, fumaric acid, adipic acid, linoleic acid dimer, malonic acid, alkyl malonic acids, alkenyl malonic acids, etc.) with a variety of alcohols (e.g., butyl alcohol, hexyl alcohol, dodecyl alcohol, 2-ethylhexyl alcohol, ethylene glycol, diethylene glycol monoether, propylene glycol, etc.). Specific examples of these esters include dibutyl adipate, di(2-ethylhexyl) sebacate, di-n-hexyl fumarate, dioctyl sebacate, diisooctyl azelate, diisodecyl azelate, dioctyl phthalate, didecyl phthalate, dieicosyl sebacate, the 2-ethylhexyl diester of linoleic acid dimer, and the complex ester formed by reacting one mole of sebacic acid with two moles of tetraethylene glycol and two moles of 2-ethylhexanoic acid, and the like.

Esters useful as synthetic oils also include those made from C.sub.5 to C.sub.12 monocarboxylic acids and polyols and polyol ethers such as neopentyl glycol, trimethylolpropane, pentaerythritol, dipentaerythritol, tripentaerythritol, and the like.

Silicon-based oils (such as the polyakyl-, polyaryl-, polyalkoxy-, or polyaryloxy-siloxane oils and silicate oils) comprise another useful class of synthetic lubricating oils. These oils include tetraethyl silicate, tetraisopropyl silicate, tetra-(2-ethylhexyl) silicate, tetra-(4-methyl-2-ethylhexyl) silicate, tetra(p-tert-butylphenyl) silicate, hexa-(4-methyl-2-pentoxy)-disiloxane, poly(methyl)-siloxanes and poly(methylphenyl) siloxanes, and the like. Other synthetic lubricating oils include liquid esters of phosphorus-containing acids (e.g., tricresyl phosphate, trioctyl phosphate, diethyl ester of decylphosphonic acid), polymeric tetrahydrofurans, polyalphaolefins, and the like.

The lubricating oil may be derived from unrefined, refined, rerefined oils, or mixtures thereof. Unrefined oils are obtained directly from a natural source or synthetic source (e.g., coal, shale, or tar sands bitumen) without further purification or treatment. Examples of unrefined oils include a shale oil obtained directly from a retorting operation, a petroleum oil obtained directly from distillation, or an ester oil obtained directly from an esterification process, each of which is then used without further treatment. Refined oils are similar to the unrefined oils except that refined oils have been treated in one or more purification steps to improve one or more properties. Suitable purification techniques include distillation, hydrotreating, dewaxing, solvent extraction, acid or base extraction, filtration, and percolation, all of which are known to those skilled in the art. Rerefined oils are obtained by treating refined oils in processes similar to those used to obtain the refined oils. These rerefined oils are also known as reclaimed or reprocessed oils and often are additionally processed by techniques for removal of spent additives and oil breakdown products.

The metal alkoxyalkylxanthate used in this invention has the general formula ##STR2## where R.sub.1 is an alkyl group (straight, branched, or cyclic), an alkoxy substituted alkyl group, a polyalkoxy substituted alkyl group, an aryl group, or a substituted aryl group.

R.sub.2 is a straight or branched alkylene group.

M is a metal

m is the oxidation state of the metal

n is an integer from 1 to 4

x is an integer from 1 to 2

y+z is an integer from 0 to 4

Preferably R.sub.1 is a straight alkyl group, a branched alkyl group, or an alkoxy substituted alkyl group. Most preferably, R.sub.1 comprises a straight chained alkyl group. Typically R.sub.1 will have from 1 to 24, preferably from 2 to 12, and more preferably from 2 to 8, carbon atoms. Typically, R.sub.2 will have from 2 to 8, preferably from 2 to 4, carbon atoms. Most preferably, R.sub.1 and R.sub.2 will each have from 2 to 4 carbon atoms. R.sub.1 and R.sub.2 together should contain a sufficient number of carbon atoms such that the metal alkoxyalkylxanthate is soluble in the oil. Examples of suitable substituted groups in R.sub.1 include alkyl, aryl, hydroxy, alkylthio, amido, amino, keto, ester groups, and the like.

M can be a variety of metals, but, in general, will comprise a metal selected from the group consisting of cadmium, chromium, germanium, hafnium, indium, manganese, nickel, niobium, tantalum, titanium, vanadium, and wolfram. Preferred metals are chromium and nickel, with nickel being most preferred.

m is the oxidation state of M and, typically, will be an integer ranging from 1 to 6, preferably from 2 to 4. Similarly, n, x, y, and z are integers whose values will vary as shown in Table 1 below.

Examples of the Various metal alkoxyalkylxanthates that can be used in this invention are nickel methoxyethylxanthate, nickel ethoxyethylxanthate, nickel phenoxyethylxanthate, nickel butoxyethylxanthate, nickel propyloxyethylxanthate, nickel isopropyloxyethylxanthate, nickel ethoxyethoxyethylxanthate, nickel 2-ethylhexyloxyxanthate, chromium ethoxyethylxanthate, chromium butoxyethylxanthate, or mixtures thereof. Preferred metal alkoxyalkylxanthates are chromium ethoxyethylxanthates, nickel ethoxyethylxanthate, nickel butoxyethylxanthate, nickel 2-ethylhexyloxyxanthate, or mixtures thereof, with nickel ethoxyethylxanthate and nickel butoxyethylxanthate being particularly preferred.

The dixanthogen used in this invention has the general formula ##STR3## where R.sub.3 and R.sub.4 are each an alkyl group (straight, branched, or cyclic), an alkoxy substituted alkyl group, a polyalkoxy substituted alkyl group, an aryl group, or a substituted aryl group.

Preferably R.sub.3 and R.sub.4 are each a straight alkyl group, a branched alkyl group, or an alkoxy substituted alkyl group. Most preferably, R.sub.3 and R.sub.4 each comprise a straight chained alkyl group. Although the number of carbon atoms in R.sub.3 and R.sub.4 could vary broadly, typically, at least one (and preferably both R.sub.3 and R.sub.4) will have from 1 to 24, preferably from 2 to 12, and more preferably from 2 to 8, carbon atoms. In addition, R.sub.3 and R.sub.4 together should contain a sufficient number of carbon atoms such that the dixanthogen is soluble in the oil. Examples of suitable substituted groups in R.sub.3 and R.sub.4 include alkyl, aryl, hydroxy, alkylthio, amido, amino, keto, ester groups, and the like.

Thus, in view of the foregoing, at least one (and preferably all) of R.sub.1, R.sub.3 and R.sub.4 is a straight alkyl group, a branched alkyl group, or an alkoxy substituted alkyl group. In addition, at least one of R.sub.1, R.sub.3 and R.sub.4 contains from 1 to 24, preferably from 2 to 12, and more preferably from 2 to 8 carbon atoms. Similarly, at least one of R.sub.1, R.sub.3, and R.sub.4 may include the substituted groups described above.

Examples of the various dixanthogens that may be used in this invention are dibutyl dixanthogen, dioctyl dixanthogen, dipropyl dixanthogen, diisobutyl dixanthogen, dimethyl dixanthogen, diethoxyethyl dixanthogen, dimethoxyethyl dixanthogen, dibutoxyethyl dixanthogen, di(butylphenoxyethyl) dixanthogen, di(dodecylphenoxyethyl) dixanthogen, isobutyloctyl dixanthogen, butyl methoxyphenoxyethyl dixanthogen, or their mixtures. Preferred dixanthogens are diethoxyethyl dixanthogen, dimethoxyethyl dixanthogen, dibutyl dixanthogen, dioctyl dixanthogen, diisobutyl dixanthoqen, dibutoxyethyl dixanthogen, di(dodecylphenoxyethyl) dixanthogen, di(butylphenoxyethyl) dixanthogen, or mixtures thereof, with diethoxyethyl dixanthogen and dibutoxyethyl dixanthogen being particularly preferred.

The metal thiophosphate used in this invention preferably comprises a metal selected from the group consisting of Group IB, IIB, VIB, VIII of the Periodic Table, and mixtures thereof. A metal dithiophosphate is a preferred metal thiophosphate, with a metal dialkyldithiophosphate being particularly preferred. Copper, nickel, and zinc are particularly preferred metals, with zinc being most preferred. The alkyl groups preferably comprise from 3 to 10 carbon atoms. Particularly preferred metal thiophosphates are zinc dialkyldithiophosphates.

The amount of metal alkoxyalkylxanthate, dixanthogen, and metal thiophosphate used in this invention need be only that which is necessary to cause an enhancement in the antiwear performance of the oil. Typically, however, the concentration of the metal alkoxyalkylxanthate in the lubricating oil will range from about 0.1 to about 5 wt.%, preferably from about 0.2 to about 1.5 wt.%, of the oil. The amount of dixanthogen in the oil will be within the same ranges as the metal alkoxyalkylxanthate. The concentration of the metal thiophosphate will range from about 0.1 to about 2 wt.%, preferably from about 0.2 to about 1 wt.%, of the lubricating oil.

Metal thiophosphates and dixanthogens are commercially available from a number of vendors. As such, their method of manufacture is well known to those skilled in the art. The metal alkoxyalkylxanthates can be readily prepared by the procedures disclosed in copending application U.S. Ser. No. 404,135 filed on the same date herewith and shown in Example 3 below.

The additives (or additive system) of this invention can be added directly to the lubricating oil. Often, however, they can be made in the form of an additive concentrate to facilitate handling and introduction of the additives into the oil. Typically, the concentrate will contain a suitable organic diluent and from about 10 to about 90 wt.%, preferably from about 30 to about 80 wt.%, of the additives. Suitable organic diluents include mineral oil, naphtha, benzene, toluene, xylene, and the like. The diluent should be compatible (e.g. soluble) with the oil and, preferably, substantially inert.

The lubricating oil (or concentrate) may also contain other additives known in the art such that a fully formulated oil is formed. Such additives include dispersants, other antiwear agents, antioxidants, corrosion inhibitors, detergents, pour point depressants, extreme pressure additives, viscosity index improvers and the like. These additives are typically disclosed, for example, in "Lubricant Additives" by C.V. Smalheer and R. Kennedy Smith, 1967, pp. 1-11 and in U.S. Pat. No. 4,105,571, the disclosures of which are incorporated herein by reference. These additives are present in proportions known in the art.

A lubricating oil containing the additive system of this invention can be used in essentially any application where wear protection is required. Thus, as used herein, "lubricating oil" (or "lubricating oil composition") is meant to include automotive lubricating oils, industrial oils, gear oils, transmission oils, and the like. In addition, the lubricating oil composition of this invention can be used in the lubrication system of essentially any internal combustion engine, including automobile and truck engines, two-cycle engines, aviation piston engines, marine and railroad engines, and the like. Also contemplated are lubricating oils for gas-fired engines, alcohol (e.g. methanol) powered engines, stationary powered engines, turbines, and the like.

This invention may be further understood by reference to the following examples which are not intended to restrict the scope of the claims.

Valve train wear tests were performed in the following examples utilizing a Ford 2.3 liter engine with the pistons and connecting rods removed. The engine was driven by an 11.2 KW (15 horsepower) DC drive motor through a 1.2 timing belt drive. The engine was equipped with Oldsmobile valve springs (146.5-148.3 KG) to increase the load between the cam lobes and the followers. Oil and coolant were circulated using engine mounted pumps. All test runs were made at an oil and coolant temperature of 90.+-.2.degree. C., an oil pressure of 330.+-.8 kPa, and an engine speed of 1,000.+-.8 rpm, with periodic stoppage for wear measurements

During operation, wear occurs on the lobes of the cam shaft and followers due to the sliding contact. Cam lobe wear was determined using the sequence V-D test described in ASTM Test No. STP 315H-Part 3 (the disclosure of which is incorporated herein by reference) by measuring the "head-to-toe" dimension (cam base circle diameter plus maximum lift) at room temperature using a digital micrometer. The difference between the dimensions of new and used cam lobes is a measure of the individual cam lobe wear, usually measured to an accuracy within about 2 microns. The individual cam lobe wear values from all eight lobes on the camshaft were averaged to provide a single value of average cam lobe wear.

About 127 g. (0.5 mole) of iodine was added to mechanically stirred solution of 204 g. (1 mole) of potassium ethoxyethylxanthate in 1500 ml of water. As the reaction proceeded, the iodine color disappeared and the mixture became turbid, with the separation of an oily product. After stirring for about one hour, 10 g. of iodine was added and the stirring continued for an additional 30 minutes. The mixture was transferred to a separatory funnel and extracted with ether (3.times.200 ml). The ether solution was washed with water, dried over anhydrous sodium sulfate, and concentrated to dryness on a Rotovap. The residual oily product was subjected to vacuum for about one hour, heated for a few minutes with 5 g of animal charcoal, and filtered through a bed of sodium sulfate. The yield of the product was 154 g. (93% conversion). Elemental analysis of the product gave the following results (in wt.%):

Found: C=36.42; H=5.50; S=38.55

Calculated for C.sub.10 H.sub.18 O.sub.2 S.sub.4 : C=36.36; H=5.45; S=38.78

A proton NMR spectra was consistent with this structure.

Portions of this product were used to formulate Oils 2 and 5 in Example 4 below.

A solution of 132 g. (2 moles) of potassium hydroxide in 100 ml of water was added (under a nitrogen blanket) to 236 g. (2 moles) of butoxy-ethanol in a mechanically stirred beaker on an ice bath. The mixture was stirred for about one hour, and then 150 g. of carbon disulfide was added through a dropping funnel. After stirring for 30 minutes, 250 g. (0.99 mole) of iodine was added (in portions) with stirring. The iodine color disappeared almost immediately. The stirring was continued for another hour. The mixture was then transferred to a separatory funnel, diluted with toluene-petroleum ether, and washed well with water. The solution was dried over magnesium sulfate and then concentrated to dryness on a Rotovap. The oily product was then subjected to vacuum at 85.degree. C. for about 4.5 hours. A proton NMR spectra on the residual oil product was consistent with the structure of dibutoxyethyl dixanthogen.

Portions of this product were used to formulate Oils 3 and 6 in Example 4 below.

About 300 ml (3 moles) of 2-ethoxyethanol and 210 ml (3.5 moles) of CS.sub.2 (added dropwise) were mixed with a mechanically stirred solution of 198 g (3 moles) of potassium hydroxide in 150 ml of water in a beaker on an ice bath. Acetone (500 ml) was then added to the resulting thick orange liquid and the mixture stirred for another hour, after which a small amount of a dark orange layer settled at the bottom of the beaker. The top layer was transferred to another beaker. The bottom layer was again extracted with acetone and the acetone solutions were combined. A solution of 360 g (1.5 moles) of NiCl.sub.2,6H.sub.2 O in 800 ml of water was added (with mechanical stirring on an ice bath) to the acetone solutions. The mixture was diluted with 700 ml of an ice-water mixture and stirred for about one hour. The resulting solid was collected, washed well with water, and air dried.

For recrystallization, the solid was dissolved in hot ethyl acetate and filtered to remove small amounts of impurities. The filtrate was concentrated under reduced pressure to a small volume. Addition of heptane to the concentrated filtrate followed by cooling in an ice-bath gave 543 g (93% conversion) of a crystalline product having a melting point of 71.5.degree. to 72.degree. C. Elemental analysis of the product gave the following results (in wt.%):

Found: C=31.05; H=4.70; Ni=15.40

Calculated for C.sub.10 H.sub.18 O.sub.4 S.sub.4 Ni: C=30.85; H=4.63; Ni=15.17

Infrared and proton NMR spectra were consistent with this structure.

Portions of this product were used to formulate Oils 4, 5, and 6 in Example 4 below.

Several test oils were formulated from a commercially available fully formulated lubricating oil from which the amount of antiwear additive (ZDDP) had been reduced until the oil contained 0.02 wt.% phosphorus (which corresponds to about 0.25 wt.% ZDDP). Different additives were then added to samples of this low phosphorus oil (Oil 1) to form the following oils:

Oil 2--contained 0.25 wt.% ZDDP and 0.5 wt.% diethoxyethyl dixanthogen

Oil 3--contained 0.25 wt.% ZDDP and 1.0 wt.% dibutoxyethyl dixanthogen

Oil 4--contained 0.25 wt.% ZDDP and 0.5 wt.% nickel ethoxyethylxanthate.

Oil 5--contained 0.25 wt.% ZDDP, 0.5 wt.% nickel ethoxyethylxanthate, and 0.5 wt.% diethoxyethyl dixanthogen.

Oil 6--contained 0.25 wt.% ZDDP, 0.5 wt.% nickel ethoxyethylxanthate, and 0.5 wt.% dibutoxyethyl dixanthogen.

A valve train wear test was performed using Oil 1. The average cam lobe wear after 20 hours was 118 micrometers(.mu.m). The test was then terminated to prevent engine seizure due to the high wear which had occurred.

Tests similar to Example 5 were performed using Oils 2-6. The average cam lobe wear obtained for each oil during 80 hours of operation is shown in FIG. 1.

The data in FIG. 1 show that the cam lobe wear was reduced for Oils 2-4 in which a single additive was added to the low phosphorus-containing oil (Oil 1). The data also show that a significant and unexpected synergistic improvement in antiwear performance resulted when a metal alkoxyalkylxanthate and a dixanthogen were present in the low phosphorus oil (Oil 5 and Oil 6). In addition, the data show that this additive system allows the formulation of a lubricating oil having enhanced wear protection at phosphorus levels significantly below those of conventional oils.