Method for improving performance of combustion engine after-treatment device

Abstract

To provide a method for improving the performance of a combustion engine after-treatment device such as a particle filter, and a lubricant composition for improving the same.SOLUTION: A method for improving the performance of an after-treatment device comprises lubricating a combustion engine with a lubricating oil composition, combusting fuel in the lubricated engine to generate an exhaust stream containing soot and / or ash particles derived from the combustion, bringing the after-treatment device into contact with the exhaust stream containing soot and / or ash particles from the combustion, wherein the lubricating oil composition comprises an additive package comprising one or more base oils of lubricating viscosity and at least one oil-soluble silicon-containing compound providing about 50 to about 500 ppm of silicon to the lubricating oil composition, and wherein the performance of the after-treatment device after at least about 120,000 miles of operation of this method is improved compared to an aftert-reatment device exposed to the exhaust stream from the combustion engine lubricated with the lubricating oil composition having about 10 ppm or less of silicon.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present disclosure relates generally to lubricating oil compositions configured to improve the performance of aftertreatment devices for combustion engines and methods of use thereof, and specifically to the use of oil-soluble silicon-containing compounds in lubricating oil compositions to improve the performance of combustion engine aftertreatment devices. [Background technology]

[0002] While traditional port fuel injection (PFI) gasoline engines tend to have very low particulate emissions, newer gasoline direct injection (GDI) and diesel engines tend to have higher particulate emissions given their combustion technology. To help reduce particulate and other exhaust emissions in both diesel and GDI engines, various so-called aftertreatment devices have been introduced. For example, particulate filters are one such aftertreatment device that is commonly used with the exhaust systems of diesel and / or GDI engines to capture and reduce particulate emissions. Three-way catalysts are another common aftertreatment device that are often used to oxidize partially burned and / or unburned components in the exhaust from such engines. However, particulate filters and / or catalyst systems are required to efficiently control vehicle emissions during a long real-world service life that may exceed 100,000 miles. However, the performance of the aftertreatment devices may be affected by combustion by-products resulting from the selected engine oil, among other issues.

[0003] The evaluation of the aftertreatment device may be determined through various performance tests and / or physical characterization. Performance tests may include, for example, measuring the oxygen storage capacity and / or light-off temperature of the catalyst system. Physical characterization may include measuring the filter and / or catalyst surface area.

[0004] Oxygen storage capacity generally refers to the ability of a three-way catalyst aftertreatment device to store excess oxygen under lean conditions and release oxygen under rich conditions. The amount of oxygen storage and release decreases as the conversion ability of the three-way catalyst decreases. Thus, a decrease in the oxygen storage capacity of a three-way catalyst over its useful life is undesirable, and a high oxygen storage capacity that is maintained over the useful life of the aftertreatment device in use is preferred.

[0005] Light-off temperature is another useful performance measure of a three-way catalyst. Light-off temperature is a measure of the exhaust gas temperature at which catalytic reactions are initiated in the three-way catalyst. Light-off temperature is generally the minimum temperature required to oxidize the products of incomplete combustion in the engine's exhaust stream. For this reason, a lower light-off temperature that is maintained over the useful life of the device is desirable.

[0006] Filter or catalyst surface area is a physical characteristic of an aftertreatment device that can be used to evaluate device performance over time. Soot or ash from combustion can reduce the surface area by clogging the filter or catalyst. Brunauer-Emmett-Teller (BET) analysis is one method used to measure the surface area of ​​solid or porous materials, and can be useful for measuring the surface area of ​​automotive aftertreatment devices such as particulate filters or three-way catalysts. A higher BET surface area of ​​the catalyst or filter that is maintained over its useful life is desired. Summary of the Invention

[0007] According to one aspect, a method for improving the performance of an aftertreatment device for a combustion engine is described herein. In one embodiment or approach of this aspect, the method includes lubricating a combustion engine with a lubricating oil composition, combusting fuel in the lubricated engine to generate an exhaust stream containing soot and / or ash particles derived from the combustion, the lubricating oil composition comprising one or more base oils of lubricating viscosity and an additive package comprising at least one oil-soluble silicon-containing compound providing the lubricating oil composition with about 50 to about 500 ppm of silicon, and contacting the aftertreatment device with the exhaust stream containing soot and / or ash particles from the combustion, and the performance of the aftertreatment device after at least about 120,000 miles of operation is improved compared to an aftertreatment device exposed to an exhaust stream from a combustion engine lubricated with a lubricating oil composition having about 10 ppm or less of silicon.

[0008] In other approaches or embodiments, the method of the preceding paragraph may include optional embodiments, features, or method steps in any combination. These optional embodiments, features, or method steps may include one or more of the following: the performance of the aftertreatment device is improved as measured by at least one of a surface area, an oxygen storage capacity, or a light-off temperature, and / or the surface area of ​​the aftertreatment device after at least about 120,000 miles of operation is substantially the same as the initial surface area of ​​the aftertreatment device, and / or the oxygen storage capacity of the aftertreatment device after at least about 120,000 miles of operation is less than 30 percent greater than the initial oxygen storage capacity of the aftertreatment device, and / or the CO T of the aftertreatment device after at least about 120,000 miles of operation is less than 30 percent greater than the initial oxygen storage capacity of the aftertreatment device. 50 The light-off temperature is the initial CO T of the aftertreatment device. 50 and / or the surface area of ​​the aftertreatment device is measured according to a Brunauer-Emmett-Teller (BET) analysis, and / or the BEP surface area of ​​the aftertreatment device is less than about 20 m after about 120,000 miles of operation. 2 g cat -1or greater, and / or the BET surface area of ​​the aftertreatment device after at least about 120,000 miles of operation is maintained at about 4 to about 10 percent of the initial BET surface area of ​​the aftertreatment device, and / or the at least one oil-soluble silicon-containing compound provides about 150 to about 250 ppm of silicon to the lubricating oil composition, and / or the aftertreatment device is selected from a three-way catalytic converter, a particulate filter, or a combination thereof, and / or the oil-soluble silicon-containing compound is an organosilane compound having a C6 to C20 hydrocarbyl chain, and / or the organosilane compound is and / or the silyl ether compound is a C6-C20 hydrocarbyl silyl ether compound, and / or the silyl ether compound is a tri-alkoxy(hydrocarbyl)silane, and / or the silyl ether compound is a C14-C20 hydrocarbyl trimethoxysilane, and / or the combustion engine is a gasoline engine or a diesel engine, and / or the soot or ash particles have a diameter of about 10 nm or less, and / or the soot or ash particles agglomerate into particles having a diameter of up to 200 micrometers, and / or the exhaust stream has a particle size of 1×10 or less as measured by particulate number (PN) during high temperature operation. 12 ~1×10 13 and / or the lubricating oil composition has a calculated SASH value (ASTM 874) of 0.4 to 2.0 weight percent.

[0009] In another aspect, a lubricating oil composition configured to improve the performance of an aftertreatment device for a combustion engine is described herein. In a further aspect embodiment or approach, the lubricating oil composition comprises one or more base oils of lubricating viscosity, one or more optional viscosity index improver additives, an additive package comprising one or more of boronated and / or non-boronated dispersants, antioxidants, friction modifiers, one or more detergents, one or more antiwear agents, pour point depressants, and antifoam agents, and at least one oil-soluble silicon-containing compound providing about 50 to about 500 ppm of silicon to the lubricating oil composition, and after contacting the aftertreatment device with an exhaust stream comprising soot and / or ash particles from the combustion of fuel in a combustion engine lubricated with the lubricating oil composition, the performance of the aftertreatment device after at least about 120,000 miles of operation is improved compared to an aftertreatment device exposed to an exhaust stream from a combustion engine lubricated with a lubricating oil composition having about 10 ppm or less of silicon.

[0010] In other embodiments, the lubricating oil composition of the preceding paragraph may include one or more of the optional features or embodiments in any combination. These optional features or embodiments may include one or more of the following: at least one oil-soluble silicon-containing compound provides about 150 to about 250 ppm of silicon to the lubricating oil composition, and / or the oil-soluble silicon-containing compound is an organosilane compound having a C6-C20 hydrocarbyl chain, and / or the organosilane compound is a C6-C20 hydrocarbyl silyl ether compound, and / or the silyl ether compound is a tri-alkoxy(hydrocarbyl)silane, and / or the silyl ether compound is a C14-C20 hydrocarbyl trimethoxysilane.

[0011] In yet another embodiment, the use of any embodiment of the lubricating oil composition or method of the present summary is also described for improving the performance of an aftertreatment device for a combustion engine, wherein the improved performance of the aftertreatment device is measured by at least one of a surface area, an oxygen storage capacity, or a light-off temperature, and / or the use achieves a surface area of ​​the aftertreatment device after at least about 120,000 miles of operation that is substantially the same as an initial surface area of ​​the aftertreatment device, and / or the use achieves an oxygen storage capacity of the aftertreatment device after at least about 120,000 miles of operation that is no more than 30 percent of the initial oxygen storage capacity of the aftertreatment device, and / or the use achieves an initial CO T of the aftertreatment device. 50 The CO T of the aftertreatment device after at least about 120,000 miles of operation is no more than 5 percent above the light-off temperature. 50 A light-off temperature is achieved and / or the surface area of ​​the aftertreatment device is measured according to Brunauer-Emmett-Teller (BET) analysis and / or the BET surface area of ​​the aftertreatment device is less than about 20 m after at least about 120,000 miles of operation. 2 g cat -1 or greater, and / or the BET surface area of ​​the aftertreatment device after at least about 120,000 miles of operation is maintained at about 4 to about 10 percent of the initial BET surface area of ​​the aftertreatment device.

[0012] Additional details and advantages of the disclosure will be set forth in part in the following description and / or may be learned by practice of the disclosure. The details and advantages of the disclosure may be realized and attained by means of the elements and combinations particularly pointed out in the appended claims. It is to be understood that both the foregoing general description and the following detailed description are exemplary and explanatory only and are not restrictive of the disclosure as claimed. [Brief description of the drawings]

[0013] [Figure 1] 4 is a speed versus time chart for an exemplary drive cycle used herein. [Diagram 2]1 is a graph of BET surface area. [Diagram 3] 1 is a graph of oxygen storage capacity. [Figure 4] 1 is a graph of light-off temperature. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0014] The present disclosure provides a method for improving the performance of a combustion engine aftertreatment device, such as a particulate filter and / or a three-way catalyst system, over its useful life by using a lubricating oil composition comprising one or more base oils of lubricating viscosity and an additive package having at least one oil-soluble silicon-containing compound providing about 50 to about 500 ppm of silicon to the lubricating oil composition. Surprisingly, a higher amount of silicon in the lubricating oil composition resulted in improved performance of the aftertreatment device, even though silicon may result in a higher ash content.

[0015] In the approach or embodiment herein, the method includes lubricating a combustion engine with a lubricating oil composition having an increased level of silicon, and burning fuel in the lubricated engine to generate an exhaust stream containing soot and / or ash particles derived from the combustion.The aftertreatment device is then contacted with the exhaust stream containing soot and / or ash particles from the combustion, and the performance of the aftertreatment device is improved compared to the aftertreatment device exposed to the exhaust stream from the combustion engine lubricated with a lubricating oil composition having a negligible level of silicon (such as about 10 ppm or less of silicon).As discussed herein, the performance of the aftertreatment device is measured after at least about 120,000 miles (preferably about at least about 125,000 miles) of engine operation according to a suitable driving cycle, such as, but not limited to, the EPA Federal Test Procedure (e.g., FTP-75), the Common Artemis Driving Cycle (CADC), or other suitable driving cycle. The performance of the aftertreatment device was improved as measured using one or more of oxygen storage capacity, light-off temperature, and / or BET surface area, and surprisingly, higher levels of silicon in the engine oil lubricant improved the performance of the filter or catalyst compared to engine oils having lower levels of silicon.

[0016] Since silicon is an inorganic material that is not burned in engines, it was expected that a higher level of silicon in engine oil would adversely affect the performance of the aftertreatment device by forming a higher level of ash that would reduce the oxygen storage capacity, light-off temperature, and / or surface area of ​​the aftertreatment device over its service life.However, on the other hand, it has been discovered herein that a higher amount of silicon from oil-soluble silicon-containing compounds in engine oil actually maintains or improves the performance of the aftertreatment device compared to the initial performance of the aftertreatment device, or at least results in better performance compared to engine oils with negligible levels of silicon (i.e., about 10 ppm or less).The lubricating oil composition herein may have a calculated SASH value of about 0.4 to about 2.0 weight percent, or about 0.4 to about 1.0, or about 0.4 to about 0.8 weight percent, as measured according to ASTM D874.

[0017] Particulate emissions of a combustion engine exhaust stream generally include soot and ash particles, which may aggregate to form larger aggregate particles. In some approaches and embodiments herein, primary soot and ash particles of the exhaust stream typically have a diameter of less than about 10 nm. In other embodiments, aggregate particles, if present, may have an average primary particle size of about 7 nm to about 60 nm. In still further embodiments, primary particles may also, in some circumstances, associate to form aggregates that may have a diameter of up to about 200 nm or even greater, for example, according to a 2017 publication by the Association for Emissions Control by Catalyst (AECC) entitled "Gasoline Particulate Filter (GPF): How can the GPF cut emissions of ultrafine particles from gasoline engines." In still further approaches, the exhaust stream herein may include a plurality of particles, each particle of the plurality of particles having a diameter of about 0.01 micrometers to about 200 micrometers. In other approaches, each particle in the plurality of particles has a diameter of about 0.05 micrometers to about 95 micrometers, about 0.10 micrometers to about 90 micrometers, about 0.15 micrometers to about 85 micrometers, or about 0.20 micrometers to about 80 micrometers. In some approaches, at least 99% of the particles in the plurality of particles have an average diameter as specified above. In other approaches, at least 98%, at least 97%, at least 96%, or at least 95% of the particles in the plurality of particles have an average diameter as specified herein. In some approaches, 5% or less of the particles have an average diameter greater than 200 micrometers. In some approaches, 5% or less of the particles have an average diameter less than 0.01 micrometers. In yet other approaches, the combustion exhaust stream has a mean diameter of about 1×10 as measured by particulate count (PN) during high temperature operation. 12 ~Approx. 1×10 13 may have soot and / or ash particles.

[0018] Oil-soluble silicon-containing compounds In an approach or embodiment, the oil-soluble silicon-containing compounds useful in the lubricating oil compositions herein for improving the performance of aftertreatment devices can be one or more organosilanes, such as one or more hydrocarbyl silyl ether compounds having a C6-C20 hydrocarbyl chain. For example, the hydrocarbyl silyl ether can be a tri-alkoxy(hydrocarbyl)silane, such as a C10-C20 hydrocarbyl trimethoxy silane, or more preferably, a C14-C20 hydrocarbyl trimethoxy silane, and most preferably, a hexadecyl trimethoxy silane.

[0019] In another approach or embodiment, the oil-soluble silicon-containing compound of the present disclosure may have the structure of Formula I:

[0020] [ka] In the formula, R1 is a hydrocarbyl group containing 2 to 20 carbon atoms (preferably an alkyl group having 6 to 20 carbon atoms, 10 to 20 carbon atoms, or 16 to 18 carbon atoms), and R2, R3, and R4 are each independently selected from a hydrocarbyl group having 1 to 10 carbon atoms (preferably an alkyl group having 1 to 3 carbon atoms, more preferably a methyl group). Optionally, R1 may be an alkyl group selected from ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octyldecyl, nonadecyl, and eicosyl, and R2, R3, and R4 may be independently alkyl groups selected from methyl, ethyl, and propyl. Preferably, R1 is an alkyl group selected from undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octyldecyl, and R2, R3 and R4 are methyl groups.

[0021] In yet another approach, the oil-soluble silicon-containing compound of the present disclosure can have an average number molecular weight of 100-400 g / mol when measured by GPC.Suitable examples of such oil-soluble silicon-containing compounds can be, but are not limited to, hexadecyltrimethoxysilane, octyltriethoxysilane, nonyltriethoxysilane, n-decyltriethoxysilane, undecyl-triethoxysilane, and tetradecyltriethoxysilane.Preferably, the oil-soluble silicon-containing compound of the present disclosure is selected from undecyl-triethoxysilane, tetradecyltriethoxysilane, and hexadecyltrimethoxysilane.

[0022] In some embodiments, suitable organosilanes include one organic substituent and three hydrolyzable substituents. In yet other embodiments, exemplary organosilanes can include, but are not limited to, the following compounds: [2-(3-cyclohexenyl)ethyl]trimethoxysilane, trimethoxy(7-octen-1-yl)silane, isooctyltrimethoxy-silane, N-(3-triethoxy-silylpropyl)methoxyethoxyethoxyethyl carbamate, N-(3-triethoxysilylpropyl)methoxyethoxyethoxyethyl carbamate, 3-(methacryloyloxy)propyltrimethoxysilane, allyltrimethoxysilane, methyl ... Silane, 3-acryloxypropyltrimethoxysilane, 3-(methacryloyloxy)propyltriethoxysilane, 3-(methacryloyloxy)propylmethyldimethoxysilane, 3-(acryloyloxypropyl)methyldimethoxysilane, -9-3-(methacryloyloxy)propyldimethylethoxysilane, 3-(methacryloyloxy)propyldimethylethoxysilane, vinyldimethylethoxysilane, phenyltrimethoxysilane, n-octyltrimethoxysilane, dodecyltrimethoxysilane, isopropyltrimethoxysilane, isooctyltrimethoxysilane, octadecyltrimethoxysilane, propyltrimethoxysilane, hexyltrimethoxysilane, vinylmethyldiacetoxysilane, vinylmethyldiethoxysilane, vinyltriacetoxysilane, vinyltriethoxysilane, vinyltriisopropoxysilane, vinyltrimethoxysilane, vinyltriphenoxysilane, vinyltri-t-butoxysilane, vinyltrisisobutoxysilane, vinyltriisopropeneoxysilane, vinyltris(2-methoxyethoxy)silane, styryl and / or combinations of two or more of the foregoing compounds.

[0023] In one approach or embodiment, the oil-soluble silicon-containing compound is present in an amount sufficient to provide the lubricating oil composition with from about 50 ppm to about 500 ppm of silicon, in another approach from about 100 ppm to about 500 ppm of silicon, from about 150 ppm to about 250 ppm of silicon, or in yet another approach from about 180 ppm to about 220 ppm of silicon, based on the total weight of the lubricating oil composition.

[0024] Such high treatment rates of silicon in the lubricating compositions herein surprisingly provide a surface area measured using Brunauer-Emmett-Teller (BET) analysis of the aftertreatment device after at least about 120,000 miles of useful life that is substantially the same as the initial measured surface area of ​​the aftertreatment device. As used herein, substantially the same in the context of BET filter surface area is considered to be within about 10 percent, within about 8 percent, or within about 5 percent of the initial surface area of ​​the aftertreatment device (or the degreened surface area as described in the examples) when measured according to Brunauer-Emmett-Teller (BET) analysis. In another approach, the BET surface area of ​​the aftertreatment device is within about 20 m after at least 120,000 miles. 2 g cat -1 or more (preferably, about 20 to about 25 m 2 g cat -1). In yet another approach, the BET surface area of ​​the aftertreatment device after 120,000 miles of operation is maintained at about 4 to about 10 percent of the initial or degreened BET surface area of ​​the aftertreatment device. Surprisingly, a lower amount of silicon-containing compound in the lubricating composition actually results in a lower BET surface area after at least about 120,000 miles, which means that the pores of the aftertreatment device are more blocked when the engine is lubricated with a composition having a low concentration of silicon, such as a lubricating oil composition having about 10 ppm or less of silicon. In comparison, as shown in the examples herein, the BET surface area of ​​a filter exposed to exhaust gases from an engine using a comparative lubricant having a negligible level of silicon (e.g., about 10 ppm or less) is 10.4 m after at least about 120,000 miles of operation. 2 g cat -1 had a much lower surface area of ​​.

[0025] Such high silicon treat rates also surprisingly maintain a low light-off temperature of the three-way catalyst after at least about 120,000 miles of useful life, as compared to lubricants having negligible levels of silicon (e.g., 10 ppm or less). As discussed above, light-off temperature is a measure of the exhaust gas temperature required to oxidize the products of incomplete combustion, such as CO and C3H8, and is generally expressed as T 50 Or T 90 It is reported as a temperature (where T 50 refers to the temperature in degrees Celsius at which 50% of CO or C3H8 is converted, and T 90 refers to the temperature in degrees Celsius at which 90% of the CO or C3H8 is converted.

[0026] The lubricants herein having a high silicon treat rate minimize any increase in light-off temperature after at least about 120,000 miles of engine operation. For example, as shown in the examples below, when using the lubricating compositions herein having higher levels of silicon, the COT 50 and T 90The light-off temperature increased by only about 3 to 5 percent, and the C3H8T 50 and T 90 The light temperature increased by only about 9 to about 18 percent. In contrast, as shown in the examples below, comparative lubricants having negligible levels of silicon (e.g., about 10 ppm or less) showed no significant COT 50 and T 90 An increase of about 9 percent or more in temperature, as well as C3H8T 50 and T 90 For example, in some embodiments, the lubricants herein had a CO T increase of 25 percent or more after at least about 120,000 miles. 50 The measured light-off temperature is about 208°C to about 212°C, and the CO T 90 The measured light-off temperature is about 210°C to about 218°C. 50 The measured light-off temperature is about 388°C to about 395°C. 90 The measured light-off temperature was about 475°C to about 485°C.

[0027] The high silicon treat rate also surprisingly maintains a high level of oxygen storage capacity of the three-way catalyst after at least about 120,000 miles of useful life. As mentioned above, oxygen storage capacity is the ability of a catalyst to oxidize partially burned and / or unburned components in the exhaust from an engine, and is generally reported in moles of oxygen per gram of catalyst. It is desirable to maintain a high oxygen storage capacity over the useful life of the catalyst, and the lubricating compositions herein with a high silicon treat rate have minimized the decrease in oxygen storage capacity. As shown in the examples, the lubricants herein had a decrease in oxygen storage capacity of less than about 30 percent after at least about 120,000 miles of operation, while lubricants with negligible levels of silicon (e.g., about 10 ppm or less) had a decrease in oxygen storage capacity of more than 35 percent. For example, in some embodiments, after at least about 120,000 miles, the lubricants herein had a decrease in oxygen storage capacity of about 0.000180 moles oxygen / gcat ~ approx. 0.000190 moles oxygen / g cat In contrast, a comparative lubricant having negligible levels of silicon (e.g., about 10 ppm or less) achieved a measured oxygen storage capacity of 0.000161 moles oxygen / g cat had a lower oxygen storage capacity.

[0028] As shown in the examples herein, the improvement in aftertreatment device performance when using lubricants with higher levels of silicon was unexpected because silicon likely results in higher levels of ash that would be expected to reduce filter or catalyst performance.

[0029] Hydrocarbon fuel Fuels suitable for the method may be applicable to the operation of diesel, jet, or gasoline engines. The engines may include both stationary engines (e.g., engines used in power generation facilities, pumping stations, etc.) and mobile engines (e.g., engines used as prime movers for automobiles, trucks, road leveling equipment, military vehicles). For example, the fuels may include any and all middle distillate fuels, diesel fuels, biorenewable fuels, biodiesel fuels, fatty acid alkyl esters, gas-to-liquid (GTL) fuels, gasoline, jet fuels, alcohols, ethers, kerosene, low sulfur fuels, Fischer-Tropsch fuels, liquid petroleum gas, bunker fuels, coal-to-liquid (CTL) fuels, biomass-to-liquid (BTL) fuels, high asphaltene fuels, coal-derived fuels (natural coal, clarified coal, and pet coke), synthetic fuels such as genetically engineered biofuels and crops and extracts therefrom, and natural gas. As used herein, "biorenewable fuel" is understood to mean any fuel derived from a source other than petroleum. Such sources include, but are not limited to, corn, maize, soybean, and other crops; grasses, such as switchgrass, miscanthus, and hybrid grass; algae, seaweed, vegetable oils; natural fats; and mixtures thereof. In one aspect, the biorenewable fuel can include monohydroxy alcohols, such as those containing 1 to about 5 carbon atoms. Non-limiting examples of suitable monohydroxy alcohols include methanol, ethanol, propanol, n-butanol, isobutanol, t-butyl alcohol, amyl alcohol, and isoamyl alcohol. Preferred fuels for the methods herein include gasoline or diesel fuel.

[0030] The fuels of the present disclosure may include one or more additives. For example, the fuels may contain conventional amounts of cetane improvers, octane improvers, corrosion inhibitors, low temperature flow improvers (CFPP additives), pour point depressants, solvents, demulsifiers, lubricity additives, friction modifiers, amine stabilizers, combustion improvers, detergents, dispersants, antioxidants, heat stabilizers, conductivity improvers, metal deactivators, marker dyes, organic nitrate light-off accelerators, cyclic aromatic manganese tricarbonyl compounds, carrier fluids, and the like, as appropriate for the type of fuel. Similarly, the fuels may contain suitable amounts of conventional fuel blending components, such as methanol, ethanol, dialkyl ethers, 2-ethylhexanol, and the like.

[0031] In some approaches, organic nitrate ignition promoters may be used, including aliphatic or cycloaliphatic nitrates where the aliphatic or cycloaliphatic groups are saturated and contain up to about 12 carbons. Examples of organic nitrate ignition promoters that may be used are methyl nitrate, ethyl nitrate, propyl nitrate, isopropyl nitrate, allyl nitrate, butyl nitrate, isobutyl nitrate, sec-butyl nitrate, tert-butyl nitrate, amyl nitrate, isoamyl nitrate, 2-amyl nitrate, 3-amyl nitrate, hexyl nitrate, heptyl nitrate, 2-heptyl nitrate, octyl nitrate, isooctyl nitrate, 2-ethylhexyl nitrate, nonyl nitrate, decyl nitrate, undecyl nitrate, dodecyl nitrate, cyclopentyl nitrate, cyclohexyl nitrate, methylcyclohexyl nitrate, cyclododecyl nitrate, 2-ethoxyethyl nitrate, 2-(2-ethoxyethoxy)ethyl nitrate, tetrahydrofuranyl nitrate, and the like. Mixtures of such materials may also be used.

[0032] Examples of suitable optional metal deactivators useful in the compositions of the present application are disclosed in U.S. Patent No. 4,482,357, the entire disclosure of which is incorporated herein by reference, including, for example, salicylidene-o-aminophenol, disalicylidene ethylenediamine, disalicylidene propylenediamine, and N,N'-disalicylidene-1,2-diaminopropane.

[0033] Suitable optional cyclic aromatic manganese tricarbonyl compounds that may be used in the compositions of the present application include, for example, cyclopentadienyl manganese tricarbonyl, methylcyclopentadienyl manganese tricarbonyl, indenyl manganese tricarbonyl, and ethylcyclopentadienyl manganese tricarbonyl. Further examples of suitable cyclic aromatic manganese tricarbonyl compounds are disclosed in U.S. Patent Nos. 5,575,823 and 3,015,668, both of which are incorporated herein by reference.

[0034] Commercially available detergents may be used in the fuels herein, including, but not limited to, succinimides, Mannich base detergents, PIB amines, quaternary ammonium salt detergents, bis-aminotriazole detergents, and reaction products of hydrocarbyl-substituted dicarboxylic acids or anhydrides with aminoguanidines, as generally described in U.S. Patent Application Nos. 13 / 450,638, and the reaction products generally described in U.S. Patent Application Nos. 13 / 240,233 and 13 / 454,697, having less than one equivalent of aminotriazole groups per molecule.

[0035] The fuels herein may also contain other optional additives as required for a particular application and may include one or more demulsifiers, corrosion inhibitors, anti-wear additives, antioxidants, metal deactivators, antistatic additives, dehaze agents, anti-knock additives, lubricity additives, and / or combustion improvers as required.

[0036] Base oil or base oil blend of the lubricating composition: The lubricating oil composition herein comprises a base oil or a blend of base oils in combination with an additive package comprising one or more oil-soluble silicon-containing compounds. The base oil herein may be one or more oils of lubricating viscosity and may be selected from any of the base oils of API Groups I to V as set forth in the American Petroleum Institute (API) Base Oil Interchangeability Guidelines. In some embodiments, the base oil blend herein, including any selected base oil for producing a lubricant in some approaches or embodiments, has a KV100 (ASTM D445) of about 2 to about 20 cSt, in other approaches, about 5 to about 15 cSt, about 8 to about 15 cSt, and in yet other approaches, about 10 to about 15 cSt. As is known, the five base oil groups are generally as shown in Table 1 below.

[0037] [Table 1]

[0038] Group I, Group II, and Group III are mineral oil process feedstocks. Group IV base oils contain true synthetic molecular species produced by polymerization of olefinically unsaturated hydrocarbons. Many Group V base oils are also true synthetic products and may include diesters, polyol esters, polyalkylene glycols, alkylated aromatics, polyphosphate esters, polyvinyl ethers, and / or polyphenyl ethers, etc., but may also be natural oils, such as vegetable oils. It should be noted that Group III base oils are derived from mineral oils, but the rigorous processing these fluids undergo makes their physical properties very similar to some true synthetic oils, such as PAOs. Thus, oils derived from Group III base oils may be referred to as synthetic fluids in the industry. Group II+ may include high viscosity index Group II.

[0039] The base oil blends used in the disclosed lubricating oil compositions can be mineral oils, animal oils, vegetable oils, synthetic oils, synthetic oil blends, or mixtures thereof. Suitable oils can be derived from hydrocracked, hydrogenated, hydrofinished, unrefined, refined, and rerefined oils, and mixtures thereof.

[0040] Unrefined oils are derived from natural, mineral, or synthetic sources with little or no further purification treatment. Refined oils are similar to unrefined oils, except that they have been treated with one or more purification steps that may result in the improvement of one or more properties. Examples of suitable purification techniques are solvent extraction, secondary distillation, acid or base extraction, filtration, percolation, etc. Oils refined to edible quality may or may not be useful. Edible oils may also be called white oils. In some embodiments, the lubricating oil composition does not include edible oils or white oils.

[0041] Rerefined oils are also known as reclaimed or reprocessed oils. These oils are obtained similarly to refined oils using the same or similar processes. Often, these oils are additionally processed by techniques directed to the removal of spent additives and oil breakdown products.

[0042] Mineral oils may include oils obtained by drilling or from plants and animals, or any mixture thereof. For example, such oils may include, but are not limited to, castor oil, lard oil, olive oil, peanut oil, corn oil, soybean oil, and linseed oil, as well as mineral lubricating oils, such as liquid petroleum oils, and solvent-treated or acid-treated mineral lubricating oils of the paraffinic, naphthenic, or mixed paraffinic-naphthenic types. Such oils may be partially or fully hydrogenated, if desired. Oils derived from coal or shale may also be useful.

[0043] Useful synthetic lubricating oils may include hydrocarbon oils such as polymerized, oligomerized, or interpolymerized olefins (e.g., polybutylene, polypropylene, propylene isobutylene copolymers); poly(1-hexene), poly(1-octene), trimers or oligomers of 1-decene, such as poly(1-decene) (such materials are often referred to as alpha-olefins), and mixtures thereof; alkyl-benzenes (e.g., dodecylbenzene, tetradecylbenzene, dinonylbenzene, di-(2-ethylhexyl)-benzene); polyphenyls (e.g., biphenyl, terphenyl, alkylated polyphenyls); diphenylalkanes, alkylated diphenylalkanes, alkylated diphenyl ethers, and alkylated diphenyl sulfides, and derivatives, analogs, and homologs thereof, or mixtures thereof. The polyalphaolefins are typically hydrogenated materials.

[0044] Other synthetic lubricating oils include polyol esters, diesters, liquid esters of phosphorus-containing acids (e.g., tricresyl phosphate, trioctyl phosphate, and diethyl ester of decane phosphonic acid), or polymeric tetrahydrofurans. Synthetic oils may be produced by the Fischer-Tropsch reaction and typically may be hydroisomerized Fischer-Tropsch hydrocarbons or waxes. In one embodiment, the oils may be prepared by the Fischer-Tropsch gas-liquid synthesis procedure, as well as other gas-liquid oils.

[0045] A major amount of base oil included in the lubricating composition may be selected from the group consisting of Group I, Group II, Group III, Group IV, Group V, and combinations of two or more of the foregoing, but the major amount of base oil is other than the base oil resulting from the provision of an additive component or viscosity index improver in the composition. In another embodiment, a major amount of base oil included in the lubricating composition may be selected from the group consisting of Group II, Group III, Group IV, Group V, and combinations of two or more of the foregoing, but the major amount of base oil is other than the base oil resulting from the provision of an additive component or viscosity index improver in the composition.

[0046] The amount of oil of lubricating viscosity present may be the remainder remaining after subtracting the sum of the amounts of performance additives, including viscosity index improvers and / or pour point depressants and / or other top treat additives, from 100% by weight. For example, the oil of lubricating viscosity may be present in the final fluid in a "major amount," such as greater than about 50% by weight, greater than about 60% by weight, greater than about 70% by weight, greater than about 80% by weight, greater than about 85% by weight, or greater than about 90% by weight.

[0047] As generally used herein, the terms "oil composition," "lubricating composition," "lubricating oil composition," "lubricant," "lubricant composition," "lubricant," and "lubricant" are considered to be synonymous and fully interchangeable terms and refer to a passenger car motor oil lubrication product that contains a major amount of a base oil component having the blending amounts set forth above, plus minor amounts of detergents, and other optional components, preferably API GF-6.

[0048] Optional Additives of the Lubricating Composition: The lubricating compositions herein may also contain several optional additives in addition to the oil-soluble silicon-containing compounds to meet performance criteria, which are described in the following paragraphs.

[0049] Dispersants: The lubricating oil composition may optionally contain one or more other dispersants or mixtures thereof. Dispersants are often referred to as ashless dispersants because they do not contain ash-forming metals prior to mixing into the lubricating oil composition and do not normally contribute ash when added to the lubricant. Ashless dispersants are characterized by having polar groups attached to a relatively high molecular weight hydrocarbon chain. Typical ashless dispersants include N-substituted long chain alkenyl succinimides. Examples of N-substituted long chain alkenyl succinimides include polyisobutylene succinimides in which the number average molecular weight of the polyisobutylene substituent ranges from about 350 to about 50,000, or from about 5,000, or from about 3,000, as measured by GPC. Succinimide dispersants and their preparation are disclosed, for example, in U.S. Pat. No. 7,897,696 or U.S. Pat. No. 4,234,435. The alkenyl substituent may be prepared from polymerizable monomers containing from about 2 to about 16, or from about 2 to about 8, or from about 2 to about 6 carbon atoms. Succinimide dispersants are typically imides formed from polyamines, typically poly(ethyleneamines).

[0050] Preferred amines are selected from polyamines and hydroxylamines. Examples of polyamines that may be used include, but are not limited to, diethylene triamine (DETA), tetraethylene pentamine (TETA), tetraethylene tetramine (TEPA), and higher homologs such as pentaethylamine hexamine (PEHA).

[0051] Suitable heavy polyamines are mixtures of polyalkylene-polyamines containing small amounts of lower polyamine oligomers such as TEPA and PEHA (pentaethylenehexamine), but primarily oligomers with 6 or more nitrogen atoms, 2 or more primary amines per molecule, and more extensive branching than conventional polyamine mixtures. Heavy polyamines preferably include polyamine oligomers containing 7 or more nitrogen atoms per molecule and having 2 or more primary amines per molecule. Heavy polyamines contain greater than 28% by weight (e.g., >32% by weight) total nitrogen and primary amine groups with an equivalent weight of 120 to 160 grams per gram equivalent.

[0052] In some approaches, suitable polyamines, commonly known as PAM, contain a mixture of ethyleneamines, with TEPA and pentaethylenehexamine (PEHA) being the major portion of the polyamine, usually less than about 80%.

[0053] Typically, PAM has 8.7-8.9 milliequivalents of primary amine per gram (115-112 milliequivalents per equivalent of primary amine) and a total nitrogen content of about 33-34% by weight. Heavier cuts of PAM oligomers that are substantially free of TEPA and contain only small amounts of PEHA, but contain primarily oligomers with more than six nitrogen atoms and more extensive branching, may produce dispersants with improved dispersancy.

[0054] In some embodiments, the present disclosure further comprises at least one polyisobutylene succinimide dispersant derived from polyisobutylene having a number average molecular weight in the range of about 350 to about 50,000, or to about 5,000, or to about 3,000, as determined by GPC. The polyisobutylene succinimide may be used alone or in combination with other dispersants.

[0055] In some embodiments, when polyisobutylene is included, the polyisobutylene may have a terminal double bond content of greater than 50 mol%, greater than 60 mol%, greater than 70 mol%, greater than 80 mol%, or greater than 90 mol%. Such PIB is also referred to as highly reactive PIB ("HR-PIB"). HR-PIB having a number average molecular weight in the range of about 800 to about 5000 as determined by GPC is suitable for use in embodiments of the present disclosure. Conventional PIB typically has a terminal double bond content of less than 50 mol%, less than 40 mol%, less than 30 mol%, less than 20 mol%, or less than 10 mol%.

[0056] HR-PIB having a number average molecular weight in the range of about 900 to about 3000 as determined by GPC may be suitable. Such HR-PIB is commercially available or can be synthesized by polymerization of isobutene in the presence of a non-chlorinated catalyst such as boron trifluoride, as described in U.S. Patent No. 4,152,499 to Boerzel, et al. and U.S. Patent No. 5,739,355 to Gateau, et al. When HR-PIB is used in the thermal ene reaction, it may result in higher conversion during the reaction and less precipitate formation due to increased reactivity. A suitable method is described in U.S. Patent No. 7,897,696.

[0057] In one embodiment, the present disclosure further includes at least one dispersant derived from polyisobutylene succinic anhydride ("PIBSA"), which may have an average of about 1.0 to about 2.0 succinic moieties per polymer.

[0058] The percent actives of the alkenyl or alkyl succinic anhydride can be determined using chromatographic techniques, which are described in U.S. Patent No. 5,334,321, columns 5 and 6.

[0059] Percent polyolefin conversion is calculated from the % actives using the formula in columns 5 and 6 of US Pat. No. 5,334,321.

[0060] Unless otherwise specified, all percentages are weight percent and all molecular weights are number average molecular weights as determined by gel permeation chromatography (GPC) using commercially available polystyrene standards (having number average molecular weights of 180 to about 18,000) as calibration standards.

[0061] In one embodiment, the dispersant may be derived from a polyalphaolefin (PAO) succinic anhydride. In one embodiment, the dispersant may be derived from an olefin maleic anhydride copolymer. As an example, the dispersant may be described as poly-PIBSA. In one embodiment, the dispersant may be derived from an anhydride grafted to an ethylene-propylene copolymer.

[0062] A suitable class of nitrogen-containing dispersants may be derived from olefin copolymers (OCPs), more specifically ethylene-propylene dispersants that may be grafted with maleic anhydride. A more complete list of nitrogen-containing compounds that may be reacted with the functionalized OCPs is described in U.S. Patent Nos. 7,485,603, 7,786,057, 7,253,231, 6,107,257, and 5,075,383, and / or is commercially available.

[0063] One class of suitable dispersants may also be Mannich bases. Mannich bases are materials formed by condensation of higher molecular weight alkyl-substituted phenols, polyalkylene polyamines, and aldehydes such as formaldehyde. Mannich bases are described in more detail in U.S. Pat. No. 3,634,515.

[0064] A suitable class of dispersants may also be high molecular weight esters or half ester amides. Suitable dispersants may also be post-treated by reaction with any of a variety of agents by conventional methods. Among these are boron, urea, thiourea, dimercaptothiadiazole, carbon disulfide, aldehydes, ketones, carboxylic acids, hydrocarbon-substituted succinic anhydrides, maleic anhydrides, nitriles, epoxides, carbonates, cyclic carbonates, hindered phenol esters, and phosphorus compounds. U.S. Patent No. 7,645,726, U.S. Patent No. 7,214,649, and U.S. Patent No. 8,048,831 are incorporated herein by reference in their entirety.

[0065] In addition to the carbonate and boric acid post-treatments, any of the compounds may be post-treated or further post-treated with a variety of post-treatments designed to improve or impart different properties. Such post-treatments include those summarized in columns 27-29 of U.S. Pat. No. 5,241,003, which is incorporated herein by reference. Such treatments include treatment with inorganic phosphoric acids or anhydrides (e.g., U.S. Pat. Nos. 3,403,102 and 4,648,980); organic phosphorus compounds (e.g., U.S. Pat. No. 3,502,677); phosphorus pentasulfide; boron compounds as already mentioned above (e.g., U.S. Pat. Nos. 3,178,663 and 4,652,387); carboxylic acids, polycarboxylic acids, anhydrides, and / or acid halides (e.g., U.S. Pat. Nos. 3,708,522 and 4,912,522); and / or carboxylic acids such as carboxylic acids, polycarboxylic acids, anhydrides, and / or acid halides (e.g., U.S. Pat. Nos. 3,708,522 and 4,912,522). 48,386; epoxides, polyepoxyates or thioepoxides (e.g., U.S. Pat. Nos. 3,859,318 and 5,026,495); aldehydes or ketones (e.g., U.S. Pat. No. 3,458,530); carbon disulfide (e.g., U.S. Pat. No. 3,256,185); glycidol (e.g., U.S. Pat. No. 4,617,137); urea, thiourea, or guanidine (e.g., U.S. Pat. No. 3,312,61 9, 3,865,813, and British Patent No. 1,065,595; organic sulfonic acids (e.g., U.S. Pat. No. 3,189,544 and British Patent No. 2,140,811); alkenyl cyanides (e.g., U.S. Pat. Nos. 3,278,550 and 3,366,569); diketenes (e.g., U.S. Pat. No. 3,546,243); diisocyanates (e.g., U.S. Pat. No. 3,573,205); alkanesuls t (e.g., U.S. Pat. No. 3,749,695); 1,3-dicarbonyl compounds (e.g., U.S. Pat. No. 4,579,675); sulfates of alkoxylated alcohols or phenols (e.g., U.S. Pat. No. 3,954,639); cyclic lactones (e.g., U.S. Pat. Nos. 4,617,138; 4,645,515; 4,668,246; 4,963,275; and 4,971,711);Cyclic carbonates or thiocarbonates, linear monocarbonates or polycarbonates, or chloroformates (e.g., U.S. Pat. Nos. 4,612,132, 4,647,390, 4,648,886, 4,670,170); nitrogen-containing carboxylic acids (e.g., U.S. Pat. No. 4,971,598 and British Patent No. 2,140,811); hydroxy-protected chlorodicarbonyloxy compounds (e.g., U.S. Pat. No. 4,614,522); lactams, thiolactams, thiolactones, or dithiolactones (e.g., U.S. Pat. No. 4,612,132, U.S. Pat. No. 4,647,390, U.S. Pat. No. 4,648,886, U.S. Pat. No. 4,670,170); Nos. 4,614,603 and 4,666,460; cyclic carbonates or thiocarbonates, linear monocarbonates or polycarbonates, or chloroformates (e.g., U.S. Pat. Nos. 4,612,132, 4,647,390, 4,646,860, and 4,670,170); nitrogen-containing carboxylic acids (e.g., U.S. Pat. No. 4,971,598 and British Patent No. 2,440,811); hydroxy-protected chlorodicarbonyloxy compounds (e.g., U.S. Pat. No. 4,614,522); lactams, thiocarbonates, etc. olactams, thiolactones, or dithiolactones (e.g., U.S. Pat. Nos. 4,614,603 and 4,666,460); cyclic carbamates, cyclic thiocarbamates, or cyclic dithiocarbamates (e.g., U.S. Pat. Nos. 4,663,062 and 4,666,459); hydroxyaliphatic carboxylic acids (e.g., U.S. Pat. Nos. 4,482,464; 4,521,318; and 4,713,189); oxidizing agents (e.g., U.S. Pat. No. 4,379,064); combinations of phosphorus pentasulfide and polyalkylene polyamines (e.g., U.S. Pat. Nos. 4,379,064); , U.S. Pat. No. 3,185,647; combinations of carboxylic acids or aldehydes or ketones and sulfur or sulfur chlorides (e.g., U.S. Pat. Nos. 3,390,086, 3,470,098); combinations of hydrazine and carbon disulfide (e.g., U.S. Pat. No. 3,519,564); combinations of aldehydes and phenols (e.g., U.S. Pat. Nos. 3,649,229, 5,030,249, 5,039,307); combinations of aldehydes and O-diesters of dithiophosphoric acids (e.g., U.S. Pat. No. 3,865,740);Combinations of hydroxyaliphatic carboxylic acids and boric acid (e.g., U.S. Pat. No. 4,554,086); combinations of hydroxyaliphatic carboxylic acids followed by formaldehyde and phenols (e.g., U.S. Pat. No. 4,636,322); combinations of hydroxyaliphatic carboxylic acids and then aliphatic dicarboxylic acids (e.g., U.S. Pat. No. 4,663,064); combinations of formaldehyde and phenols and then glycolic acid (e.g., U.S. Pat. No. 4,699,724); combinations of hydroxyaliphatic carboxylic acids or oxalic acid followed by a diisocyanate (e.g., U.S. Pat. No. 4,713,191); inorganic acids or anhydrides of phosphorus. or a combination of its partial or total sulfur analogue and a boron compound (e.g., U.S. Pat. No. 4,857,214); a combination of an organic diacid, followed by an unsaturated fatty acid, followed by a nitrosoaromatic amine, optionally followed by a boron compound, and then a glycosylation agent (e.g., U.S. Pat. No. 4,973,412); a combination of an aldehyde and a triazole (e.g., U.S. Pat. No. 4,963,278); a combination of an aldehyde and a triazole, followed by a boron compound (e.g., U.S. Pat. No. 4,981,492); a combination of a cyclic lactone and a boron compound (e.g., U.S. Pat. Nos. 4,963,275 and 4,971,711). The above-mentioned patents are hereby incorporated in their entirety;

[0066] The TBN of suitable dispersants may be from about 10 to about 65 mg KOH / g on an oil-free basis, which equates to about 5 to about 30 TBN when measured on a dispersant sample containing about 50% diluent oil. TBN is measured by the method of ASTM D2896.

[0067] In yet another embodiment, the optional dispersant additive may be a hydrocarbyl-substituted succinamide or succinimide dispersant. In some approaches, the hydrocarbyl-substituted succinamide or succinimide dispersant may be derived from a hydrocarbyl-substituted acylating agent reacted with a polyalkylene polyamine, where the hydrocarbyl substituent of the succinamide or succinimide dispersant is a linear or branched hydrocarbyl group having a number average molecular weight of about 250 to about 5,000 as measured by GPC using polystyrene as a calibration standard.

[0068] In some approaches, the polyalkylene polyamine used to form the dispersant has the formula:

[0069] [ka] wherein each R and R' is independently a divalent C1-C6 alkylene linker, each R1 and R2 is independently hydrogen, a C1-C6 alkyl group, or together with the nitrogen atom to which they are attached form a 5- or 6-membered ring optionally fused to one or more aromatic or non-aromatic rings, and n is an integer from 0 to 8. In another approach, the polyalkylene polyamine is selected from the group consisting of a mixture of polyethylene polyamines having an average of 5 to 7 nitrogen atoms, triethylenetetramine, tetraethylenepentamine, and combinations thereof.

[0070] Dispersants, when present, may be used in an amount sufficient to provide up to about 20% by weight, based on the final weight of the lubricating oil composition. Alternative amounts of dispersants that may be used may be from about 0.1 to about 15% by weight, or from about 0.1 to about 10% by weight, or from about 0.1 to about 8% by weight, or from about 1 to about 10% by weight, or from about 1 to about 8% by weight, or from about 1 to about 6% by weight, based on the final weight of the lubricating oil composition. In some embodiments, the lubricating oil composition utilizes a mixed dispersant system. A single type or a mixture of two or more types of dispersants in any desired ratio may be used.

[0071] Other antioxidants: The lubricating oil composition herein may also optionally contain one or more antioxidants. Antioxidant compounds are known and include, for example, phenates, phenate sulfides, sulfurized olefins, phosphosulfurized terpenes, sulfurized esters, aromatic amines, alkylated diphenylamines (e.g., nonyldiphenylamine, di-nonyldiphenylamine, octyldiphenylamine, di-octyldiphenylamine), phenyl-alpha-naphthylamines, alkylated phenyl-alpha-naphthylamines, hindered non-aromatic amines, phenols, hindered phenols, oil-soluble molybdenum compounds, polymeric antioxidants, or mixtures thereof. The antioxidant compounds may be used alone or in combination.

[0072] The hindered phenol antioxidant may contain secondary butyl and / or tertiary butyl groups as steric hindrance groups. The phenol group may be further substituted with a hydrocarbyl group and / or a bridging group that connects to a second aromatic group. Examples of suitable hindered phenol antioxidants include 2,6-di-tert-butylphenol, 4-methyl-2,6-di-tert-butylphenol, 4-ethyl-2,6-di-tert-butylphenol, 4-propyl-2,6-di-tert-butylphenol or 4-butyl-2,6-di-tert-butylphenol, or 4-dodecyl-2,6-di-tert-butylphenol. In one embodiment, the hindered phenol antioxidant may be an ester and may include, for example, Irganox® L-135 available from BASF or an addition product derived from 2,6-di-tert-butylphenol and an alkyl acrylate, where the alkyl group may contain from about 1 to about 18, or from about 2 to about 12, or from about 2 to about 8, or from about 2 to about 6, or about 4 carbon atoms. Another commercially available hindered phenol antioxidant may be an ester and may include Ethanox™ 4716 available from SI Group.

[0073] Useful antioxidants may include diarylamines and high molecular weight phenols. In one embodiment, the lubricating oil composition may contain a mixture of diarylamines and high molecular weight phenols, such that each antioxidant may be present in an amount sufficient to provide up to about 5 wt. %, based on the final weight of the lubricating oil composition. In one embodiment, the antioxidant may be a mixture of about 0.3 to about 1.5 wt. % diarylamines and about 0.4 to about 2.5 wt. % high molecular weight phenols, based on the final weight of the lubricating oil composition.

[0074] Examples of suitable olefins that can be sulfurized to form sulfurized olefins include propylene, butylene, isobutylene, polyisobutylene, pentene, hexene, heptene, octene, nonene, decene, undecene, dodecene, tridecene, tetradecene, pentadecene, hexadecene, heptadecene, octadecene, nonadecene, eicosene, or mixtures thereof. In one embodiment, hexadecene, heptadecene, octadecene, nonadecene, eicosene, or mixtures thereof, as well as their dimers, trimers, and tetramers, are particularly useful olefins. Alternatively, the olefins can be Diels-Alder adducts of dienes such as 1,3-butadiene and unsaturated esters such as butyl acrylate.

[0075] Another class of sulfurized olefins includes sulfurized fatty acids and their esters. The fatty acids are often derived from vegetable or animal oils and typically contain from about 4 to about 22 carbon atoms. Examples of suitable fatty acids and their esters include triglycerides, oleic acid, linoleic acid, palmitoleic acid, or mixtures thereof. Often, the fatty acids are derived from lard oil, tall oil, peanut oil, soybean oil, cottonseed oil, sunflower seed oil, or mixtures thereof. The fatty acids and / or esters may be mixed with olefins, such as α-olefins.

[0076] In another alternative embodiment, the antioxidant composition contains a molybdenum-containing antioxidant in addition to the phenolic and / or aminic antioxidants discussed above. When a combination of these three antioxidants is used, preferably the treat rate ratio of the phenolic to the amine to the molybdenum-containing components is (0-3):(0-3):(0-3).

[0077] The one or more antioxidants may be present in the range of from about 0% to about 20%, or from about 0.1% to about 10%, or from about 1% to about 5% by weight of the lubricating oil composition.

[0078] Antiwear agents: The lubricating oil compositions herein may also optionally contain one or more antiwear agents. Examples of suitable antiwear agents include, but are not limited to, metal thiophosphates; metal dialkyldithiophosphates; phosphate esters or salts thereof; phosphoric acid esters; phosphites; phosphorus-containing carboxylic acid esters, ethers, or amides; sulfurized olefins; thiocarbamate-containing compounds, such as thiocarbamate esters, alkylene-linked thiocarbamates, and bis(S-alkyldithiocarbamyl) disulfides; and mixtures thereof. A suitable antiwear agent may be molybdenum dithiocarbamate. Phosphorus-containing antiwear agents are more fully described in EP 612839. The metal in the dialkyldithiophosphate salt may be an alkali metal, alkaline earth metal, aluminum, lead, tin, molybdenum, manganese, nickel, copper, titanium, or zinc. A useful antiwear agent may be zinc dialkyldithiophosphate.

[0079] Further examples of suitable antiwear agents include titanium compounds, tartrates, tartrimides, oil-soluble amine salts of phosphorus compounds, sulfurized olefins, phosphites (e.g., dibutyl phosphite), phosphonates, thiocarbamate-containing compounds such as thiocarbamate esters, thiocarbamate amides, thiocarbamic acid ethers, alkylene-linked thiocarbamates, and bis(S-alkyldithiocarbamyl) disulfides. The tartrates or tartrimides may contain alkyl-ester groups, but the total of carbon atoms on the alkyl group may be at least 8. The antiwear agent may, in one embodiment, include citrates.

[0080] The antiwear agent may be present in ranges including from about 0 to about 15 weight percent, or from about 0.01 to about 10 weight percent, or from about 0.05 to about 5 weight percent, or from about 0.1 to about 3 weight percent of the lubricating oil composition.

[0081] Boron-containing compounds: The lubricating oil compositions herein may optionally contain one or more boron-containing compounds. Examples of boron-containing compounds include borate esters, borated fatty amines, borated epoxides, borated detergents, and borated dispersants, such as borated succinimide dispersants, as disclosed in U.S. Pat. No. 5,883,057. The boron-containing compounds, when present, may be used in an amount sufficient to provide up to about 8% by weight, about 0.01 to about 7% by weight, about 0.05 to about 5% by weight, or about 0.1 to about 3% by weight of the lubricating oil composition.

[0082] Detergents: The lubricating oil composition may optionally further comprise one or more neutral, low-based, or overbased detergents, and mixtures thereof. Suitable detergent substrates include phenates, sulfur-containing phenates, sulfonates, calixarates, salixarates, salicylates, carboxylic acids, phosphoric acids, mono- and / or di-thiophosphoric acids, alkylphenols, sulfur-linked alkylphenol compounds, or methylene-bridged phenols. Suitable detergents and their preparation methods are described in more detail in numerous patent publications, including U.S. Pat. No. 7,732,390 and references cited therein.

[0083] The detergent substrate may be salified with an alkali or alkaline earth metal, such as, but not limited to, calcium, magnesium, potassium, sodium, lithium, barium, or mixtures thereof. In some embodiments, the detergent does not contain barium. In some embodiments, the detergent may contain trace amounts of other metals, such as magnesium or calcium, in amounts such as 50 ppm or less, 40 ppm or less, 30 ppm or less, 20 ppm or less, or 10 ppm or less. Suitable detergents may include alkali or alkaline earth metal salts of petroleum sulfonic acids and long chain mono- or di-alkylaryl sulfonic acids, where the aryl groups are benzyl, tolyl, and xylyl. Examples of suitable detergents include, but are not limited to, calcium phenates, calcium sulfur-containing phenates, calcium sulfonates, calcium calixarates, calcium salixarates, calcium salicylates, calcium carboxylic acids, calcium phosphoric acids, calcium mono- and / or di-thiophosphoric acids, calcium alkyl phenols, calcium sulfur-bound alkyl phenol compounds, calcium methylene bridged phenols, magnesium phenate, magnesium sulfonate, magnesium calixarates, magnesium salixarates, magnesium salicylates, magnesium carboxylic acids, magnesium phosphoric acids, magnesium mono- and / or di-thiophosphoric acids, magnesium alkyl phenols, magnesium sulfur-bound alkyl phenol compounds, magnesium methylene bridged phenols, sodium phenate, sodium sulfonate, sodium calixarates, sodium salixarates, sodium salicylates, sodium carboxylic acids, sodium phosphoric acids, sodium mono- and / or di-thiophosphoric acids, sodium alkyl phenols, sodium sulfur-bound alkyl phenol compounds, or sodium methylene bridged phenols.

[0084] Overbased detergent additives are well known in the art and may be alkali or alkaline earth metal overbased detergent additives. Such detergent additives may be prepared by reacting a metal oxide or metal hydroxide with a substrate and carbon dioxide gas. The substrate is typically an acid, such as an aliphatic substituted sulfonic acid, an aliphatic substituted carboxylic acid, or an aliphatic substituted phenol.

[0085] The term "overbased" refers to metal salts, such as metal salts of sulfonates, carboxylates, and phenates, in which the amount of metal present exceeds the stoichiometric amount. Such salts may have a conversion level of more than 100% (i.e., such salts may contain more than 100% of the theoretical amount of metal required to convert the acid to its "standard" or "neutral" salt). The expression "metal ratio", often abbreviated as MR, is used to indicate the ratio of the total chemical equivalents of the metal in an overbased salt to the chemical equivalents of the metal in a neutral salt, according to known chemical reactivity and stoichiometry. In standard or neutral salts, the metal ratio (MR) is 1, whereas in overbased salts, the MR is greater than 1. They are generally referred to as overbased, hyperbased, or superbased salts and may be salts of organic sulfur acids, carboxylic acids, or phenols.

[0086] The overbased detergent of the lubricating oil composition may have a total base number (TBN) of about 200 mg KOH / g or greater, or, as a further example, about 250 mg KOH / g or greater, or about 350 mg KOH / g or greater, or about 375 mg KOH / g or greater, or about 400 mg KOH / g or greater, as measured by the method of ASTM D2896.

[0087] Examples of suitable overbased detergents include, but are not limited to, overbased calcium phenates, overbased calcium sulfur-containing phenates, overbased calcium sulfonates, overbased calcium calixarates, overbased calcium salixarates, overbased calcium salicylates, overbased calcium carboxylic acids, overbased calcium phosphates, overbased calcium mono- and / or di-thiophosphates, overbased calcium alkylphenols, overbased calcium sulfur-bound alkylphenol compounds, overbased calcium methylene bridged phenols, overbased magnesium phenates, overbased magnesium sulfur-containing phenates, overbased magnesium sulfonates, overbased magnesium calixarates, overbased magnesium salixarates, overbased magnesium salicylates, overbased magnesium carboxylic acids, overbased magnesium phosphates, overbased magnesium mono- and / or di-thiophosphates, overbased magnesium alkylphenols, overbased magnesium sulfur-bound alkylphenol compounds, or overbased magnesium methylene bridged phenols.

[0088] The overbased calcium phenate detergents have a total base number of at least about 150 mg KOH / g, at least about 225 mg KOH / g, at least about 225 to about 400 mg KOH / g, at least about 225 to about 350 mg KOH / g, or about 230 to about 350 mg KOH / g, all measured by the method of ASTM D 2896. When such detergent compositions are formed in an inert diluent, such as a process oil, often a mineral oil, the total base number reflects the basicity of the entire composition, including the diluent and any other materials that may be included in the detergent composition (e.g., accelerators, etc.).

[0089] The overbased detergent may have a metal to substrate ratio of 1.1:1 or greater, or 2:1 or greater, or 4:1 or greater, or 5:1 or greater, or 7:1 or greater, or 10:1 or greater. In some embodiments, the detergent is effective in reducing or preventing rust in engines or other automotive components such as transmissions or gears. The detergent may be present in the lubricating composition from about 0 to about 10 wt%, or from about 0.1 to about 8 wt%, or from about 1 to about 4 wt%, or from greater than about 4 wt% to about 8 wt%.

[0090] Extreme Pressure Agents: The lubricating oil compositions herein may also optionally contain one or more extreme pressure agents. Extreme Pressure (EP) agents that are soluble in oil include sulfur and chlorosulfur containing EP agents, chlorinated hydrocarbon EP agents, and phosphorus EP agents. Examples of such EP agents include chlorinated waxes; organic sulfides and polysulfides such as dibenzyl disulfide, bis(chlorobenzyl) disulfide, dibutyl tetrasulfide, sulfurized methyl ester of oleic acid, sulfurized alkylphenols, sulfurized dipentenes, sulfurized terpenes, and sulfurized Diels-Alder adducts; phosphorus sulfurized hydrocarbons such as the reaction products of phosphorus sulfide with turpentine or methyl oleate; dihydrocarbyl and trihydrocarbyl phosphites, for example, phosphate esters such as dibutyl phosphite, diheptyl phosphite, dicyclohexyl phosphite, pentyl phenyl phosphite; dipentyl phenyl phosphite, tridecyl phosphite, distearyl phosphite, and polypropylene substituted phenyl phosphites; metal thiocarbamates such as zinc dioctyldithiocarbamate and barium heptylphenol diacid; amine salts of alkyl and dialkyl phosphates, including, for example, the amine salt of the reaction product of a dialkyl dithiophosphoric acid with propylene oxide; and mixtures thereof.

[0091] Friction Modifiers: The lubricating oil compositions herein may also optionally contain one or more friction modifiers. Suitable friction modifiers may include metal-containing and metal-free friction modifiers, but may include, but are not limited to, imidazolines, amides, amines, succinimides, alkoxylated amines, alkoxylated ether amines, amine oxides, amidoamines, nitriles, betaines, quaternary amines, imines, amine salts, aminoguanidines, alkanolamides, phosphonates, metal-containing compounds, glycerol esters, sulfurized fatty compounds and olefins, sunflower oil, other naturally occurring vegetable or animal oils, dicarboxylic acid esters, esters or partial esters of polyols with one or more aliphatic or aromatic carboxylic acids, and the like.

[0092] Suitable friction modifiers may contain hydrocarbyl groups selected from linear, branched, or aromatic hydrocarbyl groups, or mixtures thereof, and may be saturated or unsaturated. The hydrocarbyl groups may be composed of carbon and hydrogen or heteroatoms such as sulfur or oxygen. The hydrocarbyl groups may range from about 12 to about 25 carbon atoms. In some embodiments, the friction modifier may be a long chain fatty acid ester. In other embodiments, the long chain fatty acid ester may be a mono-ester, or a di-ester, or a (tri)glyceride. The friction modifier may be a long chain fatty amide, a long chain fatty ester, a long chain fatty epoxide derivative, or a long chain imidazoline.

[0093] Other suitable friction modifiers may include organic, ashless (metal-free), nitrogen-free mechanical friction modifiers. Such friction modifiers may include esters formed by reacting carboxylic acids and anhydrides with alkanols, and generally may include polar end groups (e.g., carboxyl or hydroxyl) covalently bonded to an oleophilic hydrocarbon chain. An example of an organic ashless nitrogen-free friction modifier is commonly known as glycerol monooleate (GMO), which may include mono-, di-, and tri-esters of oleic acid. Other suitable friction modifiers are described in U.S. Patent No. 6,723,685, the entirety of which is incorporated herein by reference.

[0094] Aminic friction modifiers may include amines or polyamines. Such compounds may have hydrocarbyl groups that are either linear, saturated or unsaturated, or mixtures thereof, and may contain from about 12 to about 25 carbon atoms. Further examples of suitable friction modifiers include alkoxylated amines and alkoxylated ether amines. Such compounds may have hydrocarbyl groups that are either linear, saturated, unsaturated, or mixtures thereof. They may contain from about 12 to about 25 carbon atoms. Examples include ethoxylated amines and ethoxylated ether amines.

[0095] The amines and amides may be used by themselves or in the form of adducts or reaction products with boron compounds such as boron oxides, boron halides, metaborates, boric acid or mono-, di-, or tri-alkyl borates. Other suitable friction modifiers are described in U.S. Patent No. 6,300,291, which is incorporated herein by reference in its entirety.

[0096] Friction modifiers may optionally be present in a range such as from about 0 to about 10 weight percent, or from about 0.01 to about 8 weight percent, or from about 0.1 to about 4 weight percent.

[0097] Molybdenum-containing components: The lubricating oil compositions herein may also optionally contain one or more molybdenum-containing compounds. The oil-soluble molybdenum compounds may have the functional properties of antiwear agents, antioxidants, friction modifiers, or mixtures thereof. The oil-soluble molybdenum compounds may include molybdenum dithiocarbamates, molybdenum dialkyldithiophosphates, molybdenum dithiophosphinates, amine salts of molybdenum compounds, molybdenum xanthates, molybdenum thioxanthates, molybdenum sulfides, molybdenum carboxylates, molybdenum alkoxides, trinuclear organomolybdenum compounds, and / or mixtures thereof. Molybdenum sulfides include molybdenum disulfide. The molybdenum disulfide may be in the form of a stable dispersion. In one embodiment, the oil-soluble molybdenum compounds may be selected from the group consisting of molybdenum dithiocarbamates, molybdenum dialkyldithiophosphates, amine salts of molybdenum compounds, and mixtures thereof. In one embodiment, the oil soluble molybdenum compound can be a molybdenum dithiocarbamate.

[0098] Suitable examples of molybdenum compounds that may be used include commercially available materials sold under trade names such as Molyvan® 822, Molyvan® A, Molyvan® 2000, Molyvan® 855, Molyvan® 1055, and Molyvan® 3000 manufactured by R.T. Vanderbilt Co., Ltd., and Adeka Sakura-Lube® S-165, S-200, S-300, S-310G, S-525, S-600, S-700, and S-710 available from Adeka Corporation, and mixtures thereof. Suitable molybdenum components are described in U.S. Pat. No. 5,650,381, U.S. Reissue Pat. Nos. 37,363 (E1), 38,929 (E1), and 40,595 (E1), the entireties of which are incorporated herein by reference.

[0099] Additionally, the molybdenum compound can be an acidic molybdenum compound, including molybdic acid, ammonium molybdate, sodium molybdate, potassium molybdate, and other alkali metal molybdates and other molybdenum salts, such as sodium hydrogen molybdate, MoOCl4, MoO2Br2, Mo2O3Cl6, molybdenum trioxide, or similar acidic molybdenum compounds. Alternatively, the composition can provide the molybdenum via molybdenum / sulfur complexes of basic nitrogen compounds, as described, for example, in U.S. Pat. Nos. 4,263,152, 4,285,822, 4,283,295, 4,272,387, 4,265,773, 4,261,843, 4,259,195, and 4,259,194, and WO 94 / 06897, the foregoing patents being incorporated herein by reference in their entireties.

[0100] Another class of suitable organo-molybdenum compounds is the trinuclear molybdenum compounds, e.g., those of the formula MoS k L n Q z and mixtures thereof, where S represents sulfur, L represents an independently selected ligand having an organic group having a sufficient number of carbon atoms to render the compound soluble or dispersible in oil, n is 1 to 4, k varies from 4 to 7, Q is selected from the group of neutral electron donor compounds, such as water, amines, alcohols, phosphines, and ethers, and z ranges from 0 to 5, including non-stoichiometric values. At least 21 total carbon atoms may be present among all of the ligand organic groups, e.g., at least 25, at least 30, or at least 35 carbon atoms. Additional suitable molybdenum compounds are described in U.S. Pat. No. 6,723,685, the entirety of which is incorporated herein by reference.

[0101] The oil soluble molybdenum compound may be present in an amount sufficient to provide from about 0.5 to about 2000 ppm, from about 1 to about 700 ppm, from about 1 to about 550 ppm, from about 5 to about 300 ppm, or from about 20 to about 250 ppm of molybdenum.

[0102] Transition metal-containing compounds: In another embodiment, the oil-soluble compound may be a transition metal-containing compound or metalloid. Transition metals may include, but are not limited to, titanium, vanadium, copper, zinc, zirconium, molybdenum, tantalum, tungsten, etc. Suitable metalloids include, but are not limited to, boron, silicon, antimony, tellurium, etc.

[0103] In some embodiments, the oil-soluble transition metal-containing compound may function as an antiwear agent, a friction modifier, an antioxidant, an adhesion control additive, or two or more of these functions. In some embodiments, the oil-soluble transition metal-containing compound may be an oil-soluble titanium compound, such as titanium (IV) alkoxide. Among the titanium-containing compounds that may be used in or for the preparation of the oil-soluble material of the technology of the present disclosure, include various Ti (IV) compounds, such as titanium (IV) oxide; titanium (IV) sulfide; titanium (IV) nitrate; titanium (IV) alkoxides, such as titanium methoxide, titanium ethoxide, titanium propoxide, titanium isopropoxide, titanium butoxide, titanium 2-ethylhexoxide; and other titanium compounds or complexes, such as, but not limited to, titanium phenate; titanium carboxylates, such as titanium (IV) 2-ethyl-1,3-hexanedioate or titanium citrate or titanium oleate; and titanium (IV) (triethanolaminato) isopropoxide. Other forms of titanium encompassed by the disclosed technology include titanium phosphates, such as titanium dithiophosphates (e.g., dialkyl dithiophosphates) and titanium sulfonates (e.g., alkyl benzene sulfonates), or generally reaction products of titanium compounds with various acid materials to form salts, such as oil-soluble salts. Thus, titanium compounds may be derived from organic acids, alcohols, and glycols, among others. Ti compounds may also exist in dimeric or oligomeric forms containing Ti-O-Ti structures. Such titanium materials are commercially available or can be readily prepared by suitable synthetic techniques that will be apparent to those skilled in the art. They may exist at room temperature as solids or liquids, depending on the particular compound. They may also be provided in solution form in a suitable inert solvent.

[0104] In one embodiment, titanium may be provided as a Ti-modified dispersant, such as a succinimide dispersant. Such materials may be prepared by forming a titanium mixed anhydride between a titanium alkoxide and a hydrocarbyl-substituted succinic anhydride, such as an alkenyl-(or alkyl) succinic anhydride. The resulting titanate-succinate intermediate may be used directly or may be reacted with any of several materials, such as (a) polyamine-based succinimide / amide dispersants having free condensable -NH functional groups; (b) components of polyamine-based succinimide / amide dispersants, i.e., alkenyl (or alkyl) succinic anhydrides and polyamines; (c) hydroxy-containing polyester dispersants prepared by reaction of substituted succinic anhydrides with polyols, amino alcohols, polyamines, or mixtures thereof. Alternatively, the titanate-succinate intermediate can be reacted with other agents such as alcohols, amino alcohols, ether alcohols, polyether alcohols or polyols, or fatty acids, and the product can be used directly to impart Ti to a lubricant or can be further reacted with a succinic dispersant as described above. As an example, one part (mole) of tetraisopropyl titanate can be reacted with about two parts (mole) of polyisobutene-substituted succinic anhydride at 140-150°C for 5-6 hours to provide a titanium modified dispersant or intermediate. The resulting material (30 g) can be further reacted with a succinimide dispersant from a polyisobutene-substituted succinic anhydride and polyethylene polyamine mixture (127 grams + diluent oil) at 150°C for 1.5 hours to produce a titanium modified succinimide dispersant.

[0105] Another titanium-containing compound is titanium alkoxide and C6-C 25 It may be a reaction product with a carboxylic acid. The reaction product has the following formula:

[0106] [ka] wherein n is an integer selected from 2, 3, and 4, and R is a hydrocarbyl group containing from about 5 to about 24 carbon atoms, or the following formula:

[0107] [ka] or the titanium compound may be represented by the formula:

[0108] [ka] (wherein x ranges from 0 to 3; R1 is selected from hydrocarbyl groups containing about 6 to 25 carbon atoms; R2 and R3 are the same or different and are selected from hydrocarbyl groups containing about 1 to 6 carbon atoms; R4 is H, C6-C 25 The carboxylic acid moiety may be selected from the group consisting of

[0109] Suitable carboxylic acids may include, but are not limited to, caproic acid, caprylic acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachic acid, oleic acid, erucic acid, linoleic acid, linolenic acid, cyclohexanecarboxylic acid, phenylacetic acid, benzoic acid, neodecanoic acid, and the like.

[0110] In one embodiment, the oil soluble titanium compound may be present in the lubricating oil composition in an amount to provide from 0 to 3000 ppm by weight of titanium, or from 25 to about 1500 ppm by weight of titanium, or from about 35 ppm to about 500 ppm by weight of titanium, or from about 50 ppm to about 300 ppm by weight.

[0111] Viscosity index improver: The lubricating oil composition herein may also optionally contain one or more viscosity index improvers. Suitable viscosity index improvers may include polyolefins, olefin copolymers, ethylene / propylene copolymers, polyisobutene, hydrogenated styrene-isoprene polymers, styrene / maleic acid ester copolymers, hydrogenated styrene / butadiene copolymers, hydrogenated isoprene polymers, alpha-olefin maleic anhydride copolymers, polymethacrylates, polyacrylates, polyalkylstyrenes, hydrogenated alkenylaryl conjugated diene copolymers, or mixtures thereof. Viscosity index improvers may include star polymers, suitable examples of which are described in US Patent Application Publication No. 20120101017(A1).

[0112] The lubricating oil compositions herein may also optionally contain one or more dispersant viscosity index improvers in addition to or instead of the viscosity index improver. Suitable viscosity index improvers may include functionalized polyolefins, such as ethylene-propylene copolymers functionalized with the reaction product of an acylating agent (such as maleic anhydride) with an amine, amine-functionalized polymethacrylates, or esterified maleic anhydride-styrene copolymers reacted with amines.

[0113] The total amount of viscosity index improver and / or dispersant viscosity index improver can be from about 0 to about 20 weight percent, from about 0.1 to about 15 weight percent, from about 0.1 to about 12 weight percent, or from about 0.5 to about 10 weight percent of the lubricating oil composition.

[0114] Other optional additives: Other additives may be selected to perform one or more functions required in a lubricating fluid. Additionally, one or more of the aforementioned additives may be multifunctional and may provide functions in addition to or other than those described herein.

[0115] The lubricating oil composition according to the present disclosure may optionally contain other performance additives. The other performance additives may be in addition to the specific additives of the present disclosure and / or may include one or more of metal deactivators, viscosity index improvers, detergents, ashless TBN boosters, friction modifiers, antiwear agents, corrosion inhibitors, rust inhibitors, dispersants, dispersant viscosity index improvers, extreme pressure agents, antioxidants, foam suppressants, demulsifiers, emulsifiers, pour point depressants, seal swell agents, and mixtures thereof. Typically, a fully formulated lubricating oil will contain one or more of these performance additives.

[0116] Suitable metal deactivators may include derivatives of benzotriazole (typically tolyltriazole), dimercaptothiadiazole derivatives, 1,2,4-triazole, benzimidazole, 2-alkyldithiobenzimidazole, or 2-alkyldithiobenzothiazole; foam suppressors including copolymers of ethyl acrylate and 2-ethylhexyl acrylate and optionally vinyl acetate; demulsifiers including trialkyl phosphates, polyethylene glycol, polyethylene oxide, polypropylene oxide, and (ethylene oxide-propylene oxide) polymers; pour point depressants including esters of maleic anhydride-styrene, polymethacrylates, polyacrylates, or polyacrylamides.

[0117] Suitable suds suppressors include silicon-based compounds such as siloxanes.

[0118] Suitable pour point depressants may include polymethyl methacrylate or mixtures thereof. The pour point depressant may be present in an amount sufficient to provide from about 0 wt. % to about 1 wt. %, from about 0.01 wt. % to about 0.5 wt. %, or from about 0.02 wt. % to about 0.04 wt. %, based on the final weight of the lubricating oil composition.

[0119] A suitable rust inhibitor can be a single compound or a mixture of compounds that have the property of inhibiting corrosion of ferrous metal surfaces. Non-limiting examples of rust inhibitors useful herein include oil-soluble high molecular weight organic acids such as 2-ethylhexanoic acid, lauric acid, myristic acid, palmitic acid, oleic acid, linoleic acid, linolenic acid, behenic acid, and cerotic acid, as well as oil-soluble polycarboxylic acids including dimer and trimer acids such as those produced from tall oil fatty acids, oleic acid, and linoleic acid. Other suitable corrosion inhibitors include long chain alpha, omega-dicarboxylic acids in the molecular weight range of about 600 to about 3000, and alkenyl succinic acids in which the alkenyl group contains about 10 or more carbon atoms, such as tetrapropenyl succinic acid, tetradecenyl succinic acid, and hexadecenyl succinic acid. Another useful type of acidic corrosion inhibitor is the half ester of an alkenyl succinic acid having about 8 to about 24 carbon atoms in the alkenyl group with an alcohol, such as a polyglycol. The corresponding half amides of such alkenyl succinic acids are also useful.Useful rust inhibitors are high molecular weight organic acids.

[0120] When present, the rust inhibitor may be used in an amount sufficient to provide from about 0 to about 5 wt. %, from about 0.01 to about 3 wt. %, from about 0.1 to about 2 wt. %, based on the final weight of the lubricating oil composition.

[0121] Generally speaking, suitable lubricants containing detergent metals herein may contain additive components in the ranges listed in the table below.

[0122] [Table 2]

[0123] The percentages of each component above represent the weight percent of each component based on the weight of the final lubricant composition. The remainder of the lubricant composition consists of one or more base oils. The additives used in formulating the compositions described herein can be blended into the base oil individually or in various partial combinations. However, it may be preferred to blend all of the components simultaneously using an additive concentrate (i.e., additives plus a diluent such as a hydrocarbon solvent). Fully formulated lubricants conventionally contain an additive package, referred to herein as a dispersant / inhibitor package or DI package, that provides the characteristics required in the formulation.

[0124] definition For purposes of this disclosure, the chemical elements are identified according to the Periodic Table of the Elements, CAS version, Handbook of Chemistry and Physics, 75th Ed. Additionally, general principles of organic chemistry are described in "Organic Chemistry", Thomas Sorrell, University Science Books, Sausolito: 1999, and "March's Advanced Organic Chemistry", 5th Ed., Ed.: Smith, M. B. and March, J., John Wiley & Sons, New York: 2001, the entire contents of which are incorporated herein by reference.

[0125] As described herein, compounds may be optionally substituted with one or more substituents as illustrated generally above, or as illustrated by the specific classes, subclasses, and species of the present disclosure.

[0126] Unless otherwise clear from the context, the term "major amount" is understood to mean an amount of 50 weight percent or more, for example, about 80 to about 98 weight percent, based on the total weight of the composition. Also, as used herein, the term "minor amount" is understood to mean an amount of less than 50 weight percent, based on the total weight of the composition.

[0127] As used herein, the term "hydrocarbyl group" or "hydrocarbyl" is used in its ordinary sense, well known to those skilled in the art. Specifically, it refers to a group having a carbon atom directly attached to the remainder of the molecule and having predominantly hydrocarbon character. Examples of hydrocarbyl groups include: (1) hydrocarbon substituents, i.e., aliphatic (e.g., alkyl or alkenyl), alicyclic (e.g., cycloalkyl, cycloalkenyl) and aromatic, aliphatic and alicyclic substituted aromatic substituents, as well as cyclic substituents in which the ring is completed through another portion of the molecule (e.g., two substituents taken together form an alicyclic radical); (2) substituted hydrocarbon substituents, i.e., substituents containing non-hydrocarbon groups (e.g., halo (especially chloro and fluoro), hydroxy, alkoxy, mercapto, alkylmercapto, nitro, nitroso, amino, alkylamino and sulfoxy) that do not alter the predominantly hydrocarbon substituent in the context of the present description; (3) hetero substituents, i.e., substituents that, while having predominantly hydrocarbon character in the context of the present description, contain other than carbon in the ring or chain, otherwise composed of carbon atoms. Heteroatoms include sulfur, oxygen and nitrogen, and encompass such substituents as pyridyl, furyl, thienyl and imidazolyl. Generally, no more than 2, or as a further example, only one non-hydrocarbon substituent will be present for every 10 carbon atoms in the hydrocarbyl group, and in some embodiments, there will be no non-hydrocarbon substituents in the hydrocarbyl group.

[0128] As used herein, the term "aliphatic" encompasses the terms alkyl, alkenyl, alkynyl, each of which is optionally substituted as described below.

[0129] As used herein, an "alkyl" group refers to a saturated aliphatic hydrocarbon group containing 1 to 12 (e.g., 1 to 8, 1 to 6, or 1 to 4) carbon atoms. The alkyl group can be linear or branched. Examples of alkyl groups include, but are not limited to, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, n-heptyl, or 2-ethylhexyl. An alkyl group can have one or more substituents, such as halo, phospho, alicyclic [e.g., cycloalkyl or cycloalkenyl], heteroalicyclic [e.g., heterocycloalkyl or heterocycloalkenyl], aryl, heteroaryl, alkoxy, aroyl, heteroaroyl, acyl [e.g., (aliphatic)carbonyl, (alicyclic)carbonyl, or (heteroalicyclic)carbonyl], nitro, cyano, amido [e.g., (cycloalkylalkyl)carbonylamino, arylcarbonylamino, aralkylcarbonylamino, (heterocycloalkyl)carbonylamino, (heterocycloalkylalkyl)carbonylamino, heteroarylcarbonylamino, heteroaralkylcarbonylamino, It can be substituted (i.e., optionally substituted) with alkylaminocarbonyl, cycloalkylaminocarbonyl, heterocycloalkylaminocarbonyl, arylaminocarbonyl, or heteroarylaminocarbonyl], amino, [e.g., aliphatic amino, alicyclic amino, or heteroalicyclic amino], sulfonyl [e.g., aliphatic -SO2-], sulfinyl, sulfanyl, sulfoxy, urea, thiourea, sulfamoyl, sulfamido, oxo, carboxy, carbamoyl, alicyclicoxy, heterocycloaliphaticoxy, aryloxy, heteroaryloxy, aralkyloxy, heteroarylalkoxy, alkoxycarbonyl, alkylcarbonyloxy, or hydroxy.Without being limiting, some examples of substituted alkyl include carboxyalkyl (e.g., HOOC-alkyl, alkoxycarbonylalkyl, and alkylcarbonyloxyalkyl), cyanoalkyl, hydroxyalkyl, alkoxyalkyl, acylalkyl, aralkyl, (alkoxyaryl)alkyl, (sulfonylamino)alkyl (e.g., (alkyl-SO2-amino)alkyl), aminoalkyl, amidoalkyl, (alicyclic)alkyl, or haloalkyl.

[0130] As used herein, an "alkenyl" group refers to an aliphatic carbon group containing 2 to 8 (e.g., 2 to 12, 2 to 6, or 2 to 4) carbon atoms and at least one double bond. Like an alkyl group, an alkenyl group can be linear or branched. Examples of alkenyl groups include, but are not limited to, allyl, isoprenyl, 2-butenyl, and 2-hexenyl. An alkenyl group can have one or more substituents, such as halo, phospho, alicyclic [e.g., cycloalkyl or cycloalkenyl], heteroalicyclic [e.g., heterocycloalkyl or heterocycloalkenyl], aryl, heteroaryl, alkoxy, aroyl, heteroaroyl, acyl [e.g., (aliphatic)carbonyl, (alicyclic)carbonyl, or (heteroalicyclic)carbonyl], nitro, cyano, amido [e.g., (cycloalkylalkyl)carbonylamino, arylcarbonylamino, aralkylcarbonylamino, (heterocycloalkyl)carbonylamino, (heterocycloalkylalkyl)carbonylamino, heteroarylcarbonylamino, heteroaralkylcarbonylamino, heteroaryl ... and the like. The aryloxy group may be optionally substituted with aryl, cycloalkylaminocarbonyl, heterocycloalkylaminocarbonyl, arylaminocarbonyl, or heteroarylaminocarbonyl], amino, [e.g., aliphatic amino, alicyclic amino, heteroalicyclic amino, or aliphatic sulfonylamino], sulfonyl [e.g., alkyl-SO2-, alicyclic-SO2-, or aryl-SO2-], sulfinyl, sulfanyl, sulfoxy, urea, thiourea, sulfamoyl, sulfamido, oxo, carboxy, carbamoyl, alicyclicoxy, heteroalicyclicoxy, aryloxy, heteroaryloxy, aralkyloxy, heteroaralkoxy, alkoxycarbonyl, alkylcarbonyloxy, or hydroxy. Without limitation, some examples of substituted alkenyls include cyanoalkenyl, alkoxyalkenyl, acylalkenyl, hydroxyalkenyl, aralkenyl, (alkoxyaryl)alkenyl, (sulfonylamino)alkenyl (e.g., (alkyl-SO2-amino)alkenyl), aminoalkenyl, amidoalkenyl, (alicyclic)alkenyl, or haloalkenyl.

[0131] As used herein, an "alkynyl" group refers to an aliphatic carbon group containing 2 to 8 (e.g., 2 to 12, 2 to 6, or 2 to 4) carbon atoms and having at least one triple bond. Alkynyl groups can be linear or branched. Examples of alkynyl groups include, but are not limited to, propargyl and butynyl. Alkynyl groups can be substituted with one or more substituents, such as, for example, aroyl, heteroaroyl, alkoxy, cycloalkyloxy, heterocycloalkyloxy, aryloxy, heteroaryloxy, aralkyloxy, nitro, carboxy, cyano, halo, hydroxy, sulfo, mercapto, sulfanyl [e.g., aliphatic sulfanyl or cycloaliphatic sulfanyl], sulfinyl [e.g., aliphatic sulfinyl or cycloaliphatic sulfinyl], sulfonyl [e.g., aliphatic -SO2-, aliphatic amino-SO2-, or cycloaliphatic -SO2-], amido [e.g., aminocarbonyl, alkylaminocarbonyl, alkylcarbonylamino, cycloalkylaminocarbonyl, heterocycloalkylaminocarbonyl, cycloalkylcarbonylamino, aryl, [e.g., (alicyclic)carbonyl or (heteroalicyclic)carbonyl], amino [e.g., aliphatic amino], sulfoxy, oxo, carboxy, carbamoyl, (alicyclic)oxy, (heteroalicyclic)oxy, or (heteroaryl)alkoxy.

[0132] As used herein, an "amino" group refers to an -NR X R Y In the formula, R X and R YEach of is independently hydrogen, alkyl, cycloalkyl, (cycloalkyl)alkyl, aryl, aralkyl, heterocycloalkyl, (heterocycloalkyl)alkyl, heteroaryl, carboxy, sulfanyl, sulfinyl, sulfonyl, (alkyl)carbonyl, (cycloalkyl)carbonyl, ((cycloalkyl)alkyl)carbonyl, arylcarbonyl, (aralkyl)carbonyl, (heterocycloalkyl)carbonyl, ((heterocycloalkyl)alkyl)carbonyl, (heteroaryl)carbonyl, or (heteroaralkyl)carbonyl, each of which is defined herein and optionally substituted. Examples of amino groups include alkylamino, dialkylamino, or arylamino. When the term "amino" is not a terminal group (e.g., alkylcarbonylamino), it is not limited to -NR X - Represented by R X is as defined above.

[0133] As used herein, a "cycloalkyl" group refers to a saturated carbocyclic monocyclic or bicyclic (fused or bridged) ring of 3 to 10 (e.g., 5 to 10) carbon atoms. Examples of cycloalkyl groups include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, adamantyl, norbornyl, cubyl, octahydroindenyl, decahydronaphthyl, bicyclo[3.2.1]octyl, bicyclo[2.2.2]octyl, bicyclo[3.3.1]nonyl, bicyclo[3.3.2.]decyl, bicyclo[2.2.2]octyl, adamantyl, or ((aminocarbonyl)cycloalkyl)cycloalkyl.

[0134] As used herein, a "heterocycloalkyl" group refers to a 3- to 10-membered mono- or bicyclic (fused or bridged) (e.g., 5- to 10-membered mono- or bicyclic) saturated ring structure in which one or more of the ring atoms is a heteroatom (e.g., N, O, S, or combinations thereof). Examples of heterocycloalkyl groups include piperidyl, piperazyl, tetrahydropyranyl, tetrahydrofuryl, 1,4-dioxolanyl, 1,4-dithianyl, 1,3-dioxolanyl, oxazolidyl, isoxazolidyl, morpholinyl, thiomorpholyl, octahydrobenzofuryl, octahydrochromenyl, octahydrothiochromenyl, octahydroindolyl, octahydropyrindinyl, decahydroquinolinyl, octahydrobenzo[b]thiophenyl, 2-oxa-bicyclo[2.2.2]octyl, 1-aza-bicyclo[2.2.2]octyl, 3-aza-bicyclo[3.2.1]octyl, and 2,6-dioxa-tricyclo[3.3.1.0]nonyl. Monocyclic heterocycloalkyl groups can be fused with a phenyl moiety to form structures such as tetrahydroisoquinoline, which would be classified as heteroaryls.

[0135] As used herein, a "heteroaryl" group refers to a monocyclic, bicyclic, or tricyclic ring system having 4-15 ring atoms, where one or more ring atoms are heteroatoms (e.g., N, O, S, or combinations thereof), and the monocyclic ring system is aromatic, or at least one of the rings in the bicyclic or tricyclic ring system is aromatic. Heteroaryl groups include benzo-fused ring systems having 2-3 rings. For example, benzo-fused groups include benzo fused to one or two 4-8 membered heteroalicyclic moieties (e.g., indolyl, indolyl, isoindolyl, 3H-indolyl, indolinyl, benzo[b]furyl, benzo[b]thiophenyl, quinolinyl, or isoquinolinyl). Some examples of heteroaryl are pyridyl, 1H-indazolyl, furyl, pyrrolyl, thienyl, thiazolyl, oxazolyl, imidazolyl, tetrazolyl, benzofuryl, isoquinolinyl, benzthiazolyl, xanthene, thioxanthene, phenothiazine, dihydroindole, benzo[1,3]dioxole, benzo[b]furyl, benzo[b]thiophenyl, indazolyl, benzimidazolyl, benzthiazolyl, puryl, cinnolyl, quinolyl, quinazolyl, cinnolyl, phthalazyl, quinazolyl, quinoxalyl, isoquinolyl, 4H-quinolidyl, benzo-1,2,5-thiadiazolyl, or 1,8-naphthyridyl.

[0136] Monocyclic heteroaryls include, but are not limited to, furyl, thiophenyl, 2H-pyrrolyl, pyrrolyl, oxazolyl, thazolyl, imidazolyl, pyrazolyl, isoxazolyl, isothiazolyl, 1,3,4-thiadiazolyl, 2H-pyranyl, 4-H-pyranyl, pyridyl, pyridazyl, pyrimidyl, pyrazolyl, pyrazyl, or 1,3,5-triazyl. Monocyclic heteroaryls are numbered according to standard chemical nomenclature.

[0137] Bicyclic heteroaryls include indolizyl, indolyl, isoindolyl, 3H-indolyl, indolinyl, benzo[b]furyl, benzo[b]thiophenyl, quinolinyl, isoquinolinyl, indolizinyl, isoindolyl, indolyl, benzo[b]furyl, bexo[b]thiophenyl, indazolyl, benzimidazyl, benzthiazolyl, purinyl, 4H-quinolizyl, quinolyl, isoquinolyl, cinnolyl, phthalazyl, quinazolyl, quinoxalyl, 1,8-naphthyridyl, or pteridyl. Bicyclic heteroaryls are numbered according to standard chemical nomenclature.

[0138] As used herein, the term "treat rate" refers to the weight percentage of a component in a finished lubricant or passenger car motor oil.

[0139] The weight average molecular weight (Mw) and number average molecular weight (Mn) may be determined using a gel permeation chromatography (GPC) instrument from Waters or similar instrumentation and Waters Empower Software or similar software. The GPC instrument may be provided with a Waters separation module and a Waters refractive index detector (or similar optional instrumentation). The GPC operating conditions may include a guard column, four Agilent PLgel columns (length 300×7.5 mm, particle size 5 μ, and pore size range 100-10000 Å), and a column temperature of about 40° C. Unstabilized HPLC grade tetrahydrofuran (THF) may be used as the solvent at a flow rate of 1.0 mL / min. The GPC instrument may be calibrated with commercially available poly(methyl methacrylate) (PMMA) standards with narrow molecular weight distributions ranging from 960 to 1,568,000 g / mol. The calibration curve can be extrapolated for samples with masses less than 500 g / mol. Samples and PMMA standards are dissolved in THF, prepared at concentrations of 0.1-0.5% by weight, and can be used without filtration. GPC measurements are also described in U.S. Pat. No. 5,266,223, which is incorporated herein by reference. The GPC method additionally provides molecular weight distribution information. See, for example, W.W. Yau, J.J. Kirkland and D.D. Ly, "Modern Size Exclusion Liquid Chromatography", John Wiley and Sons, New York, 1979, which is incorporated herein by reference.

[0140] The following definitions are provided to clarify the meaning of certain terms used herein.

[0141] As used herein, the terms "oil composition," "lubricating composition," "lubricating oil composition," "lubricating oil," "lubricant composition," "lubricant composition," "fully formulated lubricant composition," and "lubricant" are considered synonymous and fully interchangeable terms and refer to a finished lubricating product that includes a major amount of a base oil and a minor amount of an additive composition.

[0142] As used herein, the terms "additive package," "additive concentrate," and "additive composition" are considered to be synonymous and fully interchangeable terms that refer to that portion of a lubricating oil composition that excludes a major amount of a base oil stock blend.

[0143] The term "overbased", unless otherwise specified, refers to metal salts such as metal salts of sulfonates, carboxylates, salicylates, and / or phenates in which the amount of metal present exceeds the stoichiometric amount. Such salts may have a conversion level of more than 100% (i.e., such salts may contain more than 100% of the theoretical amount of metal required to convert the acid to its "standard salt", "neutral salt"). The expression "metal ratio", often abbreviated as MR, is used to indicate the ratio of the total chemical equivalents of the metal in an overbased salt to the chemical equivalents of the metal in a neutral salt according to known chemical reactivity and stoichiometry. In standard or neutral salts, the metal ratio (MR) is 1, whereas in overbased salts, the MR is greater than 1. These are commonly referred to as overbased, highly based, or superbased salts and may be salts of organic sulfur acids, carboxylic acids, salicylates, sulfonates, and / or phenols.

[0144] The term "alkaline earth metals" refers to calcium, barium, magnesium, and strontium, and the term "alkali metals" refers to lithium, sodium, potassium, rubidium, and cesium.

[0145] As used herein, unless otherwise specified, the term "hydrocarbyl" or "hydrocarbyl substituent" or "hydrocarbyl group" is used in its ordinary sense, well known to those skilled in the art. Specifically, it refers to a group having a carbon atom directly attached to the remainder of the molecule and having a predominantly hydrocarbon character. Each hydrocarbyl group is independently selected from hydrocarbon substituents, the substituted hydrocarbon substituents containing one or more of halo, hydroxyl, alkoxy, mercapto, nitro, nitroso, amino, pyridyl, furyl, imidazolyl, oxygen, and nitrogen, and not more than two non-hydrocarbon substituents are present for every 10 carbon atoms in the hydrocarbyl group. In some embodiments, hydrocarbyl includes the term "alkyl". The term "alkyl" as used herein, unless otherwise specified, refers to linear, branched, cyclic, and / or substituted saturated chain moieties of about 1 to about 100 carbon atoms. The term "alkenyl" as used herein refers to straight, branched, cyclic, and / or substituted unsaturated chain moieties of about 3 to about 10 carbon atoms. The term "aryl" as used herein refers to monocyclic and polycyclic aromatic compounds that can contain alkyl, alkenyl, alkylaryl, amino, hydroxyl, alkoxy, halo substituents, and / or heteroatoms including, but not limited to, nitrogen, oxygen, and sulfur.

[0146] As used herein, unless otherwise specified, the term "hydrocarbylene substituent" or "hydrocarbylene group" is used in its ordinary sense, as is well known to those skilled in the art. Specifically, it refers to a group that is directly attached to the remainder of the molecule by carbon atoms at two locations in the molecule and has a predominantly hydrocarbon character. Each hydrocarbylene group is independently selected from divalent hydrocarbon substituents, where the substituted divalent hydrocarbon substituents include halo, alkyl, aryl, alkylaryl, arylalkyl, hydroxyl, alkoxy, mercapto, nitro, nitroso, amino, pyridyl, furyl, imidazolyl, oxygen, and nitrogen, and no more than two non-hydrocarbon substituents are present for every 10 carbon atoms in the hydrocarbylene group.

[0147] As used herein, the term "weight percent" means the percentage that the recited component represents relative to the weight of the entire composition, unless expressly stated otherwise.

[0148] The terms "soluble", "oil-soluble" or "dispersible" used herein may, but do not necessarily, indicate that a compound or additive is soluble, dissolvable, miscible, or can be suspended in oil in any proportion. However, the terms mean that they are, for example, soluble, suspendable, soluble, or stably dispersible in oil to a sufficient degree to exert their intended effect in the environment in which the oil is used. Furthermore, if desired, the incorporation of other additives may also allow the incorporation of higher levels of the specific additive.

[0149] As used herein, the term "TBN" is used to indicate the total base number in mg KOH / g, as measured by the method of ASTM D2896. EXAMPLES

[0150] A better understanding of the present disclosure and its many advantages can be made clear with the following examples. The following examples are illustrative and are not intended to limit it in scope or spirit. Those skilled in the art will readily understand that variations of the components, methods, steps, and devices described in these examples can be used. Unless otherwise stated or clear from the context of the following examples and discussion throughout this disclosure, all percentages, ratios, and parts described in this disclosure are by weight. Herein, KV100 was measured according to ASTM D445.

[0151] Example 1 The inventive and comparative lubricants were used to evaluate the performance of a three-way catalyst after approximately 125,000 miles of vehicle operation generally following the drive cycle illustrated in the speed vs. time graph of Figure 1. The inventive and comparative lubricants were used in a 2018 model Chevy Cruz having a L4-1.4L turbo engine. Throughout the evaluation, each inventive or comparative lubricant was changed and replaced with a new inventive or comparative lubricant every 5000 miles during the test.

[0152] The comparative lubricant contained a base oil blend, a DI package, and a viscosity index improver formulated as a passenger car motor oil, including dispersants, borated dispersants, antioxidants, friction modifiers, detergents, antiwear agents, pour point depressants, and antifoam agents.The comparative lubricant had a negligible level of silicon at about 6 ppm.The inventive lubricant was identical to the comparative lubricant, but was top-treated with about 0.27 weight percent hexadecyltrimethoxysilane, which provided the inventive lubricant with about 200 ppm silicon.

[0153] Example 2 The initial BET surface area was measured for the degreened three-way catalyst (approximately 7,000 miles of real-world operation) and compared to the BET surface area of ​​the used catalyst from the inventive vehicle and the comparative vehicle of Example 1 after 125,000 miles of operation using a specific drive cycle and exposure to exhaust gas from a combustion engine lubricated with either the inventive lubricant or the comparative lubricant. The surface area was measured at the Southwest Research Institute. The results are provided in Table 3 below and in Figure 2.

[0154] [Table 3] * The % reduction in surface area is the surface area at the end of the test relative to the initial (or degreened) surface area.

[0155] Example 3 The oxygen storage capacity was measured for the degreened three-way catalyst (approximately 7,000 miles of real-world operation) and compared to the oxygen storage capacity of the catalyst from the inventive vehicle and comparative vehicle of Example 1 using either the inventive lubricant or the comparative lubricant after 125,000 miles of operation. The oxygen storage capacity was measured at the Southwest Research Institute. The results are provided in Table 4 below and in Figure 3.

[0156] [Table 4] * The % reduction in oxygen storage capacity (OSC) is the OSC at the end of the test relative to the initial (or degreened) OSC.

[0157] Example 4 Light-off temperatures were measured for the degreened three-way catalyst (approximately 7,000 miles of real-world operation) and compared to the light-off temperatures of the catalysts from the inventive vehicle and comparative vehicle of Example 1 using either the inventive lubricant or the comparative lubricant after 125,000 miles of operation. Light-off temperatures were measured at the Southwest Research Institute. The results are provided in Table 5 below and in FIG. 4.

[0158] [Table 5] * The % temperature change is the end of test temperature relative to the initial (or degreening) temperature.

[0159] It should be noted that, as used in this specification and the appended claims, the singular forms "a," "an," and "the" include plural referents unless expressly and unambiguously limited to one referent. Thus, for example, reference to an "antioxidant" includes two or more different antioxidants. As used herein, the term "comprising" and grammatical variations thereof are intended to be open-ended such that the recitation of items in a list excludes other similar items that may be substituted for or added to the items in the list.

[0160] For purposes of this specification and the appended claims, unless otherwise indicated, all numbers expressing quantities, percentages or proportions, and other numerical values ​​used in the specification and claims should be understood in all instances to be modified by the term "about". Accordingly, unless indicated to the contrary, the numerical parameters set forth in the following specification and appended claims are approximations that may vary depending on the desired properties sought to be obtained by the present disclosure. At the very least, and not as an attempt to limit the application of the doctrine of equivalents to the scope of the claims, each numerical parameter should at least be construed in light of the number of reported significant digits and by applying ordinary rounding techniques.

[0161] It is understood that each component, compound, substituent, or parameter disclosed herein should be construed as disclosed for use alone or in combination with one or more of any and all other components, compounds, substituents, or parameters disclosed herein.

[0162] It is further to be understood that each range disclosed herein should be construed as a disclosure of each specific value within the disclosed range having the same number of significant digits. Thus, for example, a range of 1 to 4 should be construed as an explicit disclosure of not only the values ​​1, 2, 3, and 4, but any range of such values.

[0163] It is further understood that each lower limit of each range disclosed herein should be interpreted as being disclosed in combination with each upper limit of each range and each specific value within each range disclosed herein for the same component, compound, substituent, or parameter. Thus, the present disclosure should be interpreted as a disclosure of all ranges derived by combining each lower limit of each range with each upper limit of each range or each specific value within each range, or by combining each upper limit of each range with each specific value within each range. That is, it is further understood that any range between the endpoint values ​​within the broad range is also contemplated herein. Thus, a range of 1 to 4 also means a range of 1 to 3, 1 to 2, 2 to 4, 2 to 3, etc.

[0164] Furthermore, a specific amount / value of a component, compound, substituent, or parameter disclosed in the description or examples should be construed as a disclosure of either a lower or upper limit of a range and therefore can be combined with any other lower or upper limit of a range or specific amount / value for the same component, compound, substituent, or parameter disclosed elsewhere in this application to form a range for that component, compound, substituent, or parameter.

[0165] While particular embodiments have been described, alternatives, modifications, variations, improvements, and substantial equivalents may occur that are not presently anticipated or that cannot be currently anticipated by the applicants or others skilled in the art. It is therefore intended that the appended claims as filed, and the appended claims as they may be amended, cover all such alternatives, modifications, variations, improvements, and substantial equivalents.

Claims

1. A method for improving the performance of a three-way catalytic converter for a combustion engine, comprising: lubricating the combustion engine with a lubricating oil composition, burning fuel in the lubricated engine, and generating an exhaust stream containing soot and / or ash particles derived from the combustion, wherein the lubricating oil composition comprises one or more base oils of lubricating viscosity and an additive package comprising at least one oil-soluble silicon-containing compound providing about 50 to about 500 ppm of silicon to the lubricating oil composition; contacting the three-way catalytic converter with the exhaust stream containing the soot and / or the ash particles from the combustion; wherein the performance of the three-way catalytic converter after at least about 120,000 miles of operation is improved as compared to a three-way catalytic converter exposed to an exhaust stream from a combustion engine lubricated with a lubricating oil composition having less than about 10 ppm of silicon.

2. The method of claim 1, wherein the performance of the three-way catalytic converter is improved when measured by at least one of surface area, oxygen storage capacity, or light-off temperature.

3. The surface area of the three-way catalyst converter after operation of at least about 120,000 miles is substantially the same as the initial surface area of the three-way catalyst converter, and / or the oxygen storage capacity of the three-way catalyst converter after operation of at least about 120,000 miles does not decrease by more than 30 percent from the initial oxygen storage capacity of the three-way catalyst converter, and / or the CO T 50 light-off temperature of the three-way catalyst converter after operation of at least about 120,000 miles is the initial CO T 50 light-off temperature of the three-way catalyst converter, and does not increase by more than 5 percent from the initial CO T light-off temperature of the three-way catalyst converter. The method according to claim 2

4. The surface area of the three-way catalyst converter is measured according to Brunauer-Emmett-Teller (BET) analysis, and / or the BET surface area of the three-way catalyst converter is about 20 m 2 g cat -1 or more after operation of at least about 120,000 miles, and / or the decrease of the BET surface area of the three-way catalyst converter after operation of at least about 120,000 miles relative to the initial BET surface area of the three-way catalyst converter is in the range of about 4 to about 10 percent, the method according to claim 3.

5. The method of claim 1, wherein the at least one oil-soluble silicon-containing compound provides about 150 to about 250 ppm of silicon to the lubricating oil composition.

6. The method of claim 1, wherein the oil-soluble silicon-containing compound is an organosilane compound having a C6-C20 hydrocarbyl chain.

7. The method of claim 6, wherein the organosilane compound is a C6-C20 hydrocarbylsilyl ether compound, and / or the silyl ether compound is a tri-alkoxy(hydrocarbyl)silane, and / or the silyl ether compound is a C14-C20 hydrocarbyltrimethoxysilane.

8. The combustion engine is a gasoline engine or a diesel engine, and / or the soot or ash particles have a diameter of about 10 nm or less, and / or the soot or ash particles agglomerate into particles having a diameter of up to 200 micrometers, and / or the exhaust stream has 1×10 12 to 1×10 13 of soot and / or ash as claimed in claim 1.

9. The method of claim 1, wherein the lubricating oil composition has a calculated SASH value of 0.4 to 2.0 weight percent.

Images