Lubricating compositions for diesel particulate filter performance

Abstract

A lubricating oil composition and a method of using the lubricating oil composition to lubricate an engine equipped with a diesel particulate filter. The lubricating oil composition may contain greater than 50 wt. % of a base oil of lubricating viscosity, an amount of one or more calcium-containing detergents to provide less than 1700 ppm of calcium, an amount of one or more magnesium-containing detergents to provide less than 450 ppm of magnesium, an amount of one or more molybdenum-containing compounds to provide less than 450 ppm of molybdenum, from about 700 ppm to about 900 ppm of phosphorus, a total sulfated ash content of 1.0 wt. % or less, and a ratio, in ppm, of calcium from the one or more calcium-containing detergents to magnesium from the one or more magnesium-containing detergents of 1:1 or greater, all as measured by ASTM D874, based on the total weight of the lubricating oil composition.

Description

Technical Field

[0001] The present disclosure relates to a lubricant composition that exhibits reduced clogging in a diesel engine particulate filter.

Summary of the Invention

Problems to be Solved by the Invention

[0002] Passenger cars and small cars can be equipped with either a compression (diesel) engine or a spark ignition (gasoline) internal combustion engine. Generally, engine oils are specially formulated for use with one or the other. However, it may be beneficial to lubricate a spark ignition engine with an engine oil formulated for a compression engine. Further, since some diesel engine oils have been tested to meet the specifications of both diesel engine oils and gasoline engine oils (i.e., mixed specifications), they are recommended for use with either engine type. Therefore, an oil that meets the specifications of both diesel and gasoline engines and can accommodate each of these diverse engine conditions is desirable.

[0003] Vehicles having a compression ignition engine often are equipped with a diesel particulate filter. Such filters can become clogged with particulate matter. This particulate matter is caused by the adverse effects of ash, sulfur, and phosphorus. Reducing the levels of phosphorus and sulfur can be achieved, for example, by reducing the amount of zinc dithiophosphate and using a low sulfur base oil.

[0004] The main sources of ash in lubricating oil compositions are generally metal cleaning agents and zinc dithiophosphate wear-resistant additives used internally. Current methods to reduce clogging in diesel particulate filters involve reducing the presence of cleaning agents. However, reducing the amount of cleaning agents adversely affects the basicity of the lubricating oil composition, which is essential for neutralizing the acidic byproducts of combustion / oxidation. Therefore, it is desirable to reduce the adverse effects of ash on diesel particulate filters without compromising the basicity of the lubricating oil composition by reducing the amount of cleaning agents.

[0005] Boosted spark-ignition internal combustion engines, such as turbocharged or supercharged internal combustion engines, may exhibit abnormal combustion phenomena known as stochastic pre-ignition or low-speed pre-ignition (or "LSPI"). LSPI is a pre-ignition event that may include ultra-high pressure spikes, premature combustion during improper crank angles, and knocking. All of these, individually and in combination, can cause engine degradation and / or significant damage.

[0006] Pre-ignition is a form of combustion that results from the ignition of the air-fuel mixture in the combustion chamber before the desired ignition by the igniter. Because the heat generated by engine operation can heat a portion of the combustion chamber to a temperature sufficient to ignite the air-fuel mixture upon contact, pre-ignition is typically a problem during high-speed engine operation. This type of pre-ignition is sometimes referred to as hot-spot pre-ignition.

[0007] More recently, intermittent abnormal combustion has been observed in boosted internal combustion engines at low speeds and medium to high loads. For example, low-speed pre-ignition (LSPI) may occur randomly and probabilistically during engine operation at loads below 3000 rpm with a mean effective brake pressure (BMEP) of at least 1000 kPa. The compression stroke time is the longest during low-speed engine operation.

[0008] U.S. Patent Application Publication No. 2007 / 0129266A1 relates to a lubricating oil composition comprising a base oil and one or more magnesium detergents for reducing clogging in diesel particulate filters.

[0009] U.S. Patent Publication No. 2003 / 182847A1 relates to a fuel additive and lubricant additive for diesel engines, comprising a molybdenum compound having a measured sulfate ash content of 1.0% by weight or less, a sulfur content of 0.3% by weight or less, and a molybdenum content of 100 ppm or more, and having a diesel particulate filter.

[0010] This disclosure relates to a lubricating oil composition comprising a calcium-containing detergent and a magnesium-containing detergent, and a method for reducing clogging in a diesel particulate filter, comprising the step of operating an engine equipped with a diesel particulate filter and lubricated with the lubricating oil composition comprising the calcium-containing detergent and the magnesium-containing detergent.

[0011] In a first aspect, the present disclosure relates to a lubricating oil composition comprising one or more calcium-containing detergents and one or more magnesium-containing detergents. All lubricating oil compositions of the present disclosure, based on the total weight of the lubricating oil composition, comprise a base oil with a lubricating viscosity greater than 50% by weight as measured by ASTM D874, an amount of one or more calcium-containing detergents to provide less than 1700 ppm of calcium, an amount of one or more magnesium-containing detergents to provide less than 450 ppm of magnesium, an amount of one or more molybdenum-containing compounds to provide less than 450 ppm of molybdenum, about 700 ppm to about 900 ppm of phosphorus, a total measured sulfate ash content of 1.0% by weight or less, and a ratio in ppm of calcium from one or more calcium-containing detergents to magnesium from one or more magnesium-containing detergents of 1:1 or more.

[0012] In the embodiments described above, the lubricating oil composition may provide a diesel particulate filter delta pressure (ΔP) vs. oil consumption result of 0.6 kPa / kg or less, 0.5 kPa / kg or less, or 0.45 kPa / kg or less when measured in the VW PV 1485 test after 144 hours.

[0013] In each of the embodiments described above, the lubricating oil composition may be effective in reducing low-speed pre-ignition events in a boosted internal combustion engine lubricated with the lubricating oil composition compared to some low-speed pre-ignition events in the same engine lubricated with reference lubricant R-1, or the reduction in LSPI events may be 50% or more, where the LSPI events are LSPI counts over 25,000 engine cycles, and the engine operates at 2000 revolutions per minute with an average effective brake pressure of 1,800 kPa.

[0014] In each of the embodiments described above, one or more magnesium-containing cleaning agents may provide magnesium at a concentration of 440 ppm or less, or 430 ppm or less, or 420 ppm or less, or 410 ppm or less, based on the total weight of the lubricating oil composition.

[0015] In each of the embodiments described above, the ratio of total calcium from one or more calcium-containing detergents to total magnesium from one or more magnesium-containing detergents in ppm may be greater than 2.0, greater than 2.5, greater than 3.0, greater than 3.5, less than 10.0, less than 9.0, less than 8.5, or greater than 1.0 to less than 10.0.

[0016] In each of the embodiments described above, one or more calcium-containing detergents may be overbasic, having a total base number greater than 200 mg KOH / g, greater than 225 mg KOH / g, or greater than 250 mg KOH / g, as measured by the method of ASTM D-2896.

[0017] In each of the embodiments described above, one or more calcium-containing detergents may be present in an amount sufficient to provide less than 1670 ppm of calcium, or less than 1500 ppm of calcium, or less than 1400 ppm of calcium, or more than 1350 ppm but less than 1700 ppm of calcium, relative to the total weight of the lubricating oil composition.

[0018] In each of the embodiments described above, the total measured sulfate ash content may be less than 0.8% by weight, greater than 0.6% by weight but less than 1.0% by weight, or greater than 0.6% by weight but less than 0.8% by weight, respectively, as measured by ASTM D874.

[0019] In each of the embodiments described above, the lubricating oil composition may provide an amount of one or more calcium-containing detergents having a total base number of up to 175 mg KOH / g when measured by the method of ASTM D-2896, and, if present, provide less than 50 ppm of calcium, or less than 20 ppm of calcium, or less than 5 ppm of calcium, or about 0 ppm of calcium, relative to the total weight of the lubricating oil composition.

[0020] In each of the embodiments described above, the lubricating oil composition may contain, based on the total weight of the lubricating oil composition, less than 100 ppm of boron, or less than 75 ppm of boron, or less than 50 ppm of boron, or less than 10 ppm of boron, or about 0 ppm of boron.

[0021] In each of the embodiments described above, the lubricating oil composition may have more than 0 ppm of boron and a ratio of more than 7.5, or more than 50, or more than 75 ppm of total metals to total boron in ppm.

[0022] In each of the embodiments described above, the lubricating oil composition may contain boron in a concentration of 0 ppm to less than 100 ppm, or 0 ppm to less than 75 ppm, or 0 ppm to less than 50 ppm, or 0 ppm to less than 10 ppm.

[0023] In each of the foregoing embodiments, one or more magnesium-containing detergents can be overbased and have a total base number of greater than 225 mg KOH / g, or greater than 250 mg KOH / g, or greater than 300 mg KOH / g, or greater than 350 mg KOH / g, or greater than 400 mg KOH / g when measured by the method of ASTM D-2896.

[0024] In each of the foregoing embodiments, one or more calcium-containing detergents can optionally exclude calcium salicylate detergents.

[0025] In each of the foregoing embodiments, one or more magnesium-containing detergents can be overbased magnesium sulfonate having a total base number of greater than 225 mg KOH / g, or greater than 250 mg KOH / g, or greater than 300 mg KOH / g, or greater than 350 mg KOH / g, or greater than 400 mg KOH / g when measured by the method of ASTM D-2896.

[0026] In each of the foregoing embodiments, the lubricating composition can be an engine oil composition.

[0027] In a second aspect, the present disclosure provides a method for reducing clogging in a diesel particulate filter, the method comprising operating an engine lubricated with a lubricating oil composition, the lubricating oil composition comprising a base oil having a lubricating viscosity of greater than 50 wt% based on the total weight of all the lubricating oil composition, and an amount of one or more calcium-containing detergents providing less than 1700 ppm calcium, and an amount of one or more magnesium-containing detergents providing less than 450 ppm magnesium, and an amount of one or more molybdenum-containing compounds providing less than 450 ppm molybdenum, and from about 700 ppm to about 900 ppm phosphorus, and a total measured sulfate ash content of 1.0 wt% or less, and a ratio in ppm of calcium from one or more calcium-containing detergents to magnesium from one or more magnesium-containing detergents of 1:1 or greater.

[0028] In this second embodiment, the lubricating oil composition can provide diesel particulate filter delta pressure (ΔP) vs. oil consumption results of 0.6 kPa / kg or less, 0.5 kPa / kg or less, or 0.45 kPa / kg or less when measured in the VW PV 1485 test after 144 hours.

[0029] In each of the foregoing second embodiments, the lubricating oil composition can be effective to reduce low speed pre-ignition events in a boosted internal combustion engine lubricated with the lubricating oil composition relative to some low speed pre-ignition events in the same engine lubricated with reference lubricating oil R-1, or the reduction of LSPI events can be a reduction of 50% or more, where the LSPI event is the LSPI count during 25,000 engine cycles and the engine operates at 2000 revolutions per minute with an average effective pressure of the brake of 1800 kPa.

[0030] In each of the foregoing second embodiments, the one or more magnesium-containing detergents can provide magnesium at 440 ppm or less, or 430 ppm or less, or 420 ppm or less, or 410 ppm or less based on the total weight of the lubricating oil composition.

[0031] In each of the foregoing second embodiments, the ratio of total calcium from one or more calcium-containing detergents to total magnesium from one or more magnesium-containing detergents in ppm can be greater than 2.0, or greater than 2.5, or greater than 3.0, or greater than 3.5, or less than 10.0, or less than 9.0, or less than 8.5, or greater than 1.0 to less than 10.0.

[0032] In each of the foregoing second embodiments, the one or more calcium-containing detergents can be overbased having a total base number of greater than 200 mg KOH / g, or greater than or equal to 225 mg KOH / g, or greater than 250 mg KOH / g when measured by the method of ASTM D-2896.

[0033] In each of the second embodiments described above, one or more calcium-containing detergents may be present in an amount sufficient to provide less than 1670 ppm of calcium, or less than 1500 ppm of calcium, or less than 1400 ppm of calcium, or more than 1350 ppm but less than 1700 ppm of calcium, relative to the total weight of the lubricating oil composition.

[0034] In each of the second embodiments described above, the total measured sulfate ash content may be less than 0.8% by weight, or greater than 0.6% by weight and less than 1.0% by weight, as measured by ASTM D874.

[0035] In each of the second embodiments described above, the lubricating oil composition may provide an amount of one or more calcium-containing detergents having a total base number of up to 175 mg KOH / g when measured by the method of ASTM D-2896, and, if present, provide less than 50 ppm of calcium, or less than 20 ppm of calcium, or less than 5 ppm of calcium, or about 0 ppm of calcium, relative to the total weight of the lubricating oil composition.

[0036] In each of the second embodiments described above, the lubricating oil composition may contain, based on the total weight of the lubricating oil composition, less than 100 ppm of boron, or less than 75 ppm of boron, or less than 50 ppm of boron, or less than 10 ppm of boron, or about 0 ppm of boron.

[0037] In each of the second embodiments described above, the lubricating oil composition may have more than 0 ppm of boron and a ratio of more than 7.5, or more than 50, or more than 500 ppm of total metal to total boron in ppm.

[0038] In each of the embodiments described above, the lubricating oil composition may contain boron in a concentration of 0 ppm to less than 100 ppm, or 0 ppm to less than 75 ppm, or 0 ppm to less than 50 ppm, or 0 ppm to less than 10 ppm.

[0039] In each of the second embodiments described above, one or more magnesium-containing detergents may be overbasic, having a total base number greater than 225 mg KOH / g, or greater than 250 mg KOH / g, or greater than 300 mg KOH / g, or greater than 350 mg KOH / g, or greater than 400 mg KOH / g, as measured by the method of ASTM D-2896.

[0040] In each of the second embodiments described above, one or more calcium-containing detergents may optionally exclude calcium salicylate detergents.

[0041] In each of the second embodiments described above, one or more magnesium-containing detergents may be overbasic magnesium sulfonate detergents having a total base number greater than 225 mg KOH / g, or greater than 250 mg KOH / g, or greater than 300 mg KOH / g, or greater than 350 mg KOH / g, or greater than 400 mg KOH / g, as measured by the method of ASTM D-2896.

[0042] In each of the second embodiments described above, the lubricating composition may be an engine oil composition.

[0043] To clarify the meaning of specific terms used herein, the following definitions are provided.

[0044] The terms “oil composition,” “lubrication composition,” “lubricating oil composition,” “lubricating oil,” “lubricant composition,” “lubricating composition,” “completely formulated lubricant composition,” “lubricant,” “crankcase oil,” “crankcase lubricant,” “engine oil,” “engine lubricant,” “motor oil,” and “motor lubricant” are considered synonymous, fully interchangeable technical terms referring to the final lubrication product containing a small amount of additive composition in addition to a major amount of base oil.

[0045] As used herein, the terms “additive package,” “additive concentrate,” “additive composition,” “engine oil additive package,” “engine oil additive concentrate,” “crankcase additive package,” “crankcase additive concentrate,” “motor oil additive package,” and “motor oil concentrate” are considered synonymous, fully interchangeable technical terms referring to a portion of a lubricating oil composition excluding the main amount of base oil stock mixture. An additive package may or may not contain viscosity index improvers or pour point depressants.

[0046] The term “overbasic” refers to a metal salt, such as a metal salt of a sulfonate, carboxylate, salicylate, and / or phenate, in which the amount of metal present exceeds the theoretical amount. Such salts can have a conversion rate greater than 100% (i.e., they can contain more than 100% of the theoretical amount of metal required to convert the acid to its “standard,” “neutral” salt). The expression “metallic ratio,” often abbreviated as MR, is used to indicate the ratio of the total stoichiometric equivalents of metal in an overbasic salt to the stoichiometric equivalents of metal in a neutral salt, according to known chemical reactivity and stoichiometry. The metallic ratio is 1 for standard or neutral salts, but for overbasic salts, the MR is greater than 1. These are generally referred to as overbasic, highly basic, or ultrabasic salts and may be salts of organic sulfur acids, carboxylic acids, salicylates, and / or phenols.

[0047] As used herein, the terms “hydrocarbyl substituent” or “hydrocarbyl group” are used in the ordinary sense known to those skilled in the art. Specifically, they refer to groups having carbon atoms directly bonded to the rest of the molecule and having primarily hydrocarbon properties. Each hydrocarbyl group is independently selected from hydrocarbon substituents, the substituted hydrocarbon substituents containing one or more of the following: halo, hydroxyl, alkoxy, mercapto, nitro, nitroso, amino, pyridyl, furyl, imidazolyl, oxygen, and nitrogen, with no more than two non-hydrocarbon substituents for every 10 carbon atoms in the hydrocarbyl group.

[0048] As used herein, the terms “hydrocarbyl substituent” or “hydrocarbyl group” are used in their ordinary sense as is well known to those skilled in the art. Specifically, they refer to groups that are directly bonded to the rest of the molecule by carbon atoms at two locations on the molecule and have primarily hydrocarbon properties. Each hydrocarbylene group is independently selected from divalent hydrocarbon substituents and substituted divalent hydrocarbon substituents including halo groups, alkyl groups, aryl groups, alkylaryl groups, arylalkyl groups, hydroxyl groups, alkoxy groups, mercapto groups, nitro groups, nitroso groups, amino groups, pyridyl groups, furyl groups, imidazolyl groups, and oxygen and nitrogen, with no more than two non-hydrocarbon substituents for every 10 carbon atoms of the hydrocarbylene group.

[0049] As used herein, the term “weight percent” means the percentage of the listed ingredients relative to the total weight of the composition, unless otherwise explicitly stated.

[0050] As used herein, the terms “soluble,” “oil-soluble,” or “dispersible” may indicate, but are not necessarily, that a compound or additive is soluble, soluble, miscible, or suspendable in oil in any proportion. However, the aforementioned terms mean that they are soluble, suspendable, soluble, or stably dispersible in oil to a degree sufficient to exert their intended effect in the environment in which the oil is extracted. Furthermore, higher levels of formulation of a particular additive may be possible by incorporating other additives as needed.

[0051] As used herein, the term "TBN" is used to indicate the total base number in mgKOH / g as measured by the methods of ASTM D2896, ASTM D4739, or DIN 51639-1.

[0052] As used herein, the term "alkyl" refers to a linear, branched, cyclic, and / or substituted saturated chain portion consisting of approximately 1 to approximately 100 carbon atoms.

[0053] As used herein, the term "alkenyl" refers to a linear, branched, cyclic, and / or substituted unsaturated chain portion consisting of approximately 3 to 10 carbon atoms.

[0054] As used herein, the term "aryl" refers to monocyclic and polycyclic aromatic compounds that may contain alkyl, alkenyl, alkylaryl, amino, hydroxyl, alkoxy, halo substituents, and / or heteroatoms including nitrogen, oxygen, and sulfur.

[0055] Diesel particulate filter clogging can be measured using the Volkswagen (VW) Diesel Particulate Filter Test (DFT), VW PV 1485. The VW PV 1485 test measures the amount of sulfate ash deposits that clog the vehicle's diesel particulate filter, which reduces filter life, increases back pressure in the vehicle engine, and leads to increased fuel consumption. The diesel particulate filter test measures the increase in fuel consumption due to back pressure after 144 hours of ash loading.

[0056] The reduction of low-speed pre-ignition events may be expressed as the “LSPI ratio.” The term “LSPI ratio” refers to the ratio of the number of low-speed pre-ignition events in a boosted internal combustion engine lubricated with the lubricating oil composition of this disclosure to a certain number of low-speed pre-ignition events in the same boosted internal combustion engine lubricated with the reference lubricating oil R-1 described herein. A lubricating oil composition that reduces the LSPI ratio is effective in reducing the number of low-speed pre-ignition events in a boosted internal combustion engine lubricated with the lubricating oil composition to the number of low-speed pre-ignition events in the same engine lubricated with the reference lubricating oil R-1.

[0057] The lubricants, combinations of components, or individual components described herein may be suitable for use in various types of internal combustion engines. Suitable engine types may include, but are not limited to, heavy-duty diesel, passenger car, light-duty diesel, medium-speed diesel, or marine engines. Internal combustion engines may be diesel-fueled engines, gasoline-fueled engines, natural gas-fueled engines, biofuel engines, mixed diesel / biofuel-fuel engines, mixed gasoline / biofuel-fuel engines, alcohol-fueled engines, mixed gasoline / alcohol-fuel engines, compressed natural gas (CNG)-fueled engines, or mixtures thereof. Diesel engines may be compression-ignition engines. Gasoline engines may be spark-ignition engines, such as boosted spark-ignition engines. Internal combustion engines may also be used in combination with electric or battery power sources. Engines configured in this way are generally known as hybrid engines. Internal combustion engines may be two-stroke, four-stroke, or rotary engines. Suitable internal combustion engines include marine diesel engines (e.g., inland vessels), aviation piston engines, low-duty diesel engines, and engines for motorcycles, automobiles, locomotives, and trucks.

[0058] Passenger cars and small cars may be equipped with either a compression (diesel) engine or a spark-ignition (gasoline) internal combustion engine. Generally, engine oils are specially formulated for use with either one or the other. However, it can be beneficial to lubricate a spark-ignition engine with engine oil formulated for diesel engines. Furthermore, some diesel engine oils have been tested to meet the specifications of both diesel and gasoline engine oils (i.e., mixed specifications), and are therefore recommended for use with either engine type. Thus, an oil that meets the specifications of both diesel and gasoline engines and can accommodate each of these diverse engine conditions is desirable.

[0059] An internal combustion engine may contain one or more components from aluminum alloys, lead, tin, copper, cast iron, magnesium, ceramics, stainless steel, composites, and / or mixtures thereof. The components may be coated, for example, with diamond-like carbon coatings, lubricating coatings, phosphorus-containing coatings, molybdenum-containing coatings, graphite coatings, nanoparticle-containing coatings, and / or mixtures thereof. The aluminum alloy may contain aluminum silicate, aluminum oxide, or other ceramic materials. In one embodiment, the aluminum alloy is an aluminum silicate surface. As used herein, the term “aluminum alloy” is synonymous with “aluminum composite” and is intended to represent a component or surface containing aluminum and other components mixed or reacted at a microscopic or near-microscopic level, regardless of its detailed structure. This includes not only any conventional alloy having metals other than aluminum, but also composite or alloy-like structures having non-metallic elements or compounds such as ceramic-like materials.

[0060] Lubricating oil compositions for internal combustion engines may be suitable for any engine lubricant, regardless of sulfur, phosphorus, or ash content (ASTM D-874). The sulfur content of the engine oil lubricant may be about 1% by weight or less, or about 0.8% by weight or less, or about 0.5% by weight or less, or about 0.3% by weight or less, or about 0.2% by weight or less. In one embodiment, the sulfur content may be in the range of about 0.001% by weight to about 0.5% by weight, or about 0.01% by weight to about 0.3% by weight. The phosphorus content may be about 700 ppm to about 900 ppm, or 850 ppm or less. The total measured sulfate ash content, when measured according to ASTM D874, may be 0.5% by weight or more to 1.0% by weight or less, or less than 0.8% by weight, or greater than 0.5% by weight to less than 1.0% by weight, or greater than 0.6% by weight to less than 1.0% by weight. In another embodiment, the sulfur content may be about 0.4% by weight or less, the phosphorus content may be about 0.08% by weight or less, and the measured sulfate ash content may be 0.5% by weight or more to about 1% by weight or less. In yet another embodiment, the sulfur content may be about 0.3% by weight or less, the phosphorus content may be about 0.05% by weight or less, and the measured sulfate ash content may be about 0.8% by weight or less.

[0061] In one embodiment, the lubricating oil composition is engine oil, and the lubricating oil composition may have (i) a sulfur content of about 0.5% by weight or less, (ii) a phosphorus content of about 0.1% by weight or less, and (iii) a measured sulfate ash content of 0.5% by weight or more to 1.0% by weight or less.

[0062] In one embodiment, the lubricating oil composition contains less than 10 ppm of boron, or less than 50 ppm of boron, or less than 10 ppm of boron, or 0 ppm of boron, based on the total weight of the lubricating oil composition. In another embodiment, the lubricating oil composition has more than 0 ppm of boron, and the ratio of total metals in ppm to total boron in ppm is greater than 7.5, or greater than 50, or greater than 500.

[0063] In one embodiment, the lubricating oil composition is suitable for two-stroke or four-stroke marine diesel internal combustion engines. In one embodiment, the marine diesel combustion engine is a two-stroke engine. In some embodiments, the lubricating oil composition is not suitable for two-stroke or four-stroke marine diesel internal combustion engines for one or more reasons, including the high sulfur content of the fuel used to power the marine engine and the high TBN required for marine-suitable engine oil (e.g., more than about 40 TBN for marine-suitable engine oil).

[0064] In some embodiments, the lubricating oil composition is suitable for use in engines powered by low-sulfur fuels, such as fuels containing about 1 to about 5% sulfur. Highway vehicle fuel contains about 15 ppm of sulfur (or about 0.0015% sulfur).

[0065] Low-speed diesel typically refers to marine engines, medium-speed diesel generally refers to locomotives, and high-speed diesel typically refers to highway vehicles. The lubricating oil composition may be suitable for one or all of these types.

[0066] Furthermore, the lubricants described herein meet one or more industry specification requirements such as ILSAC GF-3, GF-4, GF-5, GF-5+, GF-6, PC-11, CF, CK-4, FA-4, CF-4, CH-4, CI-4, CJ-4, API SG, SJ, SL, SM, SN, SN+, ACEA A1 / B1, A2 / B2, A3 / B3, A3 / B4, A5 / B5, C1, C2, C3, C4, C5, E4 / E6 / E7 / E9, Euro5 / 6, Jaso DL-1, Low SAPS, Mid SAPS, or Dexos® trademark. 1, Dexos (trademark) 2, MB-Approval229.1, 229.3, 229.5, 229.31, 229.51, 229.52, 229.6 , 229.71, 226.5, 226.51, 228.0 / .1, 228.2 / .3, 228.31, 228.5, 228, 51, 228.61, VW 501.01, 502.00, 503.00 / 503.01, 504.00, 505.00, 505.01, 506.00 / 506.01, 507.00, 508.00, 509.00, 508.88, 509.99, BMW Longlife-01, Longlife-01 FE, Longlife-04, Longlife-12 FE, Longlife-14 FE+, Longlife-17 FE+, Porsche A40, C30, Peugeot Citroen Automobiles B71 2290, B71 2294, B71 2295, B71 2296, B71 2297, B71 2300, B71 2302, B71 2312, B71 2007, B71 2008, Renault RN0700, RN0710, RN0720, Ford WSS-M2C153-H, WSS-M2C930-A, WSS-M2C945-A, WSS-M2C913A, WSS-M2C913-B, WSS-M2C913-C, WSS-M2C913-D, WSS-M2C948-B, WSS-M2C948-A, GM 6094-M, Chrysler MS-6395, Fiat 9.55535 G1, G2, M2, N1, N2, Z2, S1, S2, S3, S4, T2, DS1, DSX, GH2, GS1, GSX, CR1, Jaguar Land Rover STJLR.03.5003, STJLR.03.5004, STJLR.03.It may be suitable for meeting the requirements of original equipment manufacturer specifications such as 5005, STJLR.03.5006, STJLR.03.5007, STJLR.51.5122, or any past or future PCMO or HDD specifications not mentioned herein. In some embodiments for passenger car motor oil (PCMO) applications, the amount of phosphorus in the finished fluid is 1000 ppm or less, or 900 ppm or less, or 800 ppm or less.

[0067] Other hardware may not be suitable for use with the disclosed lubricants. The term “functional fluid” includes, but is not limited to, a variety of fluids including tractor working fluids, power transmission fluids including automatic transmission fluids, continuously variable transmission fluids and manual transmission fluids, working fluids including tractor working fluids, some gear oils, power steering fluids, fluids used in wind turbines and compressors, some industrial fluids, and fluids associated with components of power transmission systems. It should be noted that within each of these fluids, such as automatic transmission fluids, there are various different types of fluids for various transmissions with different designs that require fluids with significantly different functional characteristics. This is in contrast to the term “lubricating fluid,” which is not used for power generation or transmission.

[0068] For example, with regard to hydraulic fluids for tractors, these fluids are general-purpose fluids used for all lubrication applications in the tractor, except for lubricating the engine. These lubrication applications may include lubrication of the gearbox, power take-off and clutch, rear axle, reduction gear, wet brakes, and hydraulic accessories.

[0069] If the functional fluid is an automatic transmission fluid, the automatic transmission fluid must have sufficient friction for the clutch plates to transmit power. However, the coefficient of friction of a fluid tends to decrease due to the effect of temperature as the fluid heats up during operation. It is important for the working fluid or automatic transmission fluid of a tractor to maintain a high coefficient of friction at high temperatures, otherwise the braking system or automatic transmission may fail. This is not the function of engine oil.

[0070] Tractor fluids, such as Super Tractor Universal Oil (STUO) or Universal Tractor Transmission Oil (UTTO), may combine the performance of engine oil with the performance of transmissions, differentials, final drive planetary gears, wet brakes, and hydraulics. Many of the additives used to formulate UTTO or STUO fluids are functionally similar, but can have harmful effects if not added properly. For example, certain anti-wear and extreme-pressure additives used in engine oils are highly corrosive to the copper components of hydraulic pumps. Detergents and dispersants used in gasoline or diesel engine performance can be detrimental to wet brake performance. Friction modifiers specific to quiet wet brake squeal may lack the thermal stability required for engine oil performance. Each of these fluids, regardless of functionality, tractor, or lubrication, is designed to meet specific, stringent manufacturer requirements.

[0071] This disclosure provides novel lubricant blends formulated for use as automotive crankcase lubricants. This disclosure provides novel lubricant blends formulated for use as crankcase lubricants for 2T and / or 4T motorcycles. Embodiments of this disclosure provide lubricants suitable for use in crankcases and having improved properties of air inclusion, alcohol fuel compatibility, oxidation prevention, wear resistance, biofuel compatibility, bubble reduction, friction reduction, fuel efficiency, pre-ignition prevention, rust suppression, sludge and / or soot dispersion, piston cleaning, deposit formation, and water resistance.

[0072] The engine oils of this disclosure may be formulated by adding one or more additives to a suitable base oil formulation, as described in detail below. The additives may be combined with the base oil in the form of an additive package (or concentrate), or selectively combined individually with the base oil (or a mixture of both). The fully formulated engine oils may exhibit improved performance characteristics based on the additives added and their respective proportions.

[0073] Further details and benefits of this disclosure are partially described below and / or may be acquired through the implementation of this disclosure. These details and benefits may be realized and achieved through the elements and combinations specifically indicated in the attached claims. It should be understood that both the general description above and the detailed description below are illustrative and descriptive, and do not limit the claimed disclosure. [Modes for carrying out the invention]

[0074] Various embodiments of this disclosure provide lubricating oil compositions and methods for reducing clogging in diesel particulate filters. The lubricating oil compositions may be useful in compression (diesel) engines and / or spark-ignition (gasoline) engines. In particular, engines in which the lubricating oil compositions may be used may include boosted internal combustion engines, such as turbocharged and supercharged internal combustion engines. Boosted internal combustion engines include spark-ignition engines, direct injection engines, and / or port fuel injection engines. Preferably, the boosted internal combustion engine is a spark-ignition internal combustion engine or a direct injection engine.

[0075] In a first aspect, the present disclosure provides a lubricating oil composition comprising, based on the total weight of the lubricating oil composition, a base oil with a lubricating viscosity of more than 50% by weight as measured by ASTM D874, an amount of one or more calcium-containing detergents to provide less than 1700 ppm of calcium, an amount of one or more magnesium-containing detergents to provide less than 450 ppm of magnesium, an amount of one or more molybdenum-containing compounds to provide less than 450 ppm of molybdenum, about 700 ppm to about 900 ppm of phosphorus, a total measured sulfate ash content of 1.0% by weight or less, and a ratio in ppm of calcium from one or more calcium-containing detergents to magnesium from one or more magnesium-containing detergents of 1:1 or more.

[0076] In a second aspect, the present invention relates to a method for reducing clogging in a diesel particulate filter, comprising the steps of operating an engine equipped with the diesel particulate filter and lubricated with the lubricating oil composition of this specification.

[0077] The aforementioned lubricating oil compositions and methods may provide diesel particulate filter delta pressure (ΔP) vs. oil consumption results of 0.6 kPa / kg or less, 0.5 kPa / kg or less, or 0.45 kPa / kg or less, as measured in the VW PV 1485 test after 144 hours.

[0078] Preferably, the lubricating oil composition and method are also effective for reducing low-speed pre-ignition events in a boosted internal combustion engine lubricated with the lubricating oil composition compared to some low-speed pre-ignition events in the same engine lubricated with reference lubricating oil R-1, or for providing a reduction in LSPI events of 50% or more, where the LSPI events are LSPI counts in 25,000 engine cycles, and the engine operates at 2000 revolutions per minute with a mean effective brake pressure of 1,800 kPa.

[0079] As will be described in more detail below, embodiments of the present disclosure may provide significant and unexpected improvements in reducing clogging in diesel particulate filters, and optionally, significant reductions in low-speed pre-ignition events while maintaining relatively high calcium detergent concentrations in the lubricating oil composition.

[0080] base oil The base oil used in the lubricating oil composition may be selected from any of the base oils in groups I to V, as specified in the American Petroleum Institute (API) Base Oil Interchangeability Guidelines. The five groups of base oils are as follows: [Table 1]

[0081] Groups I, II, and III are mineral oil process raw materials. Group IV base oils contain true synthetic molecular species produced by the polymerization of olefinic 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, but can also be naturally occurring oils such as vegetable oils. Although Group III base oils are derived from mineral oils, it should be noted that the harsh processing these fluids undergo makes their physical properties very similar to some true synthetics such as PAOs. Therefore, oils derived from Group III base oils are sometimes referred to as synthetic fluids in the industry. Group II+ may include high viscosity index Group II.

[0082] The base oils used in the disclosed lubricating oil compositions may be mineral oils, animal oils, vegetable oils, synthetic oils, synthetic oil blends, or mixtures thereof. Suitable oils may be derived from hydrocracking, hydrogenation, hydrofinishing, unrefined, refined, and refined oils, as well as mixtures thereof.

[0083] Unrefined oils are natural oils, mineral oils, or those derived from synthetic sources that have undergone little to no refining. Refined oils are similar to unrefined oils, except that they have been processed in one or more refining steps that may result in improvements to one or more properties. Examples of preferred refining techniques include solvent extraction, secondary distillation, acid or base extraction, filtration, and osmosis. Oils refined to edible quality may or may not be useful. Edible oils may also be called white oils. In some embodiments, lubricating oil compositions do not contain edible oils or white oils.

[0084] Refined oil is also known as recycled oil or reprocessed oil. These oils are similar to refined oil obtained using the same or similar processes. Additionally, these oils are further processed by techniques for removing spent additives and oil degradation products.

[0085] Mineral oils may include oils obtained by drilling, or oils obtained from plants and animals, or any mixture thereof. Examples of such oils include, but are not limited to, castor oil, lard, olive oil, peanut oil, corn oil, soybean oil, and linseed oil, as well as mineral lubricants such as liquid petroleum, paraffinic, naphthenic, or paraffin-naphthenic mixed-type solvent-treated or acid-treated mineral lubricants. If necessary, such oils may be partially or completely hydrogenated. Oils derived from coal or shale may also be useful.

[0086] Useful synthetic lubricants include hydrocarbon oils such as polymerized, oligomerized, or internally polymerized olefins (e.g., polybutylene, polypropylene, propylene isobutylene copolymers); trimers or oligomers of poly(1-hexene), poly(1-octene), 1-decene, e.g., poly(1-decene) (such materials are often referred to as α-olefins), and mixtures thereof; alkylbenzenes (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, as well as their derivatives, analogs, and homologs, or mixtures thereof. Polyalphaolefins are typically hydrogenated substances.

[0087] Other synthetic lubricants include polyol esters, diesters, liquid esters of phosphorus-containing acids (e.g., tricresyl phosphate, trioctyl phosphate, diethyl ester of decanephosphonic acid), or polymeric tetrahydrofurans. Synthetic oils may be produced by the Fischer-Tropsch reaction and are typically hydrogenated isomerized Fischer-Tropsch hydrocarbons or waxes. In one embodiment, the oil can be prepared by the Fischer-Tropsch gas-to-liquid synthesis procedure and other gas-to-liquid oils.

[0088] The main amount of base oil contained in the lubricating composition can be selected from groups I, II, III, IV, V, and combinations of two or more of the above, and the main amount of base oil is other than base oil resulting from the provision of additive components or viscosity index improvers in the composition. In another embodiment, the main amount of base oil contained in the lubricating composition can be selected from groups II, III, IV, V, and combinations of two or more of the above, and the main amount of base oil is other than base oil resulting from the provision of additive components or viscosity index improvers in the composition.

[0089] The amount of lubricating viscosity oil present may be the remainder after subtracting the total amount of performance additives, including viscosity index improvers and / or pour point depressants and / or other surface treatment additives, from 100% by weight. For example, the main amount of lubricating viscosity oil that may be present in the final fluid may be over 50% by weight, over 60% by weight, over 70% by weight, over 80% by weight, over 85% by weight, or over 90% by weight.

[0090] Cleaning agent The lubricating oil composition comprises one or more calcium-containing detergents and, optionally, one or more magnesium-containing detergents. The one or more calcium-containing detergents and the one or more magnesium-containing detergents may be independently selected from neutral, low-basic, or over-basic detergents, and mixtures thereof. Suitable detergent substrates include phenates, sulfur-containing phenates, sulfonic acids, calixalates, salixalates, salicylic acids, carboxylic acids, phosphoric acids, mono- and / or dithiophosphates, alkylphenols, sulfur-linked alkylphenol compounds, or methylene-crosslinked phenols. Suitable detergents and methods for their preparation are described in detail in numerous patent publications, including US7,732,390 and the references cited therein.

[0091] The detergent substrate may be based with an alkali metal or alkaline earth metal, such as calcium, magnesium, potassium, sodium, lithium, barium, or a mixture thereof, but is not limited. In some embodiments, the detergent does not contain barium. Suitable detergents may include alkali or alkaline earth metal salts of petroleum sulfonic acid and long-chain mono or dialkylaryl sulfonic acid, where the aryl group is benzyl, tolyl, or xylyl. Examples of suitable additional detergents include, but are not limited to, calcium phenate, calcium sulfur-containing phenate, calcium sulfonate, calcium calixalate, calcium salixalate, calcium salicylate, calcium carboxylate, calcium phosphate, calcium mono and / or dithiophosphate, calcium alkylphenol, calcium sulfur-linked alkylphenol compounds, calcium methylene crosslinked phenol, magnesium phenate, magnesium sulfur-containing phenate, magnesium sulfonate, magnesium calixalate, magnesium salixalate, magnesium salicylate, magnesium carboxylate, magnesium phosphate, magnesium mono and / or dithiophosphate, magnesium alkylphenol, magnesium sulfur-linked alkylphenol compounds, magnesium methylene crosslinked phenol, sodium phenate, sodium sulfur-containing phenate, sodium sulfonate, sodium calixalate, sodium salixalate, sodium salicylate, sodium carboxylate, sodium phosphate, mono and / or sodium dithiophosphate, sodium alkylphenol, sodium sulfur-linked alkylphenol compounds, or sodium methylene crosslinked phenol.

[0092] Overbasic detergents are known in the art and may be alkaline or alkaline earth metal overbasic 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.

[0093] The term “overbasic” refers to metal salts such as sulfonates, carboxylates, and phenates in which the amount of metal present exceeds the stoichiometric amount. Such salts may have a conversion level greater than 100% (i.e., they may contain more than 100% of the theoretical amount of metal required to convert an acid to its “standard” or “neutral” salt). The expression “metallic ratio,” often abbreviated as MR, is used to indicate the ratio of the total stoichiometric equivalents of metal in an overbasic salt to the stoichiometric equivalents of metal in a neutral salt, according to known chemical reactivity and stoichiometry. The metallic ratio is 1 for standard or neutral salts, but for overbasic salts, the MR is greater than 1. These are generally referred to as overbasic, highly basic, or ultrabasic salts and may be salts of organic sulfur acids, carboxylic acids, or phenols.

[0094] The overbasic cleaning agent in the lubricating oil composition may have a total base number (TBN) of about 200 mg KOH / gram or more, or, as further examples, about 250 mg KOH / gram or more, or about 350 mg KOH / gram or more, or about 375 mg KOH / gram or more, or about 400 mg KOH / gram or more.

[0095] Suitable examples of perbasic detergents include, but are not limited to, perbasic calcium phenates, perbasic calcium sulfur-containing phenates, perbasic calcium sulfonates, perbasic calcium calixalates, perbasic calcium salixalates, perbasic calcium salicylates, perbasic calcium carboxylates, perbasic calcium phosphates, perbasic calcium mono and / or dithiophosphates, perbasic calcium alkylphenols, perbasic calcium sulfur-bonded alkylphenol compounds, perbasic calcium methylene crosslinked phenols, perbasic magnesium phenates, perbasic magnesium sulfur-containing phenates, perbasic magnesium sulfonates, perbasic magnesium calixalates, perbasic magnesium salixalates, perbasic magnesium salicylates, perbasic magnesium carboxylic acids, perbasic magnesium phosphates, perbasic magnesium mono and / or dithiophosphates, perbasic magnesium alkylphenols, perbasic magnesium sulfur-bonded alkylphenol compounds, and perbasic magnesium methylene crosslinked phenols.

[0096] Overbasic calcium detergents may have a total base number of at least about 150 mg KOH / g, at least about 225 mg KOH / g, at least 225 mg KOH / g to about 400 mg KOH / g, at least about 225 mg KOH / g to about 350 mg KOH / g, or about 230 to about 350 mg KOH / g, as measured by the method of ASTM D-2896. When such a detergent composition is formed with an inert diluent, e.g., process oil, usually mineral oil, the total base number reflects the basicity of the entire composition, including the diluent and any other materials that may be contained in the detergent composition (e.g., accelerators).

[0097] The over-basic cleaning agent may have a metal-to-substrate ratio ranging from 1.1:1, 2:1, 4:1, 5:1, 7:1, or 10:1.

[0098] In some embodiments, cleaning agents are effective in reducing or preventing rust inside the engine.

[0099] The total detergent may be present in amounts up to 10% by weight, or about 8% by weight, or up to about 4% by weight, or more than about 4% by weight to about 8% by weight, based on the total weight of the lubricating oil composition.

[0100] One or more calcium-containing detergents may be present in amounts that provide less than 1700 ppm of calcium, or less than 1670 ppm of calcium, or less than 1500 ppm of calcium, or less than 1400 ppm of calcium, or more than 1350 ppm to less than 1700 ppm of calcium, or more than 1350 ppm to less than 1670 ppm of calcium, or more than 1350 ppm to less than 1500 ppm of calcium, or more than 1350 ppm to less than 1400 ppm of calcium, based on the total weight of the lubricating oil composition.

[0101] In some embodiments, one or more calcium-containing detergents are overbasic, having a total base number greater than 200 mg KOH / g, greater than 225 mg KOH / g, or greater than 250 mg KOH / g, as measured by the ASTM D-2896 method.

[0102] In some embodiments, one or more calcium-containing detergents exclude calcium salicylate.

[0103] In another embodiment, the lubricating oil composition may contain one or more calcium-containing detergents having a total base number of up to 175 mg KOH / g as measured by the ASTM D-2896 method, providing less than 50 ppm of calcium, or less than 20 ppm of calcium, or less than 5 ppm of calcium, or about 0 ppm of calcium, relative to the total weight of the lubricating oil composition.

[0104] One or more magnesium-containing detergents may be present in amounts to provide less than 450 ppm of magnesium, or 450 ppm or less of magnesium, or 440 ppm or less of magnesium, or 430 ppm or less of magnesium, or 420 ppm or less of magnesium, or 410 ppm or less of magnesium, or less than 400 ppm of magnesium, or less than 350 ppm of magnesium, or less than 300 ppm of magnesium.

[0105] In some embodiments, one or more magnesium-containing detergents are overbasic, having a total base number greater than 225 mg KOH / g, or greater than 250 mg KOH / g, or greater than 300 mg KOH / g, or greater than 350 mg KOH / g, or greater than 400 mg KOH / g, as measured by the method of ASTM D-2896.

[0106] In other embodiments, one or more magnesium-containing detergents are overbasic magnesium sulfonate detergents having a total base number greater than 225 mg KOH / g, or greater than 250 mg KOH / g, or greater than 300 mg KOH / g, or greater than 350 mg KOH / g, or greater than 400 mg KOH / g, as measured by the ASTM D-2896 method.

[0107] In some embodiments, the ratio of calcium from one or more calcium-containing detergents to magnesium from one or more magnesium-containing detergents in ppm is 1 or greater, or greater than 2.0, or greater than 2.5, or greater than 3.0, or greater than 3.5, or less than 10.0, or less than 9.0, or less than 8.5, or greater than 1.0 to less than 10.0.

[0108] In alternative embodiments, the lubricating oil composition optionally contains 15 ppm or less of magnesium from the detergent, or 10 ppm or less of magnesium.

[0109] Molybdenum-containing ingredients The lubricating oil compositions of this specification include one or more molybdenum-containing compounds. The oil-soluble molybdenum compounds may have the functional properties of abrasion inhibitors, antioxidants, friction modifiers, or mixtures thereof. The oil-soluble molybdenum compounds may include molybdenum dithiocarbamate, molybdenum dialkyldithiophosphate, molybdenum dithiophosphinate, amine salts of molybdenum compounds, molybdenum xanthogenic acid, thioxanthone molybdenum, molybdenum sulfide, molybdenum carboxylic acid, molybdenum alkoxide, trinuclear organic molybdenum compounds, and / or mixtures thereof. Molybdenum sulfide includes molybdenum disulfide. Molybdenum disulfide may be in the form of a stable dispersion. In one embodiment, the oil-soluble molybdenum compound may be selected from the group consisting of molybdenum dithiocarbamate, molybdenum dialkyldithiophosphate, amine salts of molybdenum compounds, and mixtures thereof. In one embodiment, the oil-soluble molybdenum compound may be molybdenum dithiocarbamate.

[0110] Suitable examples of molybdenum compounds that can be used include Molyvan 822®, Molyvan® A, and Molyvan 2000. (商標) This includes commercially available materials, such as those available from RTVanderbilt Co., Ltd. under trade names like Molyvan 855 (trademark), and commercially available materials sold under trade names like Sakura-Lube (trademark) S-165, S-200, S-300, S-310G, S-525, S-600, S-700, and S-710, available from Adeka Corporation, as well as mixtures thereof. Preferred molybdenum components are described in US5,650,381, US RE37,363E1, US RE38,929E1 and US RE40,595E1, which are incorporated herein by reference in their entirety. Preferably, one or more molybdenum-containing compounds may be reaction products of fatty acid esters and molybdenum oxide. Preferably, the fatty acid ester has 4 to 30 carbon atoms or 6 to 20 carbon atoms.

[0111] Additionally, the molybdenum compounds may be acidic molybdenum compounds. These include molybdic acid, ammonium molybdate, sodium molybdate, potassium molybdate, and other alkali metal molybdates and other molybdenum salts, which are sodium hydrogen molybdate, MoOCl4, MoO2Br2, Mo2O3Cl6, molybdenum trioxide, or similar acidic molybdenum compounds. Alternatively, the composition may be provided using, for example, molybdenum in molybdenum / sulfur complexes of basic nitrogen compounds described in U.S. Patents 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, as well as WO94 / 06897, all of which are incorporated herein by reference.

[0112] Another class of preferred organomolybdenum compounds are trinuclear molybdenum compounds and mixtures thereof, such as compounds of the formula Mo3SkLnQz, where S represents sulfur, L represents an independently selected ligand having enough carbon atoms to make the organic group soluble or dispersible in oil, n is 1 to 4, k is 4 to 7, Q is selected from the group of neutral electron-donating compounds such as water, amines, alcohols, phosphines, and ethers, and z is in the range of 0 to 5, including non-stoichiometric values. All ligand organic groups may contain at least 21 carbon atoms in total, such as at least 25, at least 30, or at least 35 carbon atoms. Additional preferred molybdenum compounds are described in U.S. Patent No. 6,723,685, which is incorporated herein by reference in whole.

[0113] The oil-soluble molybdenum compound may be present in an amount sufficient to provide, based on the total weight of the lubricating oil composition, molybdenum in amounts less than approximately 450 ppm, or less than approximately 420 ppm, or less than approximately 400 ppm, or less than approximately 390 ppm, or more than 5 ppm, or more than 50 ppm, or more than 80 ppm, or more than 100 ppm, or more than 5 ppm to less than 450 ppm, or more than 50 ppm to less than 420 ppm, or more than 80 ppm to less than 400 ppm, or more than 100 ppm to less than 390 ppm.

[0114] The lubricating oil composition may also contain one or more optional components selected from the various additives described below.

[0115] Boron-containing compounds The lubricating oil compositions of this specification may optionally contain one or more boron-containing compounds.

[0116] Examples of boron-containing compounds include borate esters, borate fatty amines, borate epoxides, borate detergents, and borate dispersants such as borate succinimide dispersants, as disclosed in U.S. Patent No. 5,883,057.

[0117] If present, boron-containing compounds can be used in sufficient quantities to provide a maximum of 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.

[0118] In some embodiments of the present invention, the lubricating oil composition may contain, based on the total weight of the lubricating oil composition, less than 100 ppm of boron, or less than 75 ppm of boron, or less than 50 ppm of boron, or less than 10 ppm of boron, or about 0 ppm of boron.

[0119] In some embodiments, the lubricating oil composition may have boron greater than 0 ppm and a ratio of total metals in ppm to total boron in ppm of greater than 7.5, or greater than 50, or greater than 500.

[0120] Antioxidant The lubricating oil compositions described herein may also optionally contain one or more antioxidants. Known antioxidant compounds include, for example, phenates, phenate sulfides, sulfurized olefins, phosphosulfur terpenes, sulfurized esters, aromatic amines, alkylated diphenylamines (e.g., nonyldiphenylamine, di-nonyldiphenylamine, octyldiphenylamine, dioctyldiphenylamine), phenyl-alpha-naphthylamines, alkylated phenyl-alpha-naphthylamines, hindered non-aromatic amines, phenols, hindered phenols, oil-soluble molybdenum compounds, polymeric antioxidants, or mixtures thereof. Antioxidant compounds can be used alone or in combination.

[0121] Hindered phenol antioxidants may contain secondary butyl groups and / or tertiary butyl groups as sterically hindering groups. The phenol group may be further substituted with a hydrocarbyl group and / or a crosslinking group bonded 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, 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 about 1 to about 18, or about 2 to about 12, or about 2 to about 8, or about 2 to about 6, or about 4 carbon atoms. Another commercially available hindered phenol antioxidant may be an ester, such as Ethanox available from Albemarle Corporation. (商標) It may include 4716.

[0122] 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, so that each antioxidant may be present in an amount sufficient to provide up to about 5% by weight 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% by weight of diarylamine and about 0.4 to about 2.5% by weight of high molecular weight phenol, based on the final weight of the lubricating oil composition.

[0123] 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 may be Diels-Alder adducts of dienes such as 1,3-butadiene and unsaturated esters such as butyl acrylate.

[0124] Another class of sulfurized olefins includes sulfurized fatty acids and their esters. Fatty acids are often obtained from vegetable or animal oils and typically contain 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, fatty acids are obtained from lard oil, tall oil, peanut oil, soybean oil, cottonseed oil, sunflower seed oil, or mixtures thereof. Fatty acids and / or esters may be mixed with olefins such as α-olefins.

[0125] In another alternative embodiment, the antioxidant composition also includes a molybdenum-containing antioxidant in addition to the phenolic and / or amine antioxidants described above. When a combination of these three antioxidants is used, the preferred ratio of phenol, amine, and molybdenum content is (0-2):(0-2):(0-1).

[0126] One or more antioxidants may be present in the lubricating oil composition in an amount ranging from about 0% to about 20% by weight, or about 0.1% to about 10% by weight, or about 0.6% to about 5% by weight, or about 1.0% to about 3% by weight.

[0127] Abrasion-resistant agent The lubricating oil compositions described herein may also optionally contain one or more anti-wear agents. Examples of suitable anti-wear agents include, but are not limited to, metal thiophosphates, metal dialkyldithiophosphates, phosphate esters or salts thereof, phosphate esters, phosphites, phosphorus-containing carboxylic acid esters, ethers, or amides, sulfurized olefins, thiocarbamate esters, alkylene-linked thiocarbamates, and thiocarbamate-containing compounds including bis(S-alkyldithiocarbamyl) disulfide, as well as mixtures thereof. A suitable anti-wear agent may be molybdenum dithiocarbamate. Phosphorus-containing anti-wear agents are described in detail in European Patent No. 612839. The metal in the dialkyldithiophosphate salt may be alkali metals, alkaline earth metals, aluminum, lead, tin, molybdenum, manganese, nickel, copper, titanium, or zinc. A useful anti-wear agent may be zinc dialkyldithiophosphate.

[0128] Further examples of suitable wear-resistant agents include titanium compounds, tartrates, taltrimids, oil-soluble amine salts of phosphorus compounds, sulfurized olefins, phosphates (e.g., dibutyl phosphite), phosphonates, thiocarbamate-containing compounds, such as thiocarbamate esters, thiocarbamate amides, thiocarbamate ethers, alkylene-bonded thiocarbamates, and bis(S-alkyldithiocarbamyl) disulfide. Tartrates or taltrimids may contain alkyl-ester groups, and the total number of carbon atoms on the alkyl group may be at least 8. In one embodiment, the wear-resistant agent may also contain citrates.

[0129] The anti-wear agent may be present in the range of about 0% to about 15% by weight, or about 0.01% to about 10% by weight, or about 0.05% to about 5% by weight, or about 0.1% to about 3% by weight of the lubricating oil composition.

[0130] Additional optional cleaning agents The lubricating oil composition may contain one or more neutral and / or low-basic detergents, as well as over-basic detergents that do not contain calcium or mixtures thereof. Suitable detergent substrates include phenates, sulfur-containing phenates, sulfonic acids, calixalates, salixalates, salicylic acids, carboxylic acids, phosphoric acids, mono and / or dithiophosphates, alkylphenols, sulfur-linked alkylphenol compounds, or methylene-crosslinked phenols. Suitable detergents and methods for preparing them are described in detail in numerous patent publications, including US7,732,390 and the references cited therein. The detergent substrates may be basicized with alkali metals or alkaline earth metals such as calcium, magnesium, potassium, sodium, lithium, barium, or mixtures thereof, but are not limited. In some embodiments, the detergent does not contain barium. Suitable detergents may include alkali or alkaline earth metal salts of petroleum sulfonic acids, and long-chain mono or dialkylarylsulfonic acids, where the aryl group is benzyl, tolyl, and xylyl.Examples of suitable detergents include, but are not limited to, calcium phenate, calcium sulfur-containing phenate, calcium sulfonate, calcium calixalate, calcium salixalate, calcium salicylate, calcium carboxylate, calcium phosphate, calcium mono and / or dithiophosphate, calcium alkylphenol, calcium sulfur-linked alkylphenol compounds, calcium methylene crosslinked phenol, magnesium phenate, magnesium sulfur-containing phenate, magnesium sulfonate, magnesium calixalate, magnesium salixalate, magnesium salicylate, magnesium carboxylate, magnesium phosphate, magnesium mono and / or dithiophosphate, magnesium alkylphenol, magnesium sulfur-linked alkylphenol compounds, magnesium methylene crosslinked phenol, sodium phenate, sodium sulfur-containing phenate, sodium sulfonate, sodium calixalate, sodium salixalate, sodium salicylate, sodium carboxylate, sodium phosphate, mono and / or sodium dithiophosphate, sodium alkylphenol, sodium sulfur-linked alkylphenol compounds, or sodium methylene crosslinked phenol.

[0131] Overbasic detergent additives are known in the art and may be alkaline or alkaline earth metal overbasic detergent additives. Such detergent additives can 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.

[0132] The term “overbasic” refers to metal salts such as sulfonates, carboxylates, and phenates in which the amount of metal present exceeds the stoichiometric amount. Such salts may have a conversion level greater than 100% (i.e., they may contain more than 100% of the theoretical amount of metal required to convert an acid to its “standard” or “neutral” salt). The expression “metallic ratio,” often abbreviated as MR, is used to indicate the ratio of the total stoichiometric equivalents of metal in an overbasic salt to the stoichiometric equivalents of metal in a neutral salt, according to known chemical reactivity and stoichiometry. The metallic ratio is 1 for standard or neutral salts, but for overbasic salts, the MR is greater than 1. These are generally referred to as overbasic, highly basic, or ultrabasic salts and may be salts of organic sulfur acids, carboxylic acids, or phenols.

[0133] The overbasic detergent in the lubricating oil composition may have a total base number (TBN) of more than approximately 225 mg KOH / gram, or, as further examples, approximately 250 mg KOH / gram or more, or approximately 350 mg KOH / gram or more, or approximately 375 mg KOH / gram or more, or approximately 400 mg KOH / gram or more.

[0134] Suitable examples of overbasic detergents include, but are not limited to, overbasic magnesium phenates, overbasic magnesium sulfur-containing phenates, overbasic magnesium sulfonates, overbasic magnesium calixalates, overbasic magnesium salixalates, overbasic magnesium salicylates, overbasic magnesium carboxylic acids, overbasic magnesium phosphates, overbasic magnesium mono- and / or di-thiophosphates, overbasic magnesium alkylphenols, overbasic magnesium sulfur-bonded alkylphenol compounds, or overbasic magnesium methylene crosslinked phenols.

[0135] The over-basic cleaning agent may have a metal-to-substrate ratio ranging from 1.1:1, 2:1, 4:1, 5:1, 7:1, or 10:1.

[0136] Low basic / neutral detergents have a maximum of 175 mg KOH / g or a maximum of 150 mg KOH / g TBN. Low basic / neutral detergents may include calcium-containing detergents. Low basic neutral calcium-containing detergents may be selected from calcium sulfonate detergents, calcium phenate detergents, and calcium salicylate detergents. In some embodiments, the low basic / neutral detergent is a calcium-containing detergent or a mixture of calcium-containing detergents. In some embodiments, the low basic / neutral detergent is a calcium sulfonate detergent or a calcium phenate detergent.

[0137] The low basic / neutral detergent may contain at least 2.5% by weight of the total detergent in the lubricating oil composition. In some embodiments, at least 4% by weight, or at least 6% by weight, or at least 8% by weight, or at least 10% by weight, or at least 12% by weight, or at least 20% by weight of the total detergent in the lubricating oil composition is the low basic / neutral detergent, which may optionally be a low basic / neutral calcium-containing detergent.

[0138] In certain embodiments, one or more low-basic / neutral detergents provide the lubricating oil composition with about 50 to about 1000 ppm by weight of calcium, based on the total weight of the lubricating oil composition. In some embodiments, one or more low-basic / neutral calcium-containing detergents provide the lubricating oil composition with 75 to less than 800 ppm by weight of calcium, or 100 to 600 ppm by weight, or 125 to 500 ppm by weight of calcium, based on the total weight of the lubricating oil composition.

[0139] In some embodiments, cleaning agents are effective in reducing or preventing rust inside the engine.

[0140] Dispersant This lubricating oil composition may optionally further contain one or more dispersants or mixtures thereof. Dispersants do not contain metals that form ash before being mixed into the lubricating oil composition and do not typically contribute to ash when added to the lubricant, and are therefore often called ashless dispersants. Ashless dispersants are characterized by polar groups bonded to relatively high molecular weight hydrocarbon chains, polymers, or copolymers. Typical ashless dispersants include N-substituted long-chain alkenylsuccinimides. Examples of N-substituted long-chain alkenyl succinimides include polyisobutylene succinimides with a number-average molecular weight of polyisobutylene substituents in the range of approximately 350 to approximately 50,000, or 350 to approximately 5,000, or 350 to approximately 3,000, as measured by gel permeation chromatography (GPC) using polystyrene as the calibration standard, and polyalphaolefin succinimides with a number-average molecular weight of polyalphaolefin substituents in the range of approximately 350 to approximately 10,000, or 350 to approximately 5,000, or 350 to approximately 3,000. Suitable polyalphaolefins include ethylene-alphaolefin copolymers such as ethylene-propylene copolymers.

[0141] Succinimide dispersants and their preparations are disclosed, for example, in U.S. Patent No. 7,897,696 or U.S. Patent No. 4,234,435. Polyolefins can be prepared from polymerizable monomers containing about 2 to about 16 carbon atoms, or about 2 to about 8 carbon atoms, or about 2 to about 6 carbon atoms. Succinimide dispersants are typically imides formed from polyamines, which are typically poly(ethyleneamine).

[0142] Preferred amines are selected from polyamines and hydroxyamines. Examples of polyamines that can be used include, but are not limited to, higher homologues such as diethylenetriamine (DETA), triethylenetetramine (TETA), tetraethylenepentamine (TEPA), and pentaethylaminehexamine (PEHA).

[0143] A suitable heavy polyamine is a polyalkylene-polyamine mixture containing a small amount of lower polyamine oligomers such as TEPA and PEHA (pentaethylenehexamine), but mainly containing six or more nitrogen atoms, two or more primary amines per molecule, and oligomers having a broader branching than conventional polyamine mixtures. A heavy polyamine preferably contains a polyamine oligomer containing seven or more nitrogen atoms per molecule and two or more primary amines per molecule. A heavy polyamine contains more than 28% by weight (e.g., over 32% by weight) of total nitrogen and 120 to 160 grams of primary amine groups per equivalent weight.

[0144] Suitable polyamines are generally known as PAMs and contain a mixture of ethyleneamines, with TEPA and pentaethylenehexamine (PEHA) being the main components of the polyamine, usually less than about 80%.

[0145] Typically, PAMs contain 8.7–8.9 milliequivalents of primary amine per gram (115–112 gram equivalents per primary amine equivalent) and a total nitrogen content of approximately 33–34% by weight. Heavier cuts of PAM oligomers, which are substantially TEPA-free and contain only small amounts of PEHA, but primarily oligomers with six or more nitrogen atoms and broader branching, can produce dispersants with improved dispersibility.

[0146] In one embodiment, the disclosure further comprises at least one polyisobutylene succinimide dispersant having a number-average molecular weight in the range of about 350 to about 50,000, or about 5,000, or about 3,000, as measured by gel permeation chromatography (GPC) using polystyrene as a calibration standard. The polyisobutylene succinimide may be used alone or in combination with other dispersants.

[0147] In some embodiments, polyisobutylene, when included, may have a terminal double bond content of more than 50 mol%, more than 60 mol%, more than 70 mol%, more than 80 mol%, or more than 90 mol%. Such PIBs are also called highly reactive PIBs ("HR-PIBs"). HR-PIBs having a number-average molecular weight in the range of about 800 to about 5000 are suitable for use in embodiments of this disclosure. Conventional PIBs typically have 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%.

[0148] HR-PIBs having a number-average molecular weight in the range of approximately 900 to 3000 may be preferred. Such HR-PIBs are commercially available or can be synthesized by polymerization of isobutene in the presence of a non-chlorinating catalyst such as boron trichloride, as described in U.S. Patent No. 4,152,499 by Boerzel et al. and U.S. Patent No. 5,739,355 by Gateau et al. When used in the aforementioned thermal ene reaction, HR-PIBs may result in a higher conversion rate and less precipitate formation during the reaction due to increased reactivity. A preferred method is described in U.S. Patent No. 7,897,696.

[0149] In one embodiment, the disclosure further comprises at least one dispersant derived from polyisobutylene succinic anhydride ("PIBSA"). PIBSA may have an average succinic acid moiety of about 1.0 to about 2.0 per polymer.

[0150] The activity percentage of alkenyl or alkyl succinic anhydride can be measured using chromatographic techniques. This method is described in columns 5 and 6 of U.S. Patent No. 5,334,321.

[0151] The conversion rate of polyolefins is calculated from the percentage of active substance using the formulas in columns 5 and 6 of U.S. Patent No. 5,334,321.

[0152] Unless otherwise specified, all percentages are weight percentages, and all molecular weights are number-average molecular weights.

[0153] In one embodiment, the dispersant may be derived from polyalphaolefin (PAO) succinic anhydride.

[0154] In one embodiment, the dispersant may be derived from an olefin maleic anhydride copolymer. For example, the dispersant may be described as polyPIBSA.

[0155] In one embodiment, the dispersant may be derived from an anhydrous grafted onto an ethylene-propylene copolymer.

[0156] One suitable class of dispersants may be Mannich bases. Mannich bases are substances formed by the condensation of higher molecular weight alkyl-substituted phenols, polyalkylene polyamines, and aldehydes such as formaldehyde. Mannich bases are described in detail by U.S. Patent No. 3,634,515.

[0157] Suitable classes of dispersants may include high molecular weight esters or semi-ester amides.

[0158] Suitable dispersants can also be post-treated by reacting with any of the various agents by conventional methods. These include boron, urea, thiourea, dimercaptothiadiazole, carbon disulfide, aldehydes, ketones, carboxylic acids, hydrocarbon-substituted succinic anhydride, maleic anhydride, nitriles, epoxides, carbonates, cyclic carbonates, hindered phenol esters, and phosphorus compounds. US7,645,726, US7,214,649, and US8,048,831 are incorporated herein by reference in their entirety.

[0159] In addition to carbonate and boric acid post-treatment, each compound may be post-treated or further post-treated by 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. Patent No. 5,241,003, which is incorporated herein by reference. Such treatments include, Inorganic phosphoric acid or anhydride (e.g., U.S. Patent Nos. 3,403,102 and 4,648,980), Organophosphorus compounds (e.g., U.S. Patent No. 3,502,677), Phosphorus pentasulfide, The boron compounds already mentioned above (e.g., U.S. Patent Nos. 3,178,663 and 4,652,387), Carboxylic acids, polycarboxylic acids, anhydrides, and / or acid halides (e.g., U.S. Patent Nos. 3,708,522 and 4,948,386), Epoxy polyepoxides, or thioepoxides (e.g., U.S. Patent Nos. 3,859,318 and 5,026,495), Aldehydes or ketones (e.g., U.S. Patent No. 3,458,530), Carbon disulfide (e.g., U.S. Patent No. 3,256,185), Glycidol (e.g., U.S. Patent No. 4,617,137), Urea, thiourea, or guanidine (e.g., U.S. Patent Nos. 3,312,619, 3,865,813, and UK Patent No. GB1,065,595), Organic sulfonic acids (e.g., U.S. Patent No. 3,189,544 and British Patent No. GB2,140,811), Alkenyl cyanides (e.g., U.S. Patent Nos. 3,278,550 and 3,366,569), Jiketen (e.g., U.S. Patent No. 3,546,243), Diisocyanates (e.g., U.S. Patent No. 3,573,205), Arkansulton (e.g., U.S. Patent No. 3,749,695), 1,3-Dicarbonyl compounds (e.g., U.S. Patent No. 4,579,675), Alkoxylated alcohols or sulfates of phenols (e.g., U.S. Patent No. 3,954,639), Cyclic lactones (e.g., U.S. Patent 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. Patent Nos. 4,612,132, 4,647,390, 4,648,886, and 4,670,170), Nitrogen-containing carboxylic acids (e.g., U.S. Patent No. 4,971,598 and British Patent No. GB2,140,811), Hydroxyprotected chlorodicarbonyloxy compounds (e.g., U.S. Patent No. 4,614,522), Lactams, thiolactams, thiolactones, or dithiolactones (e.g., U.S. Patent Nos. 4,614,603 and 4,666,460), Cyclic carbonates or thiocarbonates, linear monocarbonates or polycarbonates, or chloroformates (e.g., U.S. Patent Nos. 4,612,132, 4,647,390, 4,646,860, and 4,670,170), Nitrogen-containing carboxylic acids (e.g., U.S. Patent No. 4,971,598 and British Patent No. GB2,440,811), Hydroxyprotected chlorodicarbonyloxy compounds (e.g., U.S. Patent No. 4,614,522), Lactams, thiolactams, thiolactones, or dithiolactones (e.g., U.S. Patent Nos. 4,614,603 and 4,666,460), Cyclic carbamates, cyclic thiocarbamates, or cyclic dithiocarbamates (e.g., U.S. Patent Nos. 4,663,062 and 4,666,459), Hydroxyaliphatic carboxylic acids (e.g., U.S. Patent Nos. 4,482,464, 4,521,318, and 4,713,189), Oxidizing agents (e.g., U.S. Patent No. 4,379,064), A combination of phosphorus pentasulfide and polyalkylene polyamine (e.g., U.S. Patent No. 3,185,647), A combination of a carboxylic acid or aldehyde or ketone and sulfur or sulfur chloride (e.g., U.S. Patent No. 3,390,086, U.S. Patent No. 3,470,098), A combination of hydrazine and carbon disulfide (e.g., U.S. Patent No. 3,519,564), Combinations of aldehydes and phenols (e.g., U.S. Patent Nos. 3,649,229, 5,030,249, and 5,039,307), A combination of aldehydes and dithiophosphate O-diesters (e.g., U.S. Patent No. 3,865,740), A combination of hydroxyaliphatic carboxylic acid and boric acid (e.g., U.S. Patent No. 4,554,086), A combination of hydroxyaliphatic carboxylic acid followed by formaldehyde and phenol (e.g., U.S. Patent No. 4,636,322), A combination of hydroxyaliphatic carboxylic acids and subsequent aliphatic dicarboxylic acids (e.g., U.S. Patent No. 4,663,064), Formaldehyde and phenol, and subsequent glycolic acid combinations (e.g., U.S. Patent No. 4,699,724), A combination of a hydroxyaliphatic carboxylic acid or oxalic acid and a subsequent diisocyanate (e.g., U.S. Patent No. 4,713,191), A combination of an inorganic acid or anhydride of phosphorus or a part thereof or a complete sulfur analog and a boron compound (e.g., U.S. Patent No. 4,857,214), A combination of an organic diacid, followed by an unsaturated fatty acid, followed by a nitroso aromatic amine, optionally followed by a boron compound, and then a glycolating agent (e.g., U.S. Patent No. 4,973,412), Combinations of aldehydes and triazoles (e.g., U.S. Patent No. 4,963,278), Aldehydes and triazoles, followed by combinations of boron compounds (e.g., U.S. Patent No. 4,981,492), This includes treatments involving combinations of cyclic lactones and boron compounds (e.g., U.S. Patents No. 4,963,275 and No. 4,971,711). The aforementioned patents are incorporated herein by reference in their entirety.

[0160] The TBN of a suitable dispersant can be approximately 10 to 65 on an oil-free basis, which corresponds to approximately 5 to 30 TBN when measured with a dispersant sample containing approximately 50% diluted oil.

[0161] If present, the dispersant inhibitor may be used in an amount sufficient to provide up to about 20% by weight of the final weight of the lubricating oil composition. Other amounts of dispersant that may be used may be about 0.1% to about 15% by weight, or about 0.1% to about 10% by weight, or about 3% to about 10% by weight, or about 1% to 6% by weight, or about 7% to about 12% 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.

[0162] Friction modifier The lubricating oil compositions of this specification may also optionally contain one or more friction modifiers. Suitable friction modifiers may include, but are not limited to, imidazolines, amides, amines, succinimides, alkoxylated amines, alkoxylated etheramines, 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 include metal-containing and metal-free friction modifiers.

[0163] Suitable friction modifiers may include hydrocarbyl groups selected from linear, branched, or aromatic hydrocarbyl groups, or mixtures thereof, and may be saturated or unsaturated. The hydrocarbyl group may consist of carbon and a heteroatom such as hydrogen or sulfur or oxygen. The hydrocarbyl group may be in the range of 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 monoester, diester, or (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.

[0164] Other suitable friction modifiers may include organic, ashless (metal-free), and nitrogen-free organic friction modifiers. Such friction modifiers may include esters formed by reacting carboxylic acids and anhydrides with alkanols, and generally contain polar end groups (e.g., carboxyl or hydroxyl) covalently bonded to a lipophilic 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 their entirety in U.S. Patent No. 6,723,685, which is incorporated herein by reference.

[0165] Amine-based friction modifiers may contain amines or polyamines. Such compounds may have a hydrocarbyl group that is linear, saturated, unsaturated, or a mixture thereof, and may contain about 12 to about 25 carbon atoms. Further examples of suitable friction modifiers include alkoxylated amines and alkoxylated etheramines. Such compounds may have a linear hydrocarbyl group that is saturated, unsaturated, or a mixture thereof. These may contain about 12 to about 25 carbon atoms. Examples include ethoxylated amines and ethoxylated etheramines.

[0166] Amines and amides can be used on their own or as adducts or reaction products with boron compounds such as boron oxide, 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 whole.

[0167] The friction modifier may be optionally present in a range such as approximately 0% to approximately 10% by weight, or approximately 0.01% to approximately 8% by weight, or approximately 0.1% to approximately 4% by weight.

[0168] Additional molybdenum-containing ingredients The lubricating oil compositions of this specification may also optionally contain additional molybdenum-containing compounds. Oil-soluble molybdenum compounds may have the functional properties of anti-wear agents, antioxidants, friction modifiers, or mixtures thereof. Oil-soluble molybdenum compounds may include molybdenum dithiocarbamate, molybdenum dialkyldithiophosphate, molybdenum dithiophosphinate, amine salts of molybdenum compounds, molybdenum xanthogenic acid, thioxanthone molybdenum, molybdenum sulfide, molybdenum carboxylic acid, molybdenum alkoxide, trinuclear organic molybdenum compounds, and / or mixtures thereof. Molybdenum sulfide includes molybdenum disulfide. Molybdenum disulfide may be in the form of a stable dispersion. In one embodiment, the oil-soluble molybdenum compound may be selected from the group consisting of molybdenum dithiocarbamate, molybdenum dialkyldithiophosphate, amine salts of molybdenum compounds, and mixtures thereof. In one embodiment, the oil-soluble molybdenum compound may be molybdenum dithiocarbamate.

[0169] Preferred examples of molybdenum compounds that can be used include commercially available materials sold under trade names such as Molyvan 822®, Molyvan® A, Molyvan 2000®, and Molyvan 855® from RTVanderbilt Co., Ltd., as well as commercially available materials sold under trade names such as Sakura-Lube® S-165, S-200, S-300, S-310G, S-525, S-600, S-700, and S-710 from Adeka Corporation, and mixtures thereof. Preferred molybdenum components are described in US5,650,381, US RE37,363 E1, US RE38,929 E1, and US RE40,595 E1, which are incorporated herein by reference in their entirety.

[0170] Additionally, the molybdenum compounds may be acidic molybdenum compounds. These include molybdic acid, ammonium molybdate, sodium molybdate, potassium molybdate, and other alkali metal molybdates and other molybdenum salts, which are sodium hydrogen molybdate, MoOCl4, MoO2Br2, Mo2O3Cl6, molybdenum trioxide, or similar acidic molybdenum compounds. Alternatively, the composition may be provided using, for example, molybdenum in molybdenum / sulfur complexes of basic nitrogen compounds described in U.S. Patents 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, as well as WO94 / 06897, all of which are incorporated herein by reference.

[0171] Another class of preferred organomolybdenum compounds are trinuclear molybdenum compounds and mixtures thereof, such as compounds of the formula Mo3SkLnQz, where S represents sulfur, L represents an independently selected ligand having enough carbon atoms to make the organic group soluble or dispersible in oil, n is 1 to 4, k is 4 to 7, Q is selected from the group of neutral electron-donating compounds such as water, amines, alcohols, phosphines, and ethers, and z is in the range of 0 to 5, including non-stoichiometric values. All ligand organic groups may contain at least 21 carbon atoms in total, such as at least 25, at least 30, or at least 35 carbon atoms. Additional preferred molybdenum compounds are described in U.S. Patent No. 6,723,685, which is incorporated herein by reference in whole.

[0172] The oil-soluble molybdenum compound contains a sufficient amount of molybdenum to provide approximately 0.5 ppm to approximately 2000 ppm, approximately 1 ppm to approximately 700 ppm, approximately 1 ppm to approximately 550 ppm, approximately 5 ppm to approximately 300 ppm, or approximately 20 ppm to approximately 250 ppm of molybdenum.

[0173] Transition metal-containing compounds In another embodiment, the oil-soluble compound may be a transition metal-containing compound or a metalloid. The transition metal may include, but is not limited to, titanium, vanadium, copper, zinc, zirconium, molybdenum, tantalum, tungsten, and the like. Preferred metalloids include, but are not limited to, boron, silicon, antimony, tellurium, and the like.

[0174] In embodiments, the oil-soluble transition metal-containing compound can function as an anti-wear agent, friction modifier, antioxidant, adhesion control additive, or two or more of these functions. In 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 can be used in or for the preparation of oil-soluble substances, the disclosed technology includes various Ti(IV) compounds such as titanium(IV) oxide, titanium(IV) sulfide, and titanium(IV) nitrate; titanium(IV) alkoxides such as titanium methoxide, titanium ethoxide, titanium propoxide, titanium isopropoxide, titanium butoxide, and titanium 2-ethylhexoxide; and other titanium compounds or complexes including titanium phenate, but not limited to these; titanium carboxylates such as titanium(IV) 2-ethyl-1-3-hexanedioate or titanium citrate or titanium oleate; and titanium(IV)(triethanolamine) isopropoxide. Other forms of titanium encompassed in the disclosed technology include titanium phosphates such as titanium dithiophosphate (e.g., dialkyldithiothiophosphate) and titanium sulfonate (e.g., alkylbenzenesulfonic acid), or generally reaction products of titanium compounds that form salts, such as oil-soluble salts, with various acidic substances. Therefore, titanium compounds can be derived, among other things, from organic acids, alcohols, and glycols. Ti compounds can also exist in dimer or oligomeric forms containing a Ti-O-Ti structure. Such titanium materials are commercially available or can be readily prepared by suitable synthetic techniques evident to those skilled in the art. They can exist as solids or liquids at room temperature, depending on the specific compound. They may also be provided in solution form in a suitable inert solvent.

[0175] In one embodiment, titanium can be supplied as a Ti-modified dispersant, such as a succinimide dispersant. Such a material can be prepared by forming a titanium mixed anhydride between a titanium alkoxide and a hydrocarbyl-substituted succinic anhydride, such as alkenyl-(or alkyl-) succinic anhydride. The resulting succinate titanate intermediate may be used directly or reacted with any of many materials, such as (a) a polyamine-based succinimide / amide dispersant having a free condensable -NH functional group, (b) a component of a polyamine-based succinimide / amide dispersant, namely alkenyl-(or alkyl-) succinic anhydride and a polyamine, (c) a hydroxy-containing polyester dispersant prepared by the reaction of substituted succinic anhydride with a polyol, amino alcohol, or polyamine, or a mixture thereof. Alternatively, the succinate titanate intermediate may be reacted with other agents, such as alcohols, amino alcohols, ether alcohols, polyether alcohols or polyols, or fatty acids, and products either used directly to impart Ti to lubricants or further reacted with succinic acid dispersants as described above. As an example, to provide a titanium-modified dispersant or intermediate, 1 part (mol) of tetraisopropyl titanate may be reacted with about 2 parts (mol) of polyisobutene-substituted succinic anhydride at 140-150°C for 5-6 hours. The resulting material (30 g) may be further reacted at 150°C for 1.5 hours with a succinimide dispersant from a mixture of polyisobutene-substituted succinic anhydride and polyethylene polyamine (127 g + diluent oil) to produce a titanium-modified succinimide dispersant.

[0176] Other titanium-containing compounds include titanium alkoxides and C6-C 25 It can be a reaction product of a carboxylic acid. The reaction product is given by the following formula: [ka] (wherein n is an integer selected from 2, 3, and 4, and R is a hydrocarbyl group containing approximately 5 to approximately 24 carbon atoms), or formula: [ka] (wherein m+n=4, n is in the range of 1 to 3, R4 is an alkyl moiety having 1 to 8 carbon atoms, R1 is selected from hydrocarbyl groups containing approximately 6 to 25 carbon atoms, and R2 and R3 are the same or different and selected from hydrocarbyl groups containing 1 to 6 carbon atoms), or formula: [ka] (In the formula, x is in the range of 0 to 3, R1 is selected from hydrocarbyl groups containing approximately 6 to 25 carbon atoms, R2 and R3 are the same or different and selected from hydrocarbyl groups containing approximately 1 to 6 carbon atoms, and R4 is H, C6 to C) 25 It can be represented by (selected from the group consisting of any of the carboxylic acid moieties).

[0177] Suitable carboxylic acids include, but are not limited to, caproic acid, caprylic acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, oleic acid, erucic acid, linoleic acid, linolenic acid, cyclohexanecarboxylic acid, phenylacetic acid, benzoic acid, and neodecanoic acid.

[0178] In one embodiment, the oil-soluble titanium compound may be present in the lubricating oil composition in an amount sufficient to provide about 0 to about 3000 ppm by weight of titanium, or about 25 to about 1500 ppm by weight of titanium, or about 35 ppm to about 500 ppm by weight of titanium, or about 50 ppm to about 300 ppm by weight of titanium.

[0179] Viscosity index improver The lubricating oil compositions described herein may also optionally contain one or more viscosity index improvers. Suitable viscosity index improvers include polyolefins, olefin copolymers, ethylene / propylene copolymers, polyisobutene, styrene-isoprene polymers, styrene / maleate copolymers, styrene-butadiene copolymers, styrene-isoprene polymers, alpha-olefin maleic anhydride copolymers, polymethacrylates, polyacrylates, polyalkylstyrenes, hydrated alkenylaryl conjugated diene copolymers, or mixtures thereof. Viscosity index improvers may also include star polymers, and a suitable example is described in U.S. Publication No. 2012 / 0101017(A1).

[0180] The lubricating oil compositions herein may also optionally contain one or more dispersant viscosity index improvers in addition to, or in place of, the viscosity index improvers. Suitable dispersant viscosity index improvers include ethylene-propylene copolymers functionalized with a reaction product of a functionalized polyolefin, such as an acylating agent (e.g., maleic anhydride) and an amine, amine-functionalized polymethacrylates, or esterified maleic anhydride-styrene copolymers reacted with an amine.

[0181] Viscosity index improver and / or dispersant. The total amount of viscosity index improver may be about 0% to about 20% by weight, about 0.1% to about 15% by weight, about 0.1% to about 12% by weight, or about 0.5% to about 10% by weight of the lubricating oil composition.

[0182] Other optional additives Other additives may be selected to perform one or more functions required of the lubricating fluid. Furthermore, one or more of the above additives may be polyfunctional and may provide additional functions to those described herein, or other functions.

[0183] Lubricant compositions based on this disclosure may optionally include other performance additives. These other performance additives may be additions to the additives specified in this disclosure and / or may include one or more of the following: metal deactivators, viscosity index improvers, detergents, ashless TBN boosters, friction modifiers, anti-wear agents, corrosion inhibitors, rust inhibitors, dispersants, dispersant viscosity index improvers, extreme pressure agents, antioxidants, foam inhibitors, deemulsifiers, emulsifiers, pour point depressants, seal swelling agents, and mixtures thereof. Typically, a complete lubricant composition contains one or more of these performance additives.

[0184] Suitable metal deactivators include foam inhibitors comprising benzotriazole derivatives (typically toltriazole), dimercaptothiadiazole derivatives, 1,2,4-triazole, benzimidazole, 2-alkyldithiobenzimidazole, or 2-alkyldithiobenzothiazole, ethyl acrylate and 2-ethylhexyl acrylate, and optionally vinyl acetate copolymers; demulsifiers comprising trialkyl phosphates, polyethylene glycol, polyethylene oxide, polypropylene oxide, and (ethylene oxide-propylene oxide) polymers; and pour point depressants comprising maleate-styrene anhydride esters, polymethacrylate, polyacrylate, or polyacrylamide.

[0185] Suitable foam inhibitors include silicon-based compounds such as siloxanes.

[0186] Suitable pour point depressants may include polymethyl methacrylate or mixtures thereof. The pour point depressant may be present in an amount sufficient to provide about 0% to about 1% by weight, about 0.01% to about 0.5% by weight, or about 0.02% to about 0.04% by weight, based on the final weight of the lubricating oil composition.

[0187] Suitable rust inhibitors may be single compounds or mixtures of compounds having properties that inhibit corrosion of 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 dimeric and trimeric acids derived from tall oil fatty acids, oleic acid, and linoleic acid. Other suitable corrosion inhibitors include long-chain alpha- and omega-dicarboxylic acids in the molecular weight range of about 600 to about 3000, and alkenyl succinates containing about 10 or more carbon atoms in the alkenyl group, such as tetrapropenyl succinic acid, tetradecenyl succinic acid, and hexadecenyl succinic acid. Other useful types of acidic corrosion inhibitors are semi-esters of alkenyl succinates having about 8 to about 24 carbon atoms in the alkenyl group with alcohols such as polyglycols. The corresponding semiamides of such alkenyl succinic acids are also useful. Useful rust inhibitors are high molecular weight organic acids. In some embodiments, the engine oil does not contain rust inhibitors.

[0188] If present, rust inhibitors may be used in an amount sufficient to provide about 0% to about 5% by weight, about 0.01% to about 3% by weight, and about 0.1% to about 2% by weight, based on the final weight of the lubricating oil composition.

[0189] Generally speaking, a suitable lubricant may contain additive components within the range listed in the table below. [Table 2]

[0190] The percentages for each component listed above represent the weight percentage of each component based on the weight of the final lubricating oil composition. The remainder of the lubricating oil composition consists of one or more base oils.

[0191] The additives used in formulating the compositions described herein may be blended with the base oil individually or in various secondary combinations. However, it may be preferable to mix all the components simultaneously using an additive concentrate (i.e., the additive plus a diluent such as a hydrocarbon solvent). [Examples]

[0192] The following examples illustrate, but do not limit, the methods and compositions of the Disclosure. Without departing from the spirit and scope of the Disclosure, other suitable modifications and adjustments of various conditions and parameters commonly used in the art are known to those skilled in the art. All patents and publications cited herein are incorporated herein in their entirety by reference.

[0193] A series of tests were conducted to determine the effects of calcium and magnesium cleaning agents, and the contribution of ash content to diesel particulate filter clogging and low-speed pre-ignition events.

[0194] Each lubricating oil composition contained a primary amount of base oil and a base conventional dispersant inhibitor (DI) package. The DI package contained conventional amounts of dispersant, anti-wear additive, antioxidant, friction modifier, defoamer, process oil, viscosity index improver, and pour point depressant, as provided in Table 3 below. Specifically, the DI package contained succinimide dispersant, molybdenum-containing compound, antioxidant, and defoamer. The majority of the base oil was a mixture of base oils from Group III and Group IV. Modified components are specified in the table and discussion of the following examples. All values ​​listed are expressed as weight percentages of the components in the lubricating oil composition (i.e., active ingredients plus diluent oil, if any), unless otherwise specified. [Table 3]

[0195] Sulfate ash (SASH) was calculated for the total amount of metal elements contributing to the SASH in the lubricant composition, according to the following factors obtained by multiplying the amount of each metal element in the lubricant composition by the amount of each metal element in the lubricant composition, as described at http: / / konnaris.com / portals / 0 / search / calculations.htm. [Table 4]

[0196] The VW PV 1485 test is a diesel particulate filter test used to measure the clogging tendency of diesel particulate filters. The diesel particulate filter test is performed on a VW 1.9-liter, four-cylinder turbocharged direct-injection diesel engine. One complete test consists of six test cycles. The first five stages are performed to tune the engine, and the final stage implements a 144-hour ash load.

[0197] When the delta pressure (ΔP) to oil consumption (OC) ratio is 0.6 kPa / kg or less, an improvement in reducing clogging in the diesel particulate filter is observed. When ΔP to OC is 0.5 kPa / kg or less, further improvement in clogging is observed, and when ΔP to OC is 0.45 kPa / kg or less, even further improvement in clogging is observed.

[0198] Reference oil R-1 was formulated from approximately 80.7 wt% of Group III base oil, 12.1 wt% of HiTEC® 11150 PCMO additive package available from Afton Chemical Corporation, and 7.2 wt% of 35SSI ethylene / propylene copolymer viscosity index improver. The HiTEC® 11150 passenger car motor oil additive package is an API SN, ILSAC-GF-5, and ACEA A5 / B5 certified DI package. R-1 also exhibited the following properties and partial elemental analysis. [Table 5]

[0199] The following example evaluated the performance of the VW DPF. [Table 6]

[0200] The results shown in Examples 2 and 3 of the present invention demonstrate that, when the sulfate ash content level is kept constant, a lower ratio of total Ca ppm from the detergent to total Mg ppm from the detergent provides a reduction in clogging.

[0201] Furthermore, the results shown in Table 4 indicate that since Examples 2 and 3 of the present invention pass the VW PV 1485 test with a sulfate ash content of 0.8%, the VW PV 1485 test does not limit the formulations to 0.6% sulfate ash.

[0202] Low-speed pre-ignition (LSPI) events were measured in a GM 2.0-liter, 4-cylinder Ecotec turbocharged gasoline direct injection (TGDi) engine. One complete LSPI combustion engine test consisted of four test cycles. Within a single test cycle, two operating stages or segments were repeated to induce an LSPI event. In stage A, when LSPI is most likely to occur, the engine operates at approximately 2000 rpm and a mean effective brake pressure (BMEP) of approximately 1800 kPa. In stage B, when LSPI is unlikely to occur, the engine operates at approximately 1500 rpm and a BMEP of approximately 1700 kPa. For each stage, data was collected over 25,000 engine cycles. The structure of the test cycles was as follows: Stage A - Stage A - Stage B - Stage B - Stage A - Stage A. Each stage was separated by an idle period. Since LSPI is statistically significant during stage A, the LSPI event data considered in this embodiment included only LSPI events that occurred during stage A operation. Therefore, for a single complete LSPI combustion engine test, data typically occurred across 16 stages and were used to evaluate the performance of the comparative oil and the oil of the present invention.

[0203] LSPI events were determined by monitoring the peak cylinder pressure (PP) and the point at which 2% of the combustible material in the combustion chamber burns (MFB02). The peak cylinder pressure threshold was calculated for each cylinder and stage, typically ranging from 6,500 to 8,500 kPa. The MFB02 threshold was calculated for each cylinder and stage, typically ranging from approximately 3.0 to approximately 7.5 after top dead center (ATDC) crank angle (CAD). LSPI was recorded when both the PP and MFB02 thresholds were exceeded in a single engine cycle. LSPI events can be reported in numerous ways. Where different combustion engine tests may be performed with different numbers of engine cycles, the relative number of LSPI events for the comparison oil and the oil of the present invention was reported as the "LSPI ratio" to eliminate ambiguity associated with the number of reported events per engine cycle. In this way, improvements over several standard responses are clearly demonstrated.

[0204] In the following examples, the LSPI ratio is reported as the ratio of the LSPI events of the test oil to the LSPI events of the reference oil "R-1".

[0205] A significant improvement in LSPI is observed when the reduction in LSPI events relative to the reference oil R-1 exceeds 50% (LSPI ratio less than 0.5). Further improvement in LSPI is observed when the reduction in LSPI events exceeds 70% (LSPI ratio less than 0.3), even further improvement in LSPI is observed when the reduction in LSPI events exceeds 75% (LSPI ratio less than 0.25), even further improvement in LSPI is observed when the reduction in LSPI events relative to R-1 exceeds 80% (LSPI ratio less than 0.20), and even further improvement in LSPI is observed when the reduction in LSPI events relative to R-1 exceeds 90% (LSPI ratio less than 0.1). Therefore, the LSPI ratio relative to the R-1 reference oil is considered to be 1.00.

[0206] In the following examples, the LSPI ratio is reported as the ratio of the LSPI events of the test oil to the LSPI events of the reference oil "R-1". [Table 7]

[0207] The aforementioned examples demonstrate that various lubricant formulations of the present invention can provide a significant reduction in LSPI events. Additionally, Example 1 demonstrates that the lubricant of the present invention can pass a diesel particulate clogging test and significantly reduce LSPI events. This may be particularly useful in boost spark ignition combustion engines equipped with diesel particulate filters.

[0208] Other embodiments of this disclosure will become apparent to those skilled in the art from consideration of this specification and the practice of the embodiments disclosed herein. As used throughout the specification and claims, “a” and / or “an” may refer to one or more. Unless otherwise indicated, all figures used herein and in the claims to represent properties such as amounts, molecular weights, percentages, ratios, and reaction conditions of components should be understood in all cases as being modified by the term “about,” whether or not the term “about” is present. Thus, unless otherwise indicated, the numerical parameters described herein and in the claims are approximations that may vary depending on the desired properties to be obtained by this disclosure. At a minimum, each numerical parameter should be interpreted by applying at least the number of significant figures reported and common rounding techniques, not as an attempt to limit the application of the doctrine of equivalents to the claims. Although the numerical ranges and parameters described in the broad disclosure are approximations, the numerical values ​​described in specific examples are reported as accurately as possible. However, any numerical value inherently contains a certain error that inevitably arises from the standard deviation found in their respective test measurements. This specification and the examples provided are illustrative only, and the true scope and spirit of this disclosure are intended to be represented by the following claims.

[0209] The embodiments described above are actually quite subject to variation. Therefore, embodiments are not limited to the specific examples given above. Rather, the embodiments described above fall within the spirit and scope of the appended claims, including their legally available equivalents.

[0210] The patent holder does not intend to make any disclosed embodiment publicly available, and any disclosed modification or variation shall be considered part of these under the doctrine of equivalents to the extent that any such modification or variation cannot be literally part of the claims.

[0211] It should be understood that each component, compound, substituent, or parameter disclosed herein is disclosed for use alone or in combination with any one or more other components, compounds, substituents, or parameters disclosed herein.

[0212] Each quantity / value or range of quantity / value for each component, compound, substituent, or parameter disclosed herein should be interpreted as being disclosed in combination with any other quantity / value or range of quantity / value disclosed herein for any other component, compound, substituent, or parameter disclosed herein, and it should also be understood that any combination of two or more quantities / values ​​or ranges of quantity / value for two or more components, compounds, substituents, or parameters disclosed herein is therefore disclosed in combination with each other for the purposes of this description.

[0213] It should be further understood that each range disclosed herein should be interpreted as a disclosure of each specific value within the disclosure range having the same number of significant figures. Therefore, the range 1–4 should be interpreted as a clear disclosure of the values ​​1, 2, 3, and 4.

[0214] It should be 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. Therefore, this 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 with each specific value within each range, or by combining each upper limit of each range with each specific value within each range.

[0215] Furthermore, any specific amounts / values ​​of components, compounds, substituents, or parameters disclosed in the description or examples should be interpreted as disclosures of either a lower or upper limit of a range, and thus, in combination with any other lower or upper limit of ranges or specific amounts / values ​​for the same component, compound, substituent, or parameter disclosed elsewhere in this application, can form a range for that component, compound, substituent, or parameter.

Claims

1. 1. A lubricating oil composition comprising: a) greater than 50 wt. %, based on the total weight of the lubricating oil composition, of a base oil of lubricating viscosity; b) a cleaning agent comprising the following components i) and ii): i) one or more overbased calcium-containing detergents having a total base number of at least 150 mg KOH / g and excluding calcium salicylate detergents; ii) one or more overbased magnesium-containing detergents having a total base number greater than 225 mg KOH / g; c) one or more molybdenum-containing compounds; d) 700 ppm to 900 ppm phosphorus, based on the total weight of the lubricating oil composition; e) a total measured sulfated ash content of 0.8 wt. % or less, based on the total weight of the lubricating oil composition, as measured by ASTM D874; a) the concentration of calcium in the lubricating oil composition is greater than 1350 ppm and less than 1700 ppm based on the total weight of the lubricating oil composition; b) the concentration of magnesium in the lubricating oil composition is 15 ppm or less based on the total weight of the lubricating oil composition; C) the concentration of molybdenum in the lubricating oil composition is greater than 100 ppm and less than 450 ppm based on the total weight of the lubricating oil composition; D) the concentration of boron in the lubricating oil composition is from 0 ppm to less than 10 ppm based on the total weight of the lubricating oil composition; e) the ratio of calcium to magnesium in the lubricating oil composition is 3.5 or greater in ppm; and A lubricating oil composition, wherein the lubricating oil composition provides a diesel particulate filter delta pressure (ΔP) versus oil consumption result of less than 0.43 kPa / kg after 144 hours, as measured in a VW PV 1485 test.

2. 2. The lubricating oil composition of claim 1, wherein the one or more overbased calcium-containing detergents have a total base number of greater than 225 mg KOH / g as measured by the method of ASTM D-2896.

3. The lubricating oil composition of any one of claims 1 to 2, wherein the one or more overbased calcium-containing detergents have a total base number of greater than 250 mg KOH / g as measured by the method of ASTM D-2896.

4. The lubricating oil composition according to claim 1, wherein the concentration of calcium in the lubricating oil composition is less than 1670 ppm, based on the total weight of the lubricating oil composition.

5. The lubricating oil composition according to claim 1, wherein the concentration of calcium in the lubricating oil composition is less than 1500 ppm based on the total weight of the lubricating oil composition.

6. The lubricating oil composition of claim 1, wherein the total sulfated ash content in the lubricating oil composition is greater than 0.6 wt. % as measured by ASTM D874.

7. The lubricating oil composition of claim 1, wherein the one or more overbased magnesium-containing detergents have a total base number of greater than 225 mg KOH / g as measured by the method of ASTM D-2896.

8. The lubricating oil composition of claim 1, wherein the one or more overbased magnesium-containing detergents have a total base number of greater than 300 mg KOH / g as measured by the method of ASTM D-2896.

9. The lubricating oil composition of claim 1, wherein the one or more overbased magnesium-containing detergents have a total base number of greater than 350 mg KOH / g as measured by the method of ASTM D-2896.

10. The lubricating oil composition of claim 1, wherein the concentration of boron in the lubricating oil composition is 0 ppm, based on the total weight of the lubricating oil composition.

11. 10. The lubricating oil composition of any one of claims 1 to 9, wherein the lubricating oil composition has greater than 0 ppm boron and the ratio of total metals in ppm in the lubricating oil composition to total boron in ppm in the lubricating oil composition is greater than 7.

5.

12. The lubricating oil composition of any one of claims 1 to 11, wherein the one or more overbased magnesium-containing detergents have a total base number of greater than 400 mg KOH / g as measured by the method of ASTM D-2896.

13. The lubricating oil composition according to any one of claims 1 to 12, wherein the lubricating oil composition is an engine oil composition.

14. operating an engine equipped with a diesel particulate filter and lubricated with the lubricating oil composition of any one of claims 1 to 13; 1. A method for reducing plugging in a diesel particulate filter, wherein the lubricating oil composition comprises a total measured sulfated ash content of 0.5 wt.% or greater, as measured by ASTM D874, based on the total weight of the lubricating oil composition.