Lubricating composition for the performance of a diesel particulate filter

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 a reduction in clogging in a diesel engine particulate filter.

Summary of the Invention

Problems to be Solved by the Invention

[0002] Passenger cars and small vehicles 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 either one. However, it may be beneficial to lubricate a spark ignition engine with an engine oil formulated for a compression engine. Furthermore, some diesel engine oils are tested to meet the specifications of both diesel engine oils and gasoline engine oils (i.e., mixed specifications), and are thus 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 with compression ignition engines are often equipped with diesel particulate filters. 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 lubricant compositions are generally the metal detergents and zinc dialkyl dithiophosphate antiwear additives used internally. To reduce clogging in diesel particulate filters, current methods relate to reducing the presence of detergents. However, reducing the amount of detergent has an adverse effect on the basicity of the lubricant composition, which is essential for neutralizing combustion / oxidation acidic by-products. Therefore, it is desirable to reduce the adverse effect of ash on diesel particulate filters without impairing the basicity of the lubricant composition by reducing the amount of detergent.

[0005] Boosted spark-ignition internal combustion engines, such as those with a turbocharger or supercharger, can exhibit abnormal combustion phenomena known as stochastic preignition or low-speed preignition (or "LSPI"). LSPI is a preignition event that can include ultra-high pressure spikes, early combustion between inappropriate crank angles, and knocking. All of these, individually and in combination, have the potential to cause engine degradation and / or significant damage.

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

[0007] More recently, intermittent abnormal combustion has been observed in boosted internal combustion engines at low and medium to high loads. For example, low-speed preignition (LSPI) may occur in a random and probabilistic manner during engine operation at speeds below 3000 rpm under load with a brake mean effective pressure (BMEP) of at least 1,000 kPa. During low-speed engine operation, the compression stroke time is the longest.

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

[0009] U.S. Patent Application Publication No. 2003 / 182847A1 relates to a fuel additive and a lubricating oil additive for a diesel engine, which has a diesel particulate filter and contains a molybdenum compound having a measured sulfate ash content of 1.0 wt% or less, a sulfur content of 0.3 wt% or less, and a molybdenum content of 100 ppm or more.

[0010] The present disclosure relates to a method for reducing clogging in a diesel particulate filter, which includes a lubricating oil composition containing a calcium-containing detergent and a magnesium-containing detergent, and a step of operating an engine equipped with a diesel particulate filter and lubricated with a lubricating oil composition containing a calcium-containing detergent and a 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. The lubricating oil composition of the present disclosure includes, based on the total weight of all the lubricating oil compositions, a base oil having a lubricating viscosity of more than 50 wt% when measured by ASTM D874, an amount of one or more calcium-containing detergents for providing less than 1700 ppm of calcium, an amount of one or more magnesium-containing detergents for providing less than 450 ppm of magnesium, an amount of one or more molybdenum-containing compounds for providing less than 450 ppm of molybdenum, about 700 ppm to about 900 ppm of phosphorus, a total measured sulfate ash content of 1.0 wt% or less, and a ratio of calcium from one or more calcium-containing detergents to magnesium from one or more magnesium-containing detergents in ppm of 1:1 or more.

[0012] In the foregoing embodiments, the lubricating oil composition 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 when measured in the VW PV 1485 test after 144 hours.

[0013] In each of the foregoing embodiments, the lubricating oil composition may 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 lubricant R-1, or the reduction of LSPI events may 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 a mean effective pressure of the brake of 1,800 kPa.

[0014] In each of the foregoing embodiments, the one or more magnesium-containing detergents may 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.

[0015] In each of the foregoing 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 may 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.

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

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

[0018] In each of the foregoing embodiments, the total measured sulfate ash content may be less than 0.8 wt%, or more than 0.6 wt% to less than 1.0 wt%, or more than 0.6 wt% to less than 0.8 wt%, when measured by ASTM D874, respectively.

[0019] In each of the foregoing embodiments, 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 when present, provides less than 50 ppm calcium, or less than 20 ppm calcium, or less than 5 ppm calcium, or about 0 ppm calcium, based on the total weight of the lubricating oil composition.

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

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

[0022] In each of the foregoing embodiments, the lubricating oil composition may contain from 0 ppm to less than 100 ppm boron, or from 0 ppm to less than 75 ppm boron, or from 0 ppm to less than 50 ppm boron, or from 0 ppm to less than 10 ppm boron.

[0023] In each of the foregoing embodiments, one or more magnesium-containing detergents can be overbased 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 as measured by the method of ASTM D-2896.

[0024] In each of the foregoing embodiments, one or more calcium-containing detergents may 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 as 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, comprising equipping a diesel particulate filter and operating an engine lubricated with a lubricating oil composition comprising, based on the total weight of all lubricating oil compositions, a base oil having a lubricating viscosity of greater than 50 wt% as measured by ASTM D874, an amount of one or more calcium-containing detergents providing less than 1700 ppm calcium, an amount of one or more magnesium-containing detergents providing less than 450 ppm magnesium, an amount of one or more molybdenum-containing compounds providing less than 450 ppm molybdenum, about 700 ppm to about 900 ppm phosphorus, 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 lubricant R-1, or the reduction in 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 foregoing second embodiments, one or more calcium-containing detergents may be present in an amount sufficient to provide less than 1670 ppm calcium, or less than 1500 ppm calcium, or less than 1400 ppm calcium, or more than 1350 ppm and less than 1700 ppm calcium, based on the total weight of the lubricating oil composition.

[0034] In each of the foregoing second embodiments, the total measured sulfate ash content may be less than 0.8 wt%, or more than 0.6 wt% and less than 1.0 wt%, when measured by ASTM D874, respectively.

[0035] In each of the foregoing second embodiments, 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 when present, provides less than 50 ppm calcium, or less than 20 ppm calcium, or less than 5 ppm calcium, or about 0 ppm calcium, based on the total weight of the lubricating oil composition.

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

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

[0038] In each of the foregoing embodiments, the lubricating oil composition may contain from 0 ppm to less than 100 ppm boron, or from 0 ppm to less than 75 ppm boron, or from 0 ppm to less than 50 ppm boron, or from 0 ppm to less than 10 ppm boron.

[0039] In each of the foregoing second 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 as measured by the method of ASTM D-2896.

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

[0041] In each of the foregoing second embodiments, one or more magnesium-containing detergents can be overbased magnesium sulfonate detergents 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 as measured by the method of ASTM D-2896.

[0042] In each of the foregoing second embodiments, the lubricating composition can be an engine oil composition.

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

[0044] The terms "oil composition", "lubrication composition", "lubricating oil composition", "lubricating oil", "lubricant composition", "lubricating composition", "fully formulated lubricant composition", "lubricant", "crankcase oil", "crankcase lubricant", "engine oil", "engine lubricant", "motor oil", and "motor lubricant" are considered to be synonymous and fully interchangeable technical terms that refer to a final lubricating product that includes a minor amount of an 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", "motor oil concentrate" are considered to be synonymous and fully interchangeable terms that refer to a portion of a lubricating oil composition excluding a major amount of base oil stock mixture. An additive package may or may not contain a viscosity index improver or pour point depressant.

[0046] The term "overbased" relates to metal salts, such as sulfonates, carboxylates, salicylates, and / or phenates, where the amount of metal present exceeds the stoichiometric amount. Such salts can have a conversion rate greater than 100% (i.e., they can contain more than 100% of the stoichiometric amount of metal required to convert the acid to its "standard", "neutral" salt). The expression "metal ratio", often abbreviated as MR, is used to indicate the ratio of the total chemical equivalents of metal in an overbased salt to the chemical equivalents of metal in a neutral salt, according to known chemical reactivity and stoichiometry. The metal ratio is 1 for a standard or neutral salt, but MR is greater than 1 for an overbased salt. These are generally referred to as overbased, hyperbasic, or superbasic salts and may be salts of organic sulfuric acids, carboxylic acids, salicylates, and / or phenols.

[0047] As used herein, the term "hydrocarbyl substituent" or "hydrocarbyl group" is used in its ordinary meaning known to those skilled in the art. Specifically, it refers to a group having a carbon atom directly bonded to the remainder of the molecule and having predominantly hydrocarbon character. Each hydrocarbyl group is independently selected from hydrocarbon substituents, and a substituted hydrocarbon substituent contains one or more of a halo group, a hydroxyl group, an alkoxy group, a mercapto group, a nitro group, a nitroso group, an amino group, a pyridyl group, a furyl group, an imidazolyl group, oxygen, and nitrogen, with no more than two non-hydrocarbon substituents per ten carbon atoms in the hydrocarbyl group.

[0048] As used herein, the term "hydrocarbyl substituent" or "hydrocarbyl group" is used in its ordinary meaning well known to those skilled in the art. Specifically, it refers to a group that is directly bonded to the remainder of the molecule by carbon atoms at two locations in the molecule and has mainly hydrocarbon properties. Each hydrocarbylene group is independently selected from a divalent hydrocarbon substituent, and a halo group, an alkyl group, an aryl group, an alkylaryl group, an arylalkyl group, a hydroxyl group, an alkoxy group, a mercapto group, a nitro group, a nitroso group, an amino group, a pyridyl group, a furyl group, an imidazolyl group, and a substituted divalent hydrocarbon substituent containing oxygen and nitrogen, and there are two or less non-hydrocarbon substituents per 10 carbon atoms of the hydrocarbylene group.

[0049] As used herein, the term "weight percent" means the percentage that the stated component represents relative to the total weight of the composition, unless otherwise expressly stated.

[0050] As used herein, the terms "soluble", "oil-soluble", or "dispersible" may indicate that a compound or additive is soluble, soluble, miscible, or suspendable in oil in any proportion, but not necessarily so. However, the foregoing terms mean that they are soluble, suspendable, soluble, or stably dispersible in oil to such an extent that they exhibit the intended effects in the environment in which the oil is produced. Further, if necessary, higher levels of formulation of a particular additive may be made possible by incorporating other additives additionally.

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

[0052] The term "alkyl" as employed herein refers to a straight-chain, branched-chain, cyclic, and / or substituted saturated chain moiety of from about 1 to about 100 carbon atoms.

[0053] As used herein, the term "alkenyl" refers to a straight-chain, branched-chain, cyclic, and / or substituted unsaturated chain moiety of from about 3 to about 10 carbon atoms.

[0054] As used herein, the term "aryl" refers to monocyclic and polycyclic aromatic compounds which may contain alkyl, alkenyl, alkylaryl, amino, hydroxyl, alkoxy, halo substituents, and / or heteroatoms including, but not limited to, nitrogen, oxygen, and sulfur.

[0055] Plugging of the diesel particulate filter can be measured in the Volkswagen (VW) Diesel Particulate Filter Test (DFT), VW PV 1485. The VW PV 1485 test measures the amount of sulfate ash deposits plugged in the diesel particulate filter of a vehicle, which reduces the life of the filter, increases the backpressure of the vehicle engine, and results in an increase in fuel consumption. The diesel particulate filter test measures the increase in backpressure versus fuel consumption 144 hours after the ash loading stage.

[0056] Reduction of low-speed pre-ignition events can be expressed as an "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 the present disclosure to the number of some 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 for reducing the low-speed pre-ignition events in a boosted internal combustion engine lubricated with the lubricating oil composition relative 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 ingredients, or individual ingredients of this specification 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 vehicle, light-duty diesel, medium-speed diesel, or marine engines. The internal combustion engine may be a diesel fuel engine, gasoline fuel engine, natural gas fuel engine, biofuel engine, mixed diesel / biofuel - fuel engine, mixed gasoline / biofuel - fuel engine, alcohol fuel engine, mixed gasoline / alcohol fuel engine, compressed natural gas (CNG) fuel engine, or a mixture thereof. The diesel engine may be a compression ignition engine. The gasoline engine may be a spark ignition engine, such as a boosted spark ignition engine. The internal combustion engine may also be used in combination with an electric or battery power source. An engine configured in this way is generally known as a hybrid engine. The internal combustion engine may be a two-stroke, four-stroke, or rotary engine. Suitable internal combustion engines include marine diesel engines (e.g., inland vessels), aircraft piston engines, low-load diesel engines, and motorcycles, automobiles, locomotives, and truck engines.

[0058] Passenger cars and small vehicles 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 one or the other. However, it may be beneficial to lubricate a spark ignition engine with an engine oil formulated for diesel engines. Furthermore, 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.

[0059] The internal combustion engine may contain one or more components of aluminum alloy, lead, tin, copper, cast iron, magnesium, ceramic, stainless steel, composite material, and / or mixtures thereof. The components may be coated, for example, with diamond-like carbon coating, lubricating coating, phosphorus-containing coating, molybdenum-containing coating, graphite coating, nanoparticle-containing coating, and / or mixtures thereof. The aluminum alloy may include aluminum silicate, aluminum oxide, or other ceramic material. 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 that contains aluminum and other components that are mixed or reacted at the microscopic level or near the microscopic level, regardless of its detailed structure. This includes not only any conventional alloy having a metal other than aluminum, but also composite or alloy-like structures having non-metallic elements or compounds such as ceramic-like materials.

[0060] The lubricating oil composition for an internal combustion engine can 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 wt% or less, or about 0.8 wt% or less, or about 0.5 wt% or less, or about 0.3 wt% or less, or about 0.2 wt% or less. In one embodiment, the sulfur content may range from about 0.001 wt% to about 0.5 wt%, or from about 0.01 wt% to about 0.3 wt%. The phosphorus content may be about 700 ppm to about 900 ppm, or 850 ppm or less. The total measured sulfate ash content may be 0.5 wt% or more to 1.0 wt% or less, or less than 0.8 wt%, or more than 0.5 wt% to less than 1.0 wt%, or more than 0.6 wt% to less than 1.0 wt% when measured by ASTM D874. In another embodiment, the sulfur content may be about 0.4 wt% or less, the phosphorus content may be about 0.08 wt% or less, and the measured sulfate ash is 0.5 wt% or more to about 1 wt% or less. In yet another embodiment, the sulfur content may be about 0.3 wt% or less, the phosphorus content may be about 0.05 wt% or less, and the measured sulfate ash may be about 0.8 wt% or less.

[0061] In one embodiment, the lubricating oil composition is an engine oil, and the lubricating oil composition may have (i) a sulfur content of about 0.5 wt% or less, (ii) a phosphorus content of about 0.1 wt% or less, and (iii) a measured sulfate ash content of 0.5 wt% or more to 1.0 wt% 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 the total metal in ppm to the total boron in ppm is more than 7.5, or more than 50, or more than 500.

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

[0064] In some embodiments, the lubricating oil composition is suitable for use in engines powered by low sulfur fuels such as fuels containing from about 1% to about 5% sulfur. Highway vehicle fuel contains about 15 ppm 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 only one or all of these types.

[0066] Furthermore, the lubricants of this specification 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, etc., or Dexos™ 1, Dexos™ 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 to meet 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 in this specification. 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, various fluids such as tractor hydraulic fluids, power transmission fluids including automatic transmission fluids, continuously variable transmission fluids and manual transmission fluids, hydraulic fluids including tractor hydraulic fluids, some gear oils, power steering fluids, fluids used in wind turbines, compressors, some industrial fluids, and fluids associated with components of power transmission devices. It should be noted that within each of these fluids such as automatic transmission fluids, there are various different types of fluids for various different transmissions having 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 respect to tractor hydraulic fluids, these fluids are general-purpose fluids used for all lubricant applications in tractors except for lubricating the engine. These lubrication applications may include lubrication of the gearbox, power take-off and clutch, rear axle, reduction gears, wet brakes, and hydraulic accessories.

[0069] When 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 friction coefficient of the fluid tends to decrease due to temperature effects as the fluid is heated during operation. It is important for the working fluid or automatic transmission fluid of a tractor to maintain a high friction coefficient at high temperatures; otherwise, the braking system or automatic transmission may fail. This is not a 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 that of transmissions, differentials, final drive planetary gears, wet brakes, and hydraulic performance. Many of the additives used to formulate UTTO or STUO fluids are functionally similar, but if not added properly, they may have harmful effects. For example, certain anti-wear and extreme pressure additives used in engine oil are highly corrosive to the copper components of hydraulic pumps. Detergents and dispersants used for gasoline or diesel engine performance can be harmful 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 is designed to meet certain strict manufacturer requirements, regardless of functionality, tractor, or lubricity.

[0071] The present disclosure provides a novel lubricating oil blend formulated for use as an automotive crankcase lubricant. The present disclosure provides a novel lubricating oil blend formulated for use as a crankcase lubricant for 2T and / or 4T motorcycles. Embodiments of the present disclosure are suitable for use in a crankcase and provide a lubricating oil having improvements in characteristics such as air entrainment, alcohol fuel compatibility, antioxidant properties, anti-wear performance, biofuel compatibility, bubble reduction characteristics, friction reduction, fuel consumption, pre-ignition prevention, rust inhibition, sludge and / or soot dispersibility, piston cleanliness, deposit formation, and water resistance.

[0072] The engine oil of the present disclosure can 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 alternatively may be combined individually with the base oil (or a mixture of both). The fully formulated engine oil can exhibit improved performance characteristics based on the additives added and their respective proportions.

[0073] Further details and advantages of the present disclosure are described in part in the following description and / or may be learned by the practice of the present disclosure. The details and advantages of the present disclosure may be realized and achieved by the elements and combinations particularly pointed out in the appended claims. It is to be understood that both the foregoing general description and the following detailed description are exemplary and explanatory only and are not restrictive of the claimed present disclosure.

DETAILED DESCRIPTION OF THE INVENTION

[0074] Various embodiments of the present disclosure provide lubricating oil compositions and methods for reducing fouling in diesel particulate filters. The lubricating oil compositions can be useful in compression (diesel) engines and / or spark ignition (gasoline) engines. In particular, the engines in which the lubricating oil compositions can be used can include boosted internal combustion engines such as turbocharged and supercharged internal combustion engines. Examples of 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, based on the total weight of the lubricating oil composition, when measured by ASTM D874, a base oil having a lubricating viscosity of more than 50 wt% based on the total weight of the lubricating oil composition, 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 measured sulfate ash content of 1.0 wt% or less, and a ratio of calcium from one or more calcium-containing detergents to magnesium from one or more magnesium-containing detergents of 1:1 or more, in ppm, a lubricating oil composition.

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

[0077] The lubricating oil composition and method described above can 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.

[0078] Preferably, the lubricating oil composition and method also 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 a reference lubricant R-1, or the reduction of LSPI events is 50% or more, and the LSPI event is the LSPI count during 25,000 engine cycles, and the engine operates at 2000 revolutions per minute with a brake mean effective pressure of 1800 kPa.

[0079] As described in more detail below, embodiments of the present disclosure provide significant and unexpected improvements in reducing clogging in diesel particulate filters and, optionally, significant reduction of low speed preignition events while maintaining a relatively high calcium detergent concentration in the lubricating oil composition.

[0080] Base oil The base oil used in the lubricating oil composition can be selected from any of the base oils in Groups I-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 stocks. Group IV base oils contain true synthetic molecular species produced by polymerization of olefinically unsaturated hydrocarbons. Many Group V base oils are also true synthetic products and can include diesters, polyol esters, polyalkylene glycols, alkylated aromatics, polyphosphate esters, polyvinyl ethers, and / or polyphenyl ethers, etc., but can also be naturally occurring oils such as vegetable oils. It should be noted that Group III base oils are derived from mineral oils, but the severe processing these fluids undergo makes their physical properties very similar to those of some true synthetic substances such as PAO. Thus, oils derived from Group III base oils are sometimes referred to as synthetic fluids in the industry. Group II+ can include high viscosity index Group II.

[0082] The base oil used in the disclosed lubricating oil composition can be a mineral oil, animal oil, vegetable oil, synthetic oil, synthetic oil blend, or a mixture thereof. Suitable oils can be derived from hydrocracked, hydrogenated, hydrofinished, unrefined, refined and re-refined oils, and mixtures thereof.

[0083] Crude oil is derived from natural oils, mineral oils, or synthetic sources that have not undergone a refining process or have undergone very little further refining. Refined oils are similar to crude oils, except that they are processed in one or more refining steps that can result in the improvement of one or more properties. Examples of suitable refining techniques are solvent extraction, secondary distillation, acid or base extraction, filtration, osmosis, etc. Oils refined to food quality may or may not be useful. Edible oils may also be referred to as white oils. In some embodiments, the lubricating oil composition does not contain edible oils or white oils.

[0084] Re-refined oils are also known as recycled oils or reprocessed oils. These oils are similar to refined oils obtained using the same or similar processes. Additionally, these oils are further processed by techniques related to the removal of used additives and oil decomposition products.

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

[0086] Useful synthetic lubricating oils include hydrocarbon oils such as polymerized, oligomerized, or internally polymerized olefins (e.g., polybutylene, polypropylene, propylene isobutylene copolymer); poly(1-hexene), poly(1-octene), trimers or oligomers of 1-decene, e.g., poly(1-decene) (such materials are often referred to as α-olefins), and mixtures thereof; alkyl-benzenes (e.g., dodecylbenzene, tetradecylbenzene, dinonylbenzene, di-(2-ethylhexyl)-benzene); polyphenyls (e.g., biphenyl, terphenyl, alkylated polyphenyls); diphenylalkanes, alkylated diphenylalkanes, alkylated diphenyl ethers, and alkylated diphenyl sulfides, and derivatives, analogs, and homologs thereof, or mixtures thereof. Polyalphaolefins are typically hydrogenated materials.

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

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

[0089] The amount of oil having lubricating viscosity present can be the remainder after subtracting from 100% by weight the total amount of viscosity index improvers and / or pour point depressants and / or other performance additives including top surface treatment additives. For example, the oil having lubricating viscosity that can be present in the final fluid can be a major amount, such as greater than about 50% by weight, greater than about 60% by weight, greater than about 70% by weight, greater than about 80% by weight, greater than about 85% by weight, or greater than about 90% by weight.

[0090] Detergent The lubricating oil composition includes 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 can be independently selected from neutral, low-base, or overbased 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 dithiophosphoric acids, alkylphenols, sulfur-bonded alkylphenol compounds, or methylene-bridged phenols. Suitable detergents and methods for their preparation are described in detail in numerous patent publications, including US 7,732,390 and the references cited therein.

[0091] The detergent base may be basified with an alkali metal or alkaline earth metal such as, but not limited to, calcium, magnesium, potassium, sodium, lithium, barium, or mixtures thereof. In some embodiments, the detergent does not contain barium. Suitable detergents may include alkali or alkaline earth metal salts of petroleum sulfonic acids, and long-chain mono- or dialkylaryl sulfonic acids, where the aryl groups are benzyl, tolyl, and xylyl. Examples of suitable additional detergents include calcium phenate, calcium sulfur-containing phenate, calcium sulfonate, calcium calixarate, calcium salixarate, calcium salicylate, calcium carboxylate, calcium phosphate, calcium mono- and / or dithiophosphate, calcium alkylphenol, calcium sulfur-bonded alkylphenol compounds, calcium methylene-bridged phenol, magnesium phenate, magnesium sulfur-containing phenate, magnesium sulfonate, magnesium calixarate, magnesium salixarate, magnesium salicylate, magnesium carboxylate, magnesium phosphate, magnesium mono- and / or dithiophosphate, magnesium alkylphenol, magnesium sulfur-bonded alkylphenol compounds, magnesium methylene-bridged phenol, sodium phenate, sodium sulfur-containing phenate, sodium sulfonate, sodium calixarate, sodium salixarate, sodium salicylate, sodium carboxylate, sodium phosphate, mono- and / or dithiophosphate sodium, sodium alkylphenol, sodium sulfur-bonded alkylphenol compounds, or sodium methylene-bridged phenol, but are not limited thereto.

[0092] Overbased Detergent is known in the art and may be an alkali or alkaline earth metal overbased Detergent additive. Such DetergentThe additive 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.

[0093] The term "overbased" relates to metal salts such as sulfonates, carboxylates, and phenates where 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 the acid to its "standard" "neutral" salt). The expression "metal ratio", often abbreviated as MR, is used to indicate the ratio of the total chemical equivalents of metal in an overbased salt to the chemical equivalents of metal in a neutral salt, according to known chemical reactivity and stoichiometry. In a standard or neutral salt the metal ratio is 1, but in an overbased salt the MR is greater than 1. These are generally referred to as overbased, highly basic, or superbasic salts and may be salts of organic sulfuric acids, carboxylic acids, or phenols.

[0094] The overbased detergent of the lubricating oil composition may have a total base number (TBN) of about 200 mg KOH / gram or more, or as a further example, 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] Examples of suitable overbased detergents include, but are not limited to, overbased calcium phenate, overbased calcium sulfur-containing phenate, overbased calcium sulfonate, overbased calcium calyxarate, overbased calcium salixarate, overbased calcium salicylate, overbased calcium carboxylate, overbased calcium phosphate, overbased calcium mono- and / or dithiophosphate, overbased calcium alkylphenol, overbased calcium sulfur-bonded alkylphenol compound, overbased calcium methylene-bridged phenol, overbased magnesium phenate, overbased magnesium sulfur-containing phenate, overbased magnesium sulfonate, overbased magnesium calyxarate, overbased magnesium salixarate, overbased magnesium salicylate, overbased magnesium carboxylate, overbased magnesium phosphate, overbased magnesium mono- and / or dithiophosphate, overbased magnesium alkylphenol, overbased magnesium sulfur-bonded alkylphenol compound, overbased magnesium methylene-bridged phenol.

[0096] Overbased 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 when measured by the method of ASTM D-2896. When such a detergent composition is formed with an inert diluent, such as a process oil, usually a mineral oil, the total base number reflects the basicity of the entire composition including the diluent and any other materials (such as accelerators, etc.) that may be contained in the detergent composition.

[0097] Overbased detergents may have a metal to substrate ratio of from 1.1:1, or from 2:1, or from 4:1, or from 5:1, or from 7:1, or from 10:1.

[0098] In some embodiments, the detergent is effective to reduce or prevent rust in the engine.

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

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

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

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

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

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

[0105] In some embodiments, one or more magnesium-containing detergents are 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 as measured by the method of ASTM D-2896.

[0106] In other embodiments, one or more magnesium-containing detergents are overbased magnesium sulfonate detergents 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 as measured by the method of ASTM D-2896.

[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 comprises less than 15 ppm magnesium, or less than 10 ppm magnesium from the detergent.

[0109] Molybdenum-containing component The lubricant composition of the present specification contains one or more molybdenum-containing compounds. The oil-soluble molybdenum compound may have the functional performance of an anti-wear agent, an antioxidant, a friction modifier, or a mixture thereof. The oil-soluble molybdenum compound may include molybdenum dithiocarbamate, molybdenum dialkyldithiophosphate, molybdenum dithiophosphinic acid, an amine salt of a molybdenum compound, molybdenum xanthate, molybdenum thioxanthone, molybdenum sulfide, molybdenum carboxylate, molybdenum alkoxide, a trinuclear organic molybdenum compound, and / or a mixture thereof. The molybdenum sulfide includes molybdenum disulfide. The molybdenum disulfide can 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, an amine salt of a molybdenum compound, 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 are those available from R.T. Vanderbilt Co., Ltd. under trade names such as Molyvan 822 (trademark), Molyvan (trademark) A, Molyvan 2000 (商標) , and commercially available materials sold under trade names such as Sakura-Lube (trademark) S-165, S-200, S-300, S-310G, S-525, S-600, S-700, and S-710 available from Adeka Corporation, and mixtures thereof. Suitable molybdenum components are described in US5,650,381, US RE37,363E1, US RE38,929E1 and US RE40,595E1, which are hereby incorporated by reference in their entirety. Preferably, the one or more molybdenum-containing compounds can be a reaction product of a fatty acid ester and molybdenum oxide. Preferably, the fatty acid ester has 4 to 30 carbon atoms, or 6 to 20 carbon atoms.

[0111] Additionally, the molybdenum compound may be an acidic molybdenum compound. Those included are molybdic acid, ammonium molybdate, sodium molybdate, potassium molybdate, and other alkali metal molybdates and other molybdenum salts which are hydrogen sodium molybdate, MoOCl4, MoO2Br2, Mo2O3Cl6, molybdenum trioxide or similar acidic molybdenum compounds. Alternatively, the composition can be provided using molybdenum with a molybdenum / sulfur complex of a basic nitrogen compound described in, for example, U.S. Patent Nos. 4,263,152, 4,285,822, 4,283,295, 4,272,387, 4,265,773, 4,261,843, 4,259,195, and 4,259,194, and WO94 / 06897, the entireties of which are incorporated herein by reference.

[0112] Another class of suitable organic molybdenum compounds are trinuclear molybdenum compounds such as compounds of the formula Mo3SkLnQz and mixtures thereof, wherein S represents sulfur, L represents independently selected ligands having sufficient carbon atoms such that the compound is soluble or dispersible in oil, n is from 1 to 4, k is from 4 to 7, Q is selected from the group of neutral electron donating compounds such as water, amines, alcohols, phosphines and ethers, z is in the range from 0 to 5, including non-stoichiometric values. Among the organic groups of all ligands, there may be present at least 21 carbon atoms in total, such as at least 25, at least 30, or at least 35 carbon atoms. Additional suitable molybdenum compounds are described in U.S. Patent No. 6,723,685, the entirety of which is incorporated herein by reference.

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

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

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

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

[0117] When present, the boron-containing compound can be used in an amount sufficient to provide up to about 8 wt% of the lubricating oil composition, about 0.01 wt% to about 7 wt%, about 0.05 wt% to about 5 wt%, or about 0.1 wt% to about 3 wt%.

[0118] In some embodiments of the present invention, the lubricating oil composition may contain 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, based on the total weight of the lubricating oil composition.

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

[0120] Antioxidant The lubricating oil compositions of the present specification may also optionally contain one or more antioxidants. Antioxidant compounds are known and include, for example, phenates, phenate sulfides, sulfurized olefins, phosphosulfurized terpenes, sulfurized esters, aromatic amines, alkylated diphenylamines (e.g., nonyldiphenylamine, di-nonyldiphenylamine, octyldiphenylamine, di-octyldiphenylamine), phenyl-alpha-naphthylamine, alkylated phenyl-alpha-naphthylamine, hindered non-aromatic amines, phenols, hindered phenols, oil-soluble molybdenum compounds, polymeric antioxidants, or mixtures thereof. The antioxidant compounds can be used alone or in combination.

[0121] The hindered phenol antioxidant may contain a secondary butyl group and / or a tertiary butyl group as a steric hindrance group. 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 may include an addition product derived from 2,6-di-tert-butylphenol and an alkyl acrylate, and 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 and may include Ethanox (商標) 4716.

[0122] Useful antioxidants may include diarylamines and high molecular weight phenols. In one embodiment, the lubricating oil composition may contain a mixture of a diarylamine and a high molecular weight phenol, and each antioxidant may be present in an amount sufficient to provide up to about 5 wt% based on the final weight of the lubricating oil composition. In one embodiment, the antioxidant may be a mixture of about 0.3 to about 1.5 wt% diarylamine and about 0.4 to about 2.5 wt% high molecular weight phenol based on the final weight of the lubricating oil composition.

[0123] Examples of suitable olefins that can be sulfided 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 olefin may be a Diels - Alder adduct of a diene such as 1,3 - butadiene and an unsaturated ester 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 from about 4 to about 22 carbon atoms. Examples of suitable fatty acids and their esters include triglycerides, oleic acid, linoleic acid, palmitoleic acid, or mixtures thereof. Often, fatty acids are obtained from lard oil, tall oil, peanut oil, soybean oil, cottonseed oil, sunflower seed oil, or mixtures thereof. The fatty acids and / or esters may be mixed with olefins such as α - olefins.

[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, preferably, the ratio of phenolic, amine, and molybdenum - containing is (0 - 2):(0 - 2):(0 - 1).

[0126] One or more antioxidants may be present in the lubricating oil composition in the range of about 0 wt% to about 20 wt%, or about 0.1 wt% to about 10 wt%, or about 0.6 wt% to about 5 wt%, or about 1.0 to about 3 wt%.

[0127] Wear resistant agent The lubricant composition of this specification may also optionally contain one or more antiwear agents. Examples of suitable antiwear agents include, but are not limited to, metal thiophosphates, metal dialkyldithiophosphates, their phosphate esters or salts, phosphate esters, phosphites, phosphorus-containing carboxylic acid esters, ethers, or amides, sulfurized olefins, thiocarbamate esters, alkylene-bonded thiocarbamates, and thiocarbamate-containing compounds including bis(S-alkyldithiocarbamyl) disulfide, and mixtures thereof. A suitable antiwear agent can be molybdenum dithiocarbamate. Phosphorus-containing antiwear agents are described in more detail in European Patent No. 612839. The metal in the dialkyldithiophosphate salt can be an alkali metal, alkaline earth metal, aluminum, lead, tin, molybdenum, manganese, nickel, copper, titanium, or zinc. A useful antiwear agent can be zinc dialkyldithiophosphate.

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

[0129] The antiwear agent may be present in an amount ranging from about 0 wt% to about 15 wt%, or about 0.01 wt% to about 10 wt%, or about 0.05 wt% to about 5 wt%, or about 0.1 wt% to about 3 wt% of the lubricant composition.

[0130] Additional optional detergents The lubricating oil composition may contain one or more neutral and / or low basicity detergents, and overbased detergents that do not contain calcium and their mixtures. Suitable detergent substrates include phenates, sulfur-containing phenates, sulfonic acids, calixalates, salixalates, salicylic acids, carboxylic acids, phosphoric acids, mono- and / or dithiophosphoric acids, alkylphenols, sulfur-bonded alkylphenol compounds, or methylene-bridged phenols. Suitable detergents and methods for their preparation are described in detail in numerous patent publications, including US 7,732,390 and the references cited therein. The detergent substrate may be basified with an alkali metal or alkaline earth metal such as, but not limited to, calcium, magnesium, potassium, sodium, lithium, barium, or mixtures thereof. In some embodiments, the detergent does not contain barium. Suitable detergents may include alkali or alkaline earth metal salts of petroleum sulfonic acids, and long-chain mono- or dialkylarylsulfonic acids, where the aryl groups are benzyl, tolyl, and xylyl.Examples of suitable detergents include, but are not limited to, calcium phenate, calcium sulfur-containing phenate, calcium sulfonate, calcium calixarate, calcium salicylate, calcium carboxylate, calcium phosphate, calcium mono- and / or dithiophosphate, calcium alkylphenol, calcium sulfur-bonded alkylphenol compound, calcium methylene-bridged phenol, magnesium phenate, magnesium sulfur-containing phenate, magnesium sulfonate, magnesium calixarate, magnesium salicylate, magnesium carboxylate, magnesium phosphate, magnesium mono- and / or dithiophosphate, magnesium alkylphenol, magnesium sulfur-bonded alkylphenol compound, magnesium methylene-bridged phenol, sodium phenate, sodium sulfur-containing phenate, sodium sulfonate, sodium calixarate, sodium salicylate, sodium carboxylate, sodium phosphate, mono- and / or dithiophosphate sodium, sodium alkylphenol, sodium sulfur-bonded alkylphenol compound, or sodium methylene-bridged phenol.

[0131] Overbased Detergent Additives are known in the art and can be alkali or alkaline earth metal overbased 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 "overbased" relates to metal salts such as sulfonates, carboxylates, and phenates where the amount of metal present exceeds the stoichiometric amount. Such salts may have a conversion level of over 100% (i.e., they may contain more than 100% of the theoretical amount of metal required to convert the acid to its "standard" "neutral" salt). The expression "metal ratio", often abbreviated as MR, is used to indicate the ratio of the total chemical equivalents of metal in an overbased salt to the chemical equivalents of metal in a neutral salt, according to known chemical reactivity and stoichiometry. In a standard or neutral salt, the metal ratio is 1, but in an overbased salt, the MR is greater than 1. These are generally referred to as overbased, highly basic, or superbasic salts and may be salts of organic sulfuric acids, carboxylic acids, or phenols.

[0133] The overbased detergent of the lubricating oil composition may have a total base number (TBN) of greater than about 225 mg KOH / gram, or as a further example, greater than or equal to about 250 mg KOH / gram, or greater than or equal to about 350 mg KOH / gram, or greater than or equal to about 375 mg KOH / gram, or greater than or equal to about 400 mg KOH / gram.

[0134] Examples of suitable overbased detergents include, but are not limited to, overbased magnesium phenate, overbased magnesium sulfur-containing phenate, overbased magnesium sulfonate, overbased magnesium calixarate, overbased magnesium salixarate, overbased magnesium salicylate, overbased magnesium carboxylate, overbased magnesium phosphate, overbased magnesium mono- and / or di-thiophosphate, overbased magnesium alkylphenol, overbased magnesium sulfur-bonded alkylphenol compound, or overbased magnesium methylene-bridged phenol.

[0135] The overbased detergent may have a metal to substrate ratio from 1.1:1, or from 2:1, or from 4:1, or from 5:1, or from 7:1, or from 10:1.

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

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

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

[0139] In some embodiments, the detergent is effective to reduce or prevent rust in the engine.

[0140] Dispersant This lubricating oil composition may optionally further contain one or more dispersants or mixtures thereof. The dispersant does not contain a metal that forms ash before being mixed into the lubricating oil composition and typically does not contribute to ash when added to the lubricant, and is thus often referred to as an ashless type dispersant. Ashless dispersants are characterized by a relatively high molecular weight hydrocarbon chain, polymer, or copolymer to which a polar group is attached. Typical ashless dispersants include N-substituted long chain alkenyl succinimides. Examples of N-substituted long chain alkenyl succinimides include polyisobutylene succinimides having a number average molecular weight of the polyisobutylene substituent in the range of about 350 to about 50,000, or 350 to about 5,000, or 350 to about 3,000, and polyalphaolefin succinimides having a number average molecular weight of the polyalphaolefin substituent in the range of about 350 to about 10,000, or 350 to about 5,000, or 350 to about 3,000, as measured by gel permeation chromatography (GPC) using polystyrene as a calibration standard. Suitable polyalphaolefins include ethylene-alphaolefin copolymers such as ethylene-propylene copolymers.

[0141] Succinimide dispersants and their preparation are disclosed, for example, in U.S. Patent No. 7,897,696 or U.S. Patent No. 4,234,435. The polyolefin can be prepared from polymerizable monomers containing about 2 to about 16, or about 2 to about 8, or about 2 to about 6 carbon atoms. The succinimide dispersant is typically an imide formed from a polyamine, 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 pentaethyleneaminehexamine (PEHA).

[0143] Suitable heavy polyamines include small amounts of lower polyamine oligomers such as TEPA and PEHA (pentaethylenehexamine), but mainly mixtures of polyalkylene-polyamines containing six or more nitrogen atoms, two or more primary amines per molecule, and oligomers having a broader branching than conventional polyamine mixtures. The heavy polyamine preferably contains a polyamine oligomer containing seven or more nitrogens per molecule and two or more primary amines per molecule. The heavy polyamine contains more than 28% by weight (e.g., more than 32% by weight) of total nitrogen and a primary amine group with an equivalent weight of 120 to 160 grams per equivalent.

[0144] Suitable polyamines are generally known as PAM and contain mixtures of ethyleneamines, where TEPA and pentaethylenehexamine (PEHA) are the major part of the polyamine, usually less than about 80%.

[0145] Typically, PAM has 8.7 to 8.9 milliequivalents of primary amine per gram (115 to 112 grams per equivalent of primary amine) and a total nitrogen content of about 33 to 34% by weight. A heavier cut of PAM oligomers that are substantially free of TEPA and have very little PEHA but mainly contain six or more nitrogens and oligomers with broader branching can produce a dispersant with improved dispersibility.

[0146] In one embodiment, the present disclosure further comprises at least one polyisobutylene succinimide dispersant derived from polyisobutylene having a number average molecular weight in the range of about 350 to about 50,000, or ~ about 5000, or ~ about 3000, 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, when present, polyisobutylene can 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 PIB is also called high-reactivity PIB (“HR-PIB”). HR-PIB having a number average molecular weight in the range of about 800 to about 5000 is suitable for use in embodiments of the present disclosure. Conventional PIB typically has a terminal double bond content of less than 50 mol%, less than 40 mol%, less than 30 mol%, less than 20 mol%, or less than 10 mol%.

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

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

[0150] The active % 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 the polyolefin is calculated from the 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 by weight and all molecular weights are number average molecular weights.

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

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

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

[0156] One class of suitable 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 more detail in U.S. Patent No. 3,634,515.

[0157] A suitable class of dispersants may be high molecular weight esters or semi-ester amides.

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

[0159] In addition to the post-treatment with carbonates and boric acid, the compounds can all be post-treated or further post-treated by various 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 acids or anhydrides (e.g., U.S. Patent Nos. 3,403,102 and 4,648,980), organic phosphorus 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), epoxides, 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 British 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), diketenes (e.g., U.S. Patent No. 3,546,243), diisocyanates (e.g., U.S. Patent No. 3,573,205), alkane sultones (e.g., U.S. Patent No. 3,749,695), 1,3-dicarbonyl compounds (e.g., U.S. Patent No. 4,579,675), Sulfates of alkoxylated alcohols or 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, 4,670,170), Nitrogen-containing carboxylic acids (e.g., U.S. Patent No. 4,971,598 and British Patent No. GB2,140,811), Hydroxy-protected chlorodicarbonyl oxy 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, 4,670,170), Nitrogen-containing carboxylic acids (e.g., U.S. Patent No. 4,971,598 and British Patent No. GB2,440,811), Hydroxy-protected chlorodicarbonyl oxy 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), Hydroxy aliphatic carboxylic acids (e.g., U.S. Patent Nos. 4,482,464, 4,521,318, 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 an aldehyde or a ketone and sulfur or sulfur chloride (e.g., U.S. Patent Nos. 3,390,086 and 3,470,098), A combination of hydrazine and carbon disulfide (e.g., U.S. Patent No. 3,519,564), A combination of an aldehyde and a phenol (e.g., U.S. Patent Nos. 3,649,229, 5,030,249, and 5,039,307), A combination of an aldehyde and an O-diester of dithiophosphoric acid (e.g., U.S. Patent No. 3,865,740), A combination of a hydroxy aliphatic carboxylic acid and boric acid (e.g., U.S. Patent No. 4,554,086), A combination of a hydroxy aliphatic carboxylic acid, followed by formaldehyde and a phenol (e.g., U.S. Patent No. 4,636,322), A combination of a hydroxy aliphatic carboxylic acid and a subsequent aliphatic dicarboxylic acid (e.g., U.S. Patent No. 4,663,064), A combination of formaldehyde and a phenol, and a subsequent glycolic acid (e.g., U.S. Patent No. 4,699,724), A combination of a hydroxy aliphatic 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 partial or complete sulfur analog thereof and a boron compound (e.g., U.S. Patent No. 4,857,214), A combination of an organic diacid, a subsequent unsaturated fatty acid, and a subsequent nitroso aromatic amine, optionally followed by a boron compound, and a subsequent glycolating agent (e.g., U.S. Patent No. 4,973,412), A combination of an aldehyde and a triazole (e.g., U.S. Patent No. 4,963,278), Combinations of aldehydes and triazoles, followed by boron compounds (e.g., U.S. Patent No. 4,981,492), Treatment by combinations of cyclic lactones and boron compounds (e.g., U.S. Patent Nos. 4,963,275 and 4,971,711), etc. is included. The above patents are hereby incorporated by reference in their entirety.

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

[0161] When present, the dispersant inhibitor can be used in an amount sufficient to provide up to about 20 weight percent, based on the final weight of the lubricating oil composition. Another amount of dispersant that can be used is from about 0.1 weight percent to about 15 weight percent, or from about 0.1 weight percent to about 10 weight percent, or from about 3 weight percent to about 10 weight percent, or from about 1 weight percent to 6 weight percent, or from about 7 weight percent to about 12 weight percent, based on the final weight of the lubricating oil composition. In some embodiments, the lubricating oil composition utilizes a mixed dispersant system. A mixture of a single type or two or more types of dispersants in any desired ratio can be used.

[0162] Friction modifier The lubricating oil compositions herein may also optionally contain one or more friction modifiers. Suitable friction modifiers include, but are not limited to, imidazolines, amides, amines, succinimides, alkoxylated amines, alkoxylated ether amines, amine oxides, amide amines, 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, etc., including metal-containing and metal-free friction modifiers.

[0163] Suitable friction modifiers may contain a hydrocarbyl group selected from linear, branched, or aromatic hydrocarbyl groups, or mixtures thereof, and may be saturated or unsaturated. The hydrocarbyl group may be composed of carbon and hydrogen or heteroatoms such as sulfur or oxygen. The hydrocarbyl group may range from about 12 to about 25 carbon atoms. In some embodiments, the friction modifier may be a long-chain fatty acid ester. In other embodiments, the long-chain fatty acid ester may be a monoester, or a diester, or a (tri)glyceride. The friction modifier may be a long-chain fatty amide, a long-chain fatty ester, a long-chain fatty epoxide derivative, or a long-chain imidazoline.

[0164] Other suitable friction modifiers may include organic, ashless (metal-free), nitrogen-free organic friction modifiers. Such friction modifiers may include esters formed by reacting carboxylic acids and anhydrides with alkanols, and generally include polar end groups (e.g., carboxyl or hydroxyl) covalently bonded to a lipophilic hydrocarbon chain. Examples of organic ashless nitrogen-free friction modifiers are generally known as glycerol monooleate (GMO), which may include mono-, di-, and tri-esters of oleic acid. Other suitable friction modifiers are described in U.S. Patent No. 6,723,685, which is hereby incorporated by reference in its entirety.

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

[0166] Amines and amides can be used as such or in the form of 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 hereby incorporated by reference in its entirety.

[0167] The friction modifier may optionally be present in an amount ranging from about 0 wt% to about 10 wt%, or from about 0.01 wt% to about 8 wt%, or from about 0.1 wt% to about 4 wt%.

[0168] Additional molybdenum-containing component The lubricating oil compositions herein may also optionally contain additional molybdenum-containing compounds. The oil-soluble molybdenum compounds may have the functional performance of an anti-wear agent, an antioxidant, a friction modifier, or a mixture thereof. The oil-soluble molybdenum compounds may include molybdenum dithiocarbamate, molybdenum dialkyldithiophosphate, molybdenum dithiophosphinic acid, amine salts of molybdenum compounds, molybdenum xanthate, molybdenum thioxanthone, molybdenum sulfide, molybdenum carboxylate, molybdenum alkoxide, trinuclear organomolybdenum compounds, and / or mixtures thereof. The molybdenum sulfide includes molybdenum disulfide. The molybdenum disulfide can be in the form of a stable dispersion. In one embodiment, the oil-soluble molybdenum compound can 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] Suitable examples of molybdenum compounds that can be used include commercially available materials available from R.T.Vanderbilt Co.,Ltd. under trade names such as Molyvan 822(trademark), Molyvan(trademark)A, Molyvan 2000(trademark), and Molyvan 855(trademark), and those sold under trade names such as Sakura-Lube(trademark)S-165, S-200, S-300, S-310G, S-525, S-600, S-700, and S-710 available from Adeka Corporation, and mixtures thereof. Suitable molybdenum components are described in US5,650,381, US RE37,363 E1, US RE38,929 E1, and US RE40,595 E1, which are hereby incorporated by reference in their entirety.

[0170] Additionally, the molybdenum compound may be an acidic molybdenum compound. Included are molybdic acid, ammonium molybdate, sodium molybdate, potassium molybdate, and other alkali metal molybdates and other molybdenum salts, which are hydrogen sodium molybdate, MoOCl4, MoO2Br2, Mo2O3Cl6, molybdenum trioxide or similar acidic molybdenum compounds. Alternatively, the composition can be provided using molybdenum with basic nitrogen compounds described in, for example, U.S. Patent Nos. 4,263,152, 4,285,822, 4,283,295, 4,272,387, 4,265,773, 4,261,843, 4,259,195, and 4,259,194, and WO94 / 06897, which are hereby incorporated by reference in their entirety.

[0171] Suitable organomolybdenum compounds of another class are trinuclear molybdenum compounds such as compounds of the formula Mo3SkLnQz and mixtures thereof, where S represents sulfur, L represents independently selected ligands having sufficient carbon atoms to render the compound soluble or dispersible in oil, n is from 1 to 4, k is from 4 to 7, Q is selected from the group of neutral electron-donating compounds such as water, amines, alcohols, phosphines and ethers, z is in the range from 0 to 5, including non-stoichiometric values. Among the organic groups of all ligands, there may be at least 21 carbon atoms, such as at least 25, at least 30, or at least 35 carbon atoms in total. Additional suitable molybdenum compounds are described in U.S. Patent No. 6,723,685, which is hereby incorporated by reference in its entirety.

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

[0173] Transition metal-containing compound 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, etc. Suitable metalloids include, but are not limited to, boron, silicon, antimony, tellurium, etc.

[0174] In an embodiment, the oil-soluble transition metal-containing compound can function as an antiwear agent, a friction modifier, an antioxidant, an adhesion control additive, or two or more of these functions. In an embodiment, 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 for oil-soluble substances or can be used in the preparation of oil-soluble substances, the disclosed technology includes various Ti(IV) compounds such as titanium(IV) oxide, titanium(IV) sulfide, titanium(IV) nitrate, titanium methoxide, titanium ethoxide, titanium propoxide, titanium isopropoxide, titanium butoxide, titanium 2-ethylhexoxide, and other titanium(IV) alkoxides, and titanium(IV) alkoxides including, but not limited to, titanium phenates, other titanium compounds or complexes, titanium carboxylates such as titanium(IV) 2-ethyl-1,3-hexanedioate or titanium citrate or titanium oleate, and titanium(IV)(triethanolaminato) isopropoxide. Other forms of titanium included in the disclosed technology include titanium phosphates such as titanium dithiophosphate (e.g., dialkyldithiophosphoric acid) and titanium sulfonate (e.g., alkylbenzene sulfonic acid), or generally reaction products of titanium compounds that form salts such as oil-soluble salts with various acid substances. Thus, the titanium compound can be derived, inter alia, from organic acids, alcohols, and glycols. The Ti compound can also exist in a dimeric or oligomeric form containing a Ti-O-Ti structure. Such titanium materials are commercially available or can be easily prepared by suitable synthetic techniques apparent to those skilled in the art. These 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 materials 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 titanium succinate intermediate may be used directly or reacted with any of a number of materials such as (a) a polyamine-based succinimide / amide dispersant having a free condensable -NH functional group, (b) components of a polyamine-based succinimide / amide dispersant, namely alkenyl- (or alkyl-) succinic anhydride and polyamine, (c) a hydroxy-containing polyester dispersant prepared by the reaction of a substituted succinic anhydride with a polyol, amino alcohol, polyamine, or mixtures thereof. Alternatively, the titanium succinate intermediate may be reacted with other agents such as, for example, an alcohol, amino alcohol, ether alcohol, polyether alcohol or polyol, or a fatty acid, and a product that is either directly used to impart Ti to a lubricant or further reacted with a succinic acid dispersant as described above. As an example, to provide a titanium-modified dispersant or intermediate, 1 part (mole) of tetra-isopropyl titanate may be reacted with about 2 parts (mole) 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 polyisobutene-substituted succinic anhydride and polyethylene polyamine mixture (127 grams + diluent oil) to produce a titanium-modified succinimide dispersant.

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

[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, neodecanoic acid, and the like.

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

[0179] Viscosity index improver The lubricating oil composition of the present specification may also optionally contain one or more viscosity index improvers. Suitable viscosity index improvers include polyolefins, olefin copolymers, ethylene / propylene copolymers, polyisobutene, hydrogenated styrene-isoprene polymers, styrene / maleic acid ester copolymers, hydrogenated styrene / butadiene copolymers, hydrogenated isoprene polymers, alpha-olefin maleic anhydride copolymers, polymethacrylates, polyacrylates, polyalkylstyrenes, hydrogenated alkenylaryl conjugated diene copolymers, or mixtures thereof. The viscosity index improver may include star polymers, and suitable examples are described in US Publication No. 2012 / 0101017(A1).

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

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

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

[0183] The lubricating oil composition according to the present disclosure may optionally contain other performance additives. The other performance additives may be additional to the additives specified in the present disclosure and / or one or more of a metal deactivator, a viscosity index improver, a detergent, an ashless TBN booster, a friction modifier, an antiwear agent, a corrosion inhibitor, a rust inhibitor, a dispersant, a dispersant viscosity index improver, an extreme pressure agent, an antioxidant, a foam inhibitor, a demulsifier, an emulsifier, a pour point depressant, a seal swell agent, and mixtures thereof. Typically, a fully formulated lubricating oil contains one or more of these performance additives.

[0184] Suitable metal deactivators include benzotriazole derivatives (typically tolyltriazole), dimercaptothiadiazole derivatives, 1,2,4-triazole, benzimidazole, 2-alkyldithiobenzimidazole, or 2-alkyldithiobenzothiazole, a foam inhibitor including a copolymer of ethyl acrylate and 2-ethylhexyl acrylate and optionally vinyl acetate, a demulsifier including trialkyl phosphate, polyethylene glycol, polyethylene oxide, polypropylene oxide, and (ethylene oxide - propylene oxide) polymers, and a pour point depressant including an ester of maleic anhydride - styrene, polymethacrylate, polyacrylate, or polyacrylamide.

[0185] Suitable foam inhibitors include silicone - 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 from about 0 wt% to about 1 wt%, from about 0.01 wt% to about 0.5 wt%, or from about 0.02 wt% to about 0.04 wt% based on the final weight of the lubricating oil composition.

[0187] Suitable rust inhibitors may be a single compound or a mixture of compounds having the property of suppressing corrosion of the ferrous metal surface. 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, and oil-soluble polycarboxylic acids including dimeric and trimeric acids formed from tall oil fatty acids, oleic acid, and linoleic acid. Other suitable corrosion inhibitors include long-chain alpha, omega-dicarboxylic acids in the molecular weight range of about 600 to about 3000, and alkenyl succinic acids such as tetrapropenyl succinic acid, tetradecenyl succinic acid, and hexadecenyl succinic acid having an alkenyl group containing about 10 or more carbon atoms. Another useful type of acidic corrosion inhibitor is a semi-ester of an alkenyl succinic acid having about 8 to about 24 carbon atoms in the alkenyl group and an alcohol such as polyglycol. The corresponding semi-amides 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 a rust inhibitor.

[0188] When present, the rust inhibitor can be used in an amount sufficient to provide from about 0 wt% to about 5 wt%, from about 0.01 wt% to about 3 wt%, from about 0.1 wt% to about 2 wt% based on the final weight of the lubricating oil composition.

[0189] Generally speaking, suitable lubricants can include additive components in the ranges listed in the following table.

Table 2

[0190] The percentages of the above components represent the weight percentages of the components based on the weight of the final lubricating oil composition. The balance of the lubricating oil composition consists of one or more base oils.

[0191] When formulating the compositions described herein, the additives used may be blended into the base oil individually or in various secondary combinations. However, it may be preferred to use additive concentrates (i.e., additives plus diluents such as hydrocarbon solvents) to simultaneously mix all of the components.

Examples

[0192] The following examples illustrate, but do not limit, the methods and compositions of the present disclosure. Other suitable modifications and adjustments of the various conditions and parameters commonly used in the art can be known to those skilled in the art without departing from the spirit and scope of the present disclosure. All patents and publications cited herein are hereby incorporated by reference in their entirety into this specification.

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

[0194] Each of the lubricating oil compositions contained a major amount of base oil and a base conventional dispersant inhibitor (DI) package. The DI package contained conventional amounts of dispersant, antiwear additive, antioxidant, friction modifier, antifoaming agent, 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 antifoaming agent. Most of the base oil was a mixture of Group III and Group IV base oils. The modified components are specified in the tables and discussions of the following examples. All values listed are described 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] Sulfated ash (SASH) was calculated for the total metal elements contributing to SASH in the lubricant composition according to the following factors, which were multiplied by the amount of each metal element in the lubricant composition, according to 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 carried out in a VW 1.9 liter, 4-cylinder direct injection diesel engine with a turbocharger. One complete test includes six test cycles. The first five stages are carried out to adjust the engine, and the last stage implements a 144-hour ash loading.

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

[0198] Reference oil R-1 was formulated from approximately 80.7 wt% Group III base oil, 12.1 wt% HiTEC® 11150 PCMO additive package available from Afton Chemical Corporation, and 7.2 wt% 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 approved DI package. R-1 also showed the following properties and partial elemental analysis.

Table 5

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

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

[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 at a sulfate ash content of 0.8%, the VW PV 1485 test does not limit the formulation 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 with turbocharger. One complete LSPI combustion engine test consisted of four test cycles. Within a single test cycle, two operating phases or segments were repeated to generate LSPI events. In Phase A, when LSPI is most likely to occur, the engine operates at approximately 2000 rpm and a brake mean effective pressure (BMEP) of approximately 1800 kPa. In Phase B, when LSPI is less likely to occur, the engine operates at approximately 1500 rpm and approximately 1700 kPa BMEP. For each phase, data was collected over 25,000 engine cycles. The structure of the test cycle is as follows: Phase A - Phase A - Phase B - Phase B - Phase A - Phase A. Each phase is separated by an idle period. Since LSPI is statistically significant during Phase A, the LSPI event data considered in this example included only LSPI events that occurred during Phase A operation. For this reason, for one complete LSPI combustion engine test, the data typically occurred over a total of 16 phases and was used to evaluate the performance of the comparative oil and the oil of the present invention.

[0203] The LSPI event was determined by monitoring the peak cylinder pressure (ΡΡ) and when 2% of the combustible material in the combustion chamber burned (MFB02). The threshold of the peak cylinder pressure was calculated for each cylinder and each stage, and was typically 6,500 - 8,500 kPa. The threshold of MFB02 was calculated for each cylinder and each stage, and was typically in the range of about 3.0 to about 7.5 crank angle degrees (CAD) after top dead center (ATDC). LSPI was recorded when the thresholds of both PP and MFB02 were exceeded in a single engine cycle. LSPI events can be reported in a number of ways. When different combustion engine tests can be performed with different numbers of engine cycles, to remove the ambiguity related to the number of reports per engine cycle, the relative numbers of LSPI events of the comparison oil and the oil of the present invention were reported as the "LSPI ratio". In this way, the improvements for some standard responses were clearly demonstrated.

[0204] In the following examples, the LSPI ratio was 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 is more than 50% (LSPI ratio less than 0.5). A further improvement in LSPI is observed when the reduction in LSPI events is more than 70% (LSPI ratio less than 0.3), and an even further improvement in LSPI is observed when the reduction in LSPI events is more than 75% (LSPI ratio less than 0.25). An even further improvement in LSPI is observed when the reduction in LSPI events relative to R-1 is more than 80% (LSPI ratio less than 0.20), and an even further improvement in LSPI is observed when the reduction in LSPI events relative to R-1 is more than 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 was 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 foregoing examples show that various lubricant formulations of the present invention can provide a significant reduction in LSPI events. Additionally, Example 1 demonstrates that the lubricating oil of the present invention passes the diesel particulate plugging test and can significantly reduce LSPI events. This may be particularly useful in boosted spark ignition combustion engines equipped with diesel particulate filters.

[0208] Other embodiments of the present disclosure will be apparent to those skilled in the art from consideration of the specification and practice of the embodiments disclosed herein. As used throughout the specification and the claims, "a" and / or "an" can refer to one or more than one. Unless otherwise indicated, all numbers expressing quantities of ingredients, molecular weights, percentages, ratios, reaction conditions, and other properties used in the specification and claims are to be understood as being modified in all instances by the term "about" whether or not the term "about" is present. Accordingly, unless indicated to the contrary, the numerical parameters set forth in the specification and claims are approximations that can vary depending upon the desired properties sought to be obtained by the present disclosure. At the very least, and not as an attempt to limit the application of the doctrine of equivalents to the claims, each numerical parameter should be construed in light of the number of reported significant digits and by applying ordinary rounding techniques. Notwithstanding that the numerical ranges and parameters setting forth the broad scope of the disclosure are approximations, the numerical values set forth in the specific examples are reported as precisely as possible. However, any numerical value inherently contains certain errors resulting from the standard deviation found in their respective testing measurements. The specification and examples are illustrative only, and the true scope and spirit of the present disclosure are intended to be indicated by the following claims.

[0209] The foregoing embodiments are actually quite susceptible to significant variations. Accordingly, the embodiments are not limited to the specific exemplifications above. Rather, the above embodiments are within the spirit and scope of the appended claims, including their legally available equivalents.

[0210] The patent owner does not generally intend to disclose any of the disclosed embodiments, and to the extent that any disclosed modifications or variations may not literally fall within the scope of the claims, they are considered to be a part of these under the doctrine of equivalents.

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

[0212] Each amount / value or range of amounts / values for each component, compound, substituent, or parameter disclosed herein should be construed as being disclosed in combination with each amount / value or range of amounts / values disclosed for any other component, compound, substituent, or parameter disclosed herein, and any combination of amounts / values or ranges of amounts / values for two or more components, compounds, substituents, or parameters disclosed herein should also be understood to be 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 construed as a disclosure of each specific value within the disclosed range having the same number of significant digits. Accordingly, the range of 1 to 4 should be construed as a distinct disclosure of the values 1, 2, 3, and 4.

[0214] It should be further understood that each lower limit of each range disclosed in this specification is to be construed as disclosed in combination with each upper limit of each range and each specific value within each range for the same component, compound, substituent, or parameter. Thus, the present disclosure should be construed as disclosing all ranges that are 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, a specific amount / value of a component, compound, substituent, or parameter disclosed in the description or examples should be construed as a disclosure of either a lower or upper limit of a range, and thus can form a range for that component, compound, substituent, or parameter in combination with any other lower or upper limit of a range or specific amount / value for the same component, compound, substituent, or parameter disclosed elsewhere in this application.

Claims

1. A lubricating oil composition comprising: a) a base oil having a lubricating viscosity of more than 50% by weight based on the total weight of the lubricating oil composition; b) a detergent 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 of more than 225 mg KOH / g; c) one or more molybdenum-containing compounds; d) phosphorus in an amount of 700 ppm to 900 ppm based on the total weight of the lubricating oil composition; e) a total measured sulfate ash content of 0.8% by weight or less when measured by ASTM D874, based on the total weight of the lubricating oil composition, and i) the concentration of calcium in the lubricating oil composition is more than 1350 ppm and less than 1700 ppm based on the total weight of the lubricating oil composition; ii) the concentration of magnesium in the lubricating oil composition is 15 ppm or less based on the total weight of the lubricating oil composition; iii) the concentration of molybdenum in the lubricating oil composition is more than 100 ppm and less than 450 ppm based on the total weight of the lubricating oil composition; iv) the concentration of boron in the lubricating oil composition is 0 ppm to less than 10 ppm based on the total weight of the lubricating oil composition; v) the ratio of calcium to magnesium in the lubricating oil composition in ppm is 3.5 or more, and the lubricating oil composition provides a diesel particulate filter delta pressure (ΔP) to oil consumption result of less than 0.43 kPa / kg when measured by the VW PV 1485 test after 144 hours. A lubricating oil composition.

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

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

4. The lubricating oil composition according to any one of claims 1 to 3, 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 any one of claims 1 to 4, 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 according to any one of claims 1 to 5, wherein the total sulfate ash content in the lubricating oil composition is more than 0.6% by weight when measured by ASTM D874.

7. The lubricating oil composition according to any one of claims 1 to 6, wherein the one or more overbased magnesium-containing detergents have a total base number of more than 225 mg KOH / g when measured by the method of ASTM D-2896.

8. The lubricating oil composition according to any one of claims 1 to 7, wherein the one or more overbased magnesium-containing detergents have a total base number of more than 300 mg KOH / g when measured by the method of ASTM D-2896.

9. The lubricating oil composition according to any one of claims 1 to 8, wherein the one or more overbased magnesium-containing detergents have a total base number of more than 350 mg KOH / g when measured by the method of ASTM D-2896.

10. The lubricating oil composition according to any one of claims 1 to 9, wherein the concentration of boron in the lubricating oil composition is 0 ppm based on the total weight of the lubricating oil composition.

11. The lubricating oil composition according to any one of claims 1 to 9, which has more than 0 ppm of boron, and the ratio of total metal in ppm in the lubricating oil composition to total boron in ppm in the lubricating oil composition is more than 7.

5.

12.

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

13.

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. 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 according to any one of claims 1 to 13, wherein the lubricating oil composition contains a total measured sulfate ash content of 0.5% by weight or more when measured by ASTM D874 based on the total weight of the lubricating oil composition. ​

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