COMPOSITION OF LUBRICANT OIL, AND METHOD FOR OPERATION IN AN PUSHED INTERNAL COMBUSTION ENGINE

专利摘要:
a lubricating oil composition and method for operating a reinforced internal combustion engine. the lubricating oil composition includes greater than 50% by weight of a base oil, one or more superbased calcium-containing detergents having a tbn greater than 225 mg koh/g, and one or more magnesium-containing detergents. a total amount of calcium from the one or more superbased calcium-containing detergents is from 900 ppm to less than 2400 ppm by weight and a total amount of magnesium from the one or more magnesium-containing detergents is from 50 ppm to 500 ppm by weight, both based on in a total weight of the lubricating oil composition. The lubricating oil composition and the method of using it are effective in reducing low speed pre-ignition events in a reinforced internal combustion engine lubricated with the lubricating oil composition.
公开号:BR112018000615B1
申请号:R112018000615-7
申请日:2016-07-14
公开日:2022-01-18
发明作者:Kristin Fletcher；William Y. Lam；Kongsheng Yang；Jeremy Styer
申请人:Afton Chemical Corporation；
IPC主号:

专利说明:

TECHNICAL FIELD
[001] The disclosure relates to lubricating compositions containing one or more oil-soluble magnesium-containing additives and the use of such lubricating oil compositions to improve low-speed pre-ignition events. FUNDAMENTALS
[002] Turbocharged or supercharged engines (i.e. hardened internal combustion engines) may exhibit an abnormal combustion phenomenon known as stochastic pre-ignition or low speed pre-ignition (or "LSPI"). LSPI is a pre-ignition event that can include very high pressure spikes, early combustion during an inappropriate crank angle, and detonation. All of these, individually and in combination, have the potential to cause severe engine degradation and/or damage. However, as LSPI events occur sporadically and in an uncontrolled way, it is difficult to identify the causes of this phenomenon and develop solutions to suppress it.
[003] Pre-ignition is a form of combustion that results from the ignition of the air-fuel mixture in the combustion chamber before the desired ignition of the air-fuel mixture by the ignitor. Pre-ignition has typically been a problem during high-speed engine operation, as the heat from engine operation can heat a portion of the combustion chamber to a temperature sufficient to ignite the air-fuel mixture upon contact. This type of pre-ignition is sometimes called a hot spot pre-ignition.
[004] More recently, abnormal intermittent combustion has been observed in boosted internal combustion engines at low speeds and medium to high loads. For example, when operating the engine at 3000 rpm or less, under load, with an average effective brake pressure (BMEP) of at least 10 bar, low speed pre-ignition (LSPI) may occur randomly and stochastically. . During low speed engine running, the compression stroke time is the longest.
[005] Several published studies have demonstrated that turbocharger usage, engine design, engine coatings, piston shape, fuel choice and/or engine oil additives can contribute to an increase in LSPI events. . One theory suggests that auto-ignition of engine oil droplets entering the engine's combustion chamber from the piston slot (the space between the piston ring pack and the cylinder liner) may be one of the causes of LSPI events. Consequently, there is a need for engine oil additive components and/or combinations that are effective in reducing or eliminating LSPI in hardened internal combustion engines. SUMMARY AND TERMS
[006] The present disclosure relates to a lubricating oil composition and a method for operating a powered internal combustion engine. The lubricating oil composition includes greater than 50% by weight of a base oil of lubricating viscosity and one or more calcium-containing alkaline detergents having a total base number greater than 225 mg KOH/g as measured by the method of ASTM D-2896 and one or more detergents containing magnesium. The one or more calcium-containing alkaline detergent compounds provide 900 ppm by weight to less than 2400 ppm by weight of calcium for the lubricating oil composition and the one or more magnesium-containing detergents provide 50 ppm by weight to 1000 ppm by weight of magnesium for the lubricating oil composition, both based on the total weight of the lubricating oil composition. The lubricating oil composition can be effective in reducing low speed pre-ignition events in the internal combustion engine lubricated with the lubricating oil composition.
[007] In another embodiment, the disclosure provides a method for reducing low speed pre-ignition events in a powered internal combustion engine. The method includes a step of lubricating the driven internal combustion engine with a lubricating oil composition comprising greater than 50% by weight of a lubricating viscosity base oil, one or more calcium-containing alkaline detergents having a total base number greater than 225. mg KOH/g measured by the method of ASTM D-2896 and one or more magnesium-containing detergents. The one or more calcium-containing alkaline detergents provide 900 ppm by weight to less than 2400 ppm by weight of calcium for the lubricating oil composition and the one or more magnesium-containing detergents provide 50 ppm by weight to 1000 ppm by weight of magnesium for the lubricating oil composition, both based on the total weight of the lubricating oil composition. The driven internal combustion engine is operated and lubricated with the lubricating oil composition so that low speed pre-ignition events in the lubricating oil composition lubricated engine can be reduced.
[008] In any of the foregoing embodiments, the one or more alkaline calcium-containing detergents comprise a compound selected from an alkaline calcium sulfonate detergent, an alkaline calcium phenate detergent and alkaline calcium salicylate detergent and mixtures thereof. In some embodiments, the alkaline detergent is a mixture of two or more alkaline calcium-containing detergents. In each of the foregoing embodiments, the one or more alkaline calcium-containing detergents can provide from about 900 to about 2,000 ppm by weight of calcium to the lubricating oil composition based on a total weight of the lubricating oil composition.
[009] In each of the foregoing embodiments, the amount of the magnesium-containing detergent may be sufficient to provide from about 100 ppm by weight to about 800 ppm by weight of magnesium to the lubricating oil composition based on the total weight of the composition. of lubricating oil. In each of the foregoing embodiments, the one or more magnesium-containing detergent compounds may be alkaline magnesium-containing detergents having a total base number greater than 225 mg KOH/g as measured by ASTM D-2896 and the one or more alkaline magnesium-containing detergents may be selected from an alkaline magnesium sulfonate detergent, an alkaline magnesium phenate detergent, a magnesium salicylate detergent and mixtures thereof.
[0010] In each of the foregoing embodiments, the lubricating oil composition may have a ratio of total metal mmol (M) to total base number (TBN) ranging from greater than 4.5 to about 10.0 or from greater than 8 to about 10.
[0011] In each of the foregoing embodiments, the total base number of the lubricating oil composition may be at least 7.5 mg KOH/g.
[0012] In each of the previous embodiments, the reduction in low speed pre-ignition (LSPI) events can be expressed as a ratio of LSPI events from a test oil to LSPI events from a reference oil (hereinafter “the LSPI Ratio”), wherein the reference oil R-1 includes a detergent containing alkali calcium as the only detergent in the lubricating oil composition in an amount that provides about 2400 ppm of calcium to the composition of lubricant. Additional R-1 reference oil details are set out below. In previous embodiments, LSPI events can be expressed as LSPI counts over 25,000 engine cycles, where the engine is operated at 2,000 revolutions per minute (RPM) with a mean brake effective pressure (BMEP) of 18,000 kPA.
[0013] In each of the above embodiments, the base oil may be selected from Group I, Group II, Group III, Group IV or Group V base oils and a combination of two or more of the above. In other embodiments, greater than 50% by weight of the base oil is selected from the group consisting of Group II, Group III, Group IV or Group V base oils and a combination of two or more of the foregoing, wherein more than 50% in base oil weight is different from thinner oils which result from the provision of additive or viscosity index improver components in the composition.
[0014] In each of the foregoing embodiments, the lubricating oil composition may include one or more components selected from friction modifiers, anti-wear agents, dispersants, antioxidants, and viscosity index improvers.
[0015] In previous embodiments of the method described here, the engine in operation can generate a Mean Effective Brake Pressure (BMEP) level greater than 1,500 kPa at an engine speed of less than 3,000 revolutions per minute (rpm) or a BMEP of 1800 kPa at an engine speed of 2000 rpm.
[0016] In each of the foregoing embodiments, the lubricating oil composition can be effective to pass a TEOST-33 banded oxidation test.
[0017] In each of the foregoing embodiments, the lubricating oil composition may further include at least 0.2% by weight of a low base/neutral calcium containing detergent having a TBN of up to 175 mg KOH/g measured by the method ASTM D-2896 based on a total weight of lubricating oil composition. The low base/neutral detergent may be a combination of two or more low base and/or neutral detergents each having a TBN of up to 175 µg KOH/g. In each of the foregoing embodiments, the one or more low-base/neutral calcium-containing detergents comprise a compound selected from an alkaline calcium sulfonate detergent, an alkaline calcium phenate detergent, an alkaline calcium salicylate detergent, and mixtures of the same. In some examples, “alkaline” may be abbreviated “OB” and in some examples “low base/neutral” may be abbreviated “LB/N”.
[0018] In each of the foregoing embodiments, the total calcium supplied to the lubricating oil composition by the alkaline detergent may be from 1,000 ppm to 1,800 ppm by weight, or from 1,050 ppm to 1,650 ppm by weight based on the total weight of the composition. of lubricating oil.
[0019] In each of the foregoing embodiments, the total calcium supplied to the lubricating oil composition by the low-base/neutral calcium-containing detergent may be from 50 ppm to 1000 ppm by weight based on the total weight of the lubricating oil composition.
[0020] In each of the foregoing embodiments, the lubricating oil composition may comprise not more than 10% by weight of a Group IV base oil, a Group V base oil or a combination thereof. In each of the foregoing embodiments, the compositions and lubricating oil comprise less than 5% by weight of a Group V base oil.
[0021] In each of the foregoing embodiments, the alkaline calcium-containing detergent may be an alkaline calcium sulfonate detergent.
[0022] In each of the foregoing embodiments, the alkaline calcium-containing detergent may optionally exclude alkaline calcium salicylate detergents.
[0023] In each of the foregoing embodiments, the lubricating oil composition may optionally exclude any magnesium-containing detergents or the lubricating oil composition may be free of magnesium.
[0024] In each of the foregoing embodiments, the lubricating oil composition may not contain any Group IV base oils.
[0025] In each of the foregoing embodiments, the lubricating oil composition may not contain any Group V base oils.
[0026] The following definitions of terms are provided to clarify the meanings of certain terms as used herein.
[0027] The terms "oil composition", "lubrication composition", "lubricating oil composition", "lubricating oil", "lubricating composition", "lubrication composition", "fully formulated lubricating composition", "lubricant" , "crankcase oil", "crankcase oil", "engine oil", "engine oil", "engine oil" and "engine lubricant" are considered synonymous, fully interchangeable terminology referring to the finished lubrication product comprising more than 50% by weight of a base oil plus a minor amount of an additive composition.
[0028] As used herein, the terms "additive package", "additive concentrate", "additive composition", "engine oil additive package", "engine oil additive concentrate", "packaging "Crankcase Additive Concentrate", "Crankcase Additive Concentrate", "Engine Oil Additive Pack", "Engine Oil Concentrate", are considered synonymous, fully interchangeable terminology referring to the portion of the lubricating oil composition, excluding a maximum of 50% by weight base oil blend. The additive package may or may not include the viscosity index improver or pour point depressant.
[0029] The term "alkaline" refers to metal salts, such as metal salts of sulfonates, carboxylates, salicylates and/or phenates, in which the amount of metal present exceeds the stoichiometric amount. These salts can have a conversion level greater than 100% (ie, they can comprise more than 100% of the theoretical amount of metal needed to convert the acid to its "normal", "neutral" salt). The term "metal ratio", often abbreviated as MR, is used to designate the ratio of total chemical equivalents of metal in the alkaline salt to chemical equivalents of the metal in a neutral salt according to known chemical reactivity and stoichiometry. In a normal or neutral salt, the metal ratio is one, and in an alkaline salt the MR is greater than one. They are commonly referred to as alkaline, hyperbasified, or superbasified salts and can be salts of sulfur organic acids, carboxylic acids, salicylates, and/or phenols. In the present disclosure, the alkaline detergent has a TBN of greater than 225 mg KOH/g. The alkaline detergent may be a combination of two or more alkaline detergents, each with a TBN greater than 225 mg KOH/g.
[0030] The term "whole metal" refers to the whole metal, metalloid or transition metal in the lubricating oil composition including the metal contributed by the detergent component(s) of the lubricating oil composition.
[0031] As used herein, the term "hydrocarbyl substituent" or "hydrocarbyl group" is used in its common sense, which is well known to those skilled in the art. Specifically, it refers to a group with a carbon atom directly attached to the rest of the molecule and predominantly of a hydrocarbon character. Examples of hydrocarbyl groups include: (a) hydrocarbon substituents, i.e., aliphatic substituents (e.g., alkyl or alkenyl), alicyclic substituents (e.g., cycloalkyl, cycloalkenyl), and substituted aromatic, aliphatic, and alicyclic substituents, as well as cyclic in which the ring is completed through another portion of the molecule (for example, two substituents together form an alicyclic portion); (b) substituted hydrocarbon substituents, i.e., substituents containing non-hydrocarbon groups which, in the context of this disclosure, do not change the predominantly hydrocarbon substituent (e.g. halo (especially chloro and fluoro), hydroxide, alkoxy, mercapto, alkylmercapto nitro , nitroso, amino, alkylamino and sulfoxy); and (c) hetero substituents, that is, substituents which, while having a predominantly hydrocarbon character, in the context of this disclosure, contain other than carbon in a ring or chain, otherwise composed of carbon atoms. Heteroatoms can include sulfur, oxygen and nitrogen, and encompass substituents such as pyridyl, furyl, thienyl and imidazolyl. In general, not more than two, for example, not more than one non-hydrocarbon substituent will be present for every ten carbon atoms in the hydrocarbyl group; typically, there will be no non-hydrocarbon substituents on the hydrocarbyl group.
[0032] As used herein, the term "percent by weight", unless expressly stated otherwise, means the percentage that the recited component represents to the weight of the entire composition.
[0033] The terms "soluble", "oil soluble" or "dispersible" used herein may, but do not necessarily, indicate that the compounds or additives are soluble, soluble, miscible or capable of being suspended in the oil in all proportions. The foregoing terms mean, however, that they are, for example, soluble, suspendable, dissolvable or stably dispersible in oil to a level sufficient to exert their intended effect in the environment in which the oil is used. In addition, the additional incorporation of other additives may also allow for the incorporation of higher levels of a particular additive, if desired.
[0034] The term "TBN", as used herein, is used to denote the total base number in mg KOH/g composition, as measured by the ASTM method D2896.
[0035] The term "alkyl" as used herein refers to saturated, straight-chain, branched, cyclic and/or substituted moieties of from about 1 to about 100 carbon atoms.
[0036] The term "alkenyl", as used herein, refers to unsaturated, straight, branched, cyclic and/or substituted moieties of about 3 to about 10 carbon atoms.
[0037] The term "aryl", as used herein, refers to single and multiple ring aromatic compounds which may include alkyl, alkenyl, alkylaryl, amino, hydroxyl, alkoxy, halo and/or heteroatoms substituents including, but not limited to limiting to nitrogen, oxygen, and sulfur.
[0038] A reduction in low speed pre-ignition events can be expressed as an "LSPI ratio". The term "LSPI ratio" refers to a ratio of the number of low speed pre-ignition events in a propelled internal combustion engine lubricated with the lubricating oil composition of the disclosure to a series of low speed pre-ignition events. speed in the same internal combustion engine lubricated with R-1 reference lubricating oil described here. A lubricating oil composition that reduces the LSPI ratio is effective in reducing low speed pre-ignition events in a powered internal combustion engine lubricated with the lubricating oil composition over a series of pre-ignition events low speed in the same engine lubricated with R-1 reference lubricating oil.
[0039] The lubricants, component combinations or individual components of the present disclosure may be suitable for use in various types of internal combustion engines. Suitable engine types may include, but are not limited to, heavy duty diesel, passenger car, light diesel, medium speed diesel, marine engines or motorcycle engines. An internal combustion engine can be a diesel powered engine, a gasoline powered engine, a natural gas powered engine, a biofuel powered engine, a blended diesel/biofuel powered engine, a blended gasoline/biofuel powered engine, a alcohol-powered engine, a gasoline/alcohol blended engine, a compressed natural gas (CNG) engine, or mixtures thereof. A diesel engine can be a compression ignition engine. A diesel engine can be a compression ignition engine with a spark ignition assist. A gasoline engine can be a spark-powered engine. An internal combustion engine can also be used in combination with an electrical or battery power source. An engine so configured is commonly known as a hybrid engine. The internal combustion engine can be a 2-stroke, 4-stroke or rotary engine. Suitable internal combustion engines include marine diesel engines (such as inland marine engines), aviation piston engines, low load diesel engines and motorcycle, automobile, locomotive and truck engines.
[0040] The internal combustion engine may contain components of one or more of an alloy of aluminum, lead, tin, copper, cast iron, magnesium, ceramics, stainless steel, composites and/or mixtures thereof. The components can be coated, for example, with a diamond-like carbon coating, a lubricated coating, a phosphorus-containing coating, a molybdenum-containing coating, a graphite coating, a coating containing nanoparticles and/or mixtures thereof. The aluminum alloy may include aluminum silicates, aluminum oxides or other ceramic materials. In one embodiment, the aluminum alloy is an aluminum silicate surface. As used herein, the term "aluminum alloy" is intended to be synonymous with "aluminum composite" and to describe a component or surface comprising aluminum and another component mixed or reacted at a microscopic or near-microscopic level, regardless of the detailed structure thereof. . This includes any conventional alloys with metals other than aluminum, as well as composite-type structures or alloys with non-metallic elements or composites with ceramic-like materials.
[0041] The composition of lubricating oil for an internal combustion engine can be suitable for any engine regardless of the content of sulfur, phosphorus or sulfated ash (ASTM D-874). The sulfur content of the engine oil lubricant can be about 1% by weight or less, or about 0.8% by weight or less, or about 0.5% by weight or less, or about 0 .3% by weight or less, or about 0.2% by weight or less. In one embodiment, the sulfur content can range from about 0.001% by weight to about 0.5% by weight, or about 0.01% by weight to about 0.3% by weight. The phosphorus content may be about 0.2% by weight or less, or about 0.1% by weight or less, or about 0.085% by weight or less, or about 0.08% by weight or less. less, or even about 0.06% by weight or less, about 0.055% by weight or less, or about 0.05% by weight or less. In one embodiment, the phosphorus content can be from about 50 ppm to about 1000 ppm, or from about 325 ppm to about 850 ppm. The total sulfated ash content can be about 2% by weight or less, or about 1.5% by weight or less, or about 1.1% by weight or less, or about 1% by weight or less. less, or about 0.8% by weight or less, or about 0.5% by weight or less. In one embodiment, the sulfated ash content can be from about 0.05% by weight to about 0.9% by weight, or about 0.1% by weight, or about 0.2% by weight to about of 0.45% by weight. In one embodiment, the sulfur content can be about 0.4% by weight or less, the phosphorus content can be about 0.08% by weight or less, and the sulfated ash is about 1% by weight. weight or less. In yet another embodiment, the sulfur content can be about 0.3% by weight or less, the phosphorus content is about 0.05% by weight or less, and the sulfated ash can be about 0.05% by weight or less. 0.8% by weight or less.
[0042] In one embodiment, the lubricating oil composition is an engine oil, wherein the lubricating oil composition may have (i) a sulfur content of about 0.5% by weight or less, (ii) a phosphorus content of about 0.1% by weight or less, and (iii) a sulfated ash content of about 1.5% by weight or less.
[0043] In some embodiments, the lubricating oil composition is suitable for use with engines fueled by low sulfur fuels, such as fuels containing about 1 to about 5% sulfur. Road vehicle fuels contain about 15 ppm sulfur (or approximately 0.0015% sulfur). The lubricating oil composition is suitable for use with heavy-duty internal combustion engines, including turbocharged or supercharged internal combustion engines.
[0044] In addition, the lubricants of the present description may be suitable to satisfy one or more industry specification requirements, such as ILSAC GF-3, GF-4, GF-5, GF-6, PC-11, CI- 4, CJ-4, ACEA A1/B1, A2/B2, A3/B3, A3/B4, A5/B5, C1, C2, C3, C4, C5, E4/E6/E7/E9, Euro 5/6, Jaso DL-1, Low SAPS, Mid SAPS, u OEM specifications such as DexosTM 1, DexosTM 2, MB-Approval 229.51/229.31, VW 502.00, 503.00/503.01, 504.00, 505.00, 506.00/506.01, 507.00 , 508.00, 509.00, BMW Longlife-04, Porsche C30, Peugeot Citroen Automobiles B71 2290, B71 2296, B71 2297, B71 2300, B71 2302, B71 2312, B71 2007, B71 2008, Ford WSS-M2C153-H, WSS3 -A, WSS-M2C945-A, WSS-M2C913A, WSS-M2C913-B, WSS-M2C913-C, GM 6094M, Chrysler MS-6395, or any past or future PCMO or HDD specifications not mentioned here. In some embodiments for passenger car engine 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.
[0045] Other hardware may not be suitable for use with the lubricant described. A "functional fluid" is a term that encompasses a variety of fluids, including but not limited to tractor hydraulic fluids, power transmission fluids including automatic transmission fluids, continuously variable transmission fluids and manual transmission fluids, hydraulic fluids , including tractor hydraulic fluids, certain gear oils, power steering fluids, fluids used in wind turbines, compressors, certain industrial fluids and fluids related to power train components. It should be noted that within each of these fluids, such as automatic transmission fluids, there are a variety of different types of fluids due to the various transmissions with different designs that have led to the need for fluids of markedly different functional characteristics. This is contrasted by the term "lubricating fluid" which is not used to generate or transfer energy.
[0046] With regard to tractor hydraulic fluids, for example, these fluids are general purpose products used for all lubricant applications in a tractor, except for lubricating the engine. These lubrication applications can include lubrication of gearboxes, PTO and clutch(s), rear axles, reduction gears, wet brakes and hydraulic accessories.
[0047] When a working fluid is an automatic transmission fluid, the automatic transmission fluids must have enough friction so that the clutch plates can transfer energy. However, the coefficient of friction of fluids tends to decrease due to the effects of temperature as the fluid heats up during operation. It is important that the tractor's hydraulic fluid or automatic transmission fluid maintains its high coefficient of friction at elevated temperatures, otherwise brake systems or automatic transmissions may fail. This is not a function of an engine oil.
[0048] Tractor fluids, e.g. Super Tractor Universal Oils (STUOs) or Universal Tractor Transmission Oil (UTTOs), can match the performance of engine oils with transmissions, differentials, final drive planetary gears, wet brakes and hydraulic performance. While many of the additives used to formulate a UTTO or STUO fluid are similar in functionality, they can have deleterious effects if not properly incorporated. For example, some extreme pressure and anti-wear additives used in engine oils can be extremely corrosive to copper components in hydraulic pumps. Detergents and dispersants used for gasoline or diesel engine performance can impair wet brake performance. Friction modifiers specific to the silent noise of wet brakes may not have the thermal stability required for engine oil performance. Each of these fluids, whether functional, tractor or lubricant, are designed to meet specific and stringent manufacturer requirements.
[0049] The present disclosure provides novel lubricating oil blends formulated for use as automobile crankcase lubricants. Embodiments of the present disclosure can provide lubricating oils suitable for crankcase applications and with improvements in the following characteristics: air drag, fuel alcohol compatibility, antioxidant, anti-wear performance, biofuels compatibility, foam reduction properties, friction reduction, economy fuel pressure, pre-ignition prevention, rust inhibition, soot dispersion and/or dispersibility, piston cleaning, deposit formation and water tolerance.
[0050] The engine oils of the present disclosure may be formulated by adding one or more additives, as described in detail below, to an appropriate base oil formulation. Additives can be combined with a base oil in the form of an additive package (or concentrate) or alternatively they can be combined individually with a base oil (or a mixture of both). Fully formulated engine oil can exhibit improved performance properties, based on the additives added and their respective proportions.
[0051] Additional details and advantages of disclosure will be presented in part in the description that follows, and/or may be learned by practice of disclosure. The details and advantages of the disclosure can be realized and achieved through the elements and combinations particularly pointed out in the appended claims. It is to be understood that the foregoing general description and the following detailed description are exemplary and explanatory only and are not restrictive of the disclosure as claimed. DETAILED DESCRIPTION
[0052] Various embodiments of the disclosure provide a lubricating oil composition and methods that can be used to reduce low speed pre-ignition (LSPI) events in a powered internal combustion engine. In particular, the hardened internal combustion engines of the present disclosure include turbocharged and supercharged internal combustion engines. Heavy-duty internal combustion engines include ignition injection, direct injection, and/or intake manifold injection engines. Spark-ignited internal combustion engines can be gasoline engines.
[0053] The composition of the invention includes a lubricating oil composition containing a lubricating viscosity base oil and a particular additive composition. The methods of the present disclosure employ the lubricating oil composition containing the additive composition. As described in more detail below, the lubricating oil composition can surprisingly be effective for use in reducing low speed pre-ignition events in a propelled internal combustion engine lubricated with the lubricating oil composition.
[0054] In another embodiment, the disclosure provides a method for reducing low speed pre-ignition events in a powered internal combustion engine. The method includes a step of lubricating the driven internal combustion engine with a lubricating oil composition including greater than 50% by weight of a base oil of lubricating viscosity having a total base number greater than 225 mg KOH/g measured by the method of ASTM D-2896 and one or more detergents containing magnesium. The one or more calcium-containing alkaline detergents provide 900 ppm by weight to less than 2400 ppm by weight of calcium for the lubricating oil composition and the one or more magnesium-containing detergents provide 50 ppm by weight to 1000 ppm by weight of magnesium for the lubricating oil composition. The driven internal combustion engine is operated and lubricated with the lubricating oil composition, whereby the low speed pre-ignition events in the lubricating oil lubricated engine can be reduced.
[0055] In some embodiments, the combustion chamber or cylinder walls of a spark ignition direct injection engine or intake manifold fuel injectable internal combustion engine with a turbocharger or supercharger are operated and lubricated with the lubricating oil composition, whereby low speed pre-ignition events in the engine lubricated with the lubricating oil composition can be reduced.
[0056] Optionally, the methods of the present invention may include a step of measuring low speed pre-ignition events of the internal combustion engine lubricated with the lubricating oil. In such methods, the internal combustion engine the reduction of LSPI events is a reduction of 50% or greater or, more preferably, a reduction of 75% or greater, and the LSPI events are counts of LSPI during 25,000 engine cycles, in that the engine is operated at 2000 revolutions per minute with an average effective brake pressure of 18,000 kPa.
[0057] As described in more detail below, embodiments of the disclosure can provide a significant and unexpected improvement in reducing LSPI events while maintaining a relatively high calcium detergent concentration in the lubricating oil composition. Disclosure modalities can also provide unexpected improvement in TEOST 33 test, while also reducing LSPI events. In some embodiments, the lubricating oil compositions and methods of the present invention can reduce the LSPI ratio.
[0058] In embodiments of the disclosure, the lubricating oil composition may also pass a TEOST 33 test. The lubricating oil compositions of the present invention may have a total base number of at least 7.5 mg KOH/g. The lubricating oil composition can have a ratio of total mmol metal (M) to total base number (TBN) ranging from greater than 4.5 to about 10.0 or greater than about 8 to about 8. 10. base oil
[0059] The base oil used in the lubricating oil compositions herein may be selected from any of the base oils in Groups IV as specified in the Base Oil Interconnection Guidelines of the American Petroleum Institute (API). The five base oil groups are as follows: Table 1

[0060] Groups I, II and III are mineral oil process stocks. Group IV base oils contain true synthetic molecular species, which are 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 esters and/or polyphenyl ethers and the like, but can also be naturally occurring oils such as vegetable oils. It should be noted that while Group III base oils are derived from mineral oil, the rigorous processing these fluids undergo makes their physical properties very similar to some true synthetics such as PAOs. Therefore, oils derived from Group III base oils may be referred to as synthetic fluids in the industry.
[0061] The base oil used in the disclosed lubricating oil composition can be a mineral oil, animal oil, vegetable oil, synthetic oil or mixtures thereof. Suitable oils may be derived from hydrocracking, hydrogenation, hydrofinishing, unrefined, refined and re-refined oils and mixtures thereof.
[0062] Unrefined oils are those derived from a natural, mineral or synthetic source with little or no purification treatment. Refined oils are similar to unrefined oils, except that they have been treated in one or more purification steps, which may result in the improvement of one or more properties. Examples of suitable purification techniques are solvent extraction, secondary distillation, acid or base extraction, filtration, percolation and the like. Oils refined to edible quality may or may not be helpful. Edible oils can also be called white oils. In some embodiments, the lubricating oil compositions are free of edible or white oils.
[0063] Re-refined oils are also known as recovered or reprocessed oils. These oils are obtained similarly to refined oils using the same or similar processes. Often these oils are further processed by techniques aimed at removing used additives and oil degradation products.
[0064] Mineral oils may include oils obtained by drilling or from plants and animals or any mixtures thereof. For example, such oils may include, but are not limited to, castor oil, lard oil, olive oil, peanut oil, corn oil, soybean oil and linseed oil, as well as lubricating mineral oils such as petroleum oils. solvent-treated or acid-treated, paraffinic, naphthenic or mixed paraffinic-naphthenic acid-treated liquids and lubricating oils. Such oils may be partially or fully hydrogenated, if desired. Oils derived from coal or shale may also be useful.
[0065] Useful synthetic lubricating oils may include hydrocarbon oils, such as polymerized, oligomerized or interpolymerized olefins (e.g., polybutylenes, polypropylenes, propylene/isobutylene copolymers); poly(1-hexenes), poly(1-octenes), 1-decene trimers or oligomers, for example poly(1-decenes), such materials are often referred to as α-olefins and mixtures thereof; alkylbenzenes (e.g. dodecylbenzenes, tetradecylbenzenes, dinonylbenzenes, di-(2-ethylhexyl)benzenes); polyphenols (e.g. biphenyls, terphenyls, alkylated polyphenols); diphenyl alkanes, alkylated diphenyl alkanes, alkylated diphenyl ethers and alkylated diphenyl sulfides and derivatives, analogues and homologues or mixtures thereof. Polyalphaolefins are typically hydrogenated materials.
[0066] Other synthetic lubricating oils include esters of polyols, diesters, liquid esters of phosphorus-containing acids (eg, tricresyl phosphate, trioctyl phosphate, and decane phosphonic acid diethyl ester) or polymeric tetrahydrofurans. Synthetic oils can be produced by Fischer-Tropsch reactions and typically can be hydroisomerized by hydrocarbons or Fischer-Tropsch waxes. In one embodiment, the oils may be prepared by a Fischer-Tropsch gas-to-liquid synthesis procedure as well as other gas-to-liquid oils.
[0067] A further 50% by weight of base oil included in a lubricating composition may be selected from the group consisting of Group I, Group II, Group III, Group IV, Group V and a combination of two or more of the above and wherein more that 50% by weight of base oil is different from base oils that result from the provision of additive components or viscosity index improvers in the composition. In another embodiment, greater than 50% by weight of the base oil included in a lubricant composition may be selected from the group consisting of Group II base oils, a Group III, a Group IV, a Group V and a combination of two or more than the foregoing and wherein more than 50% by weight of the base oil is different from the diluent oils that result from the provision of additive or viscosity index improver components in the composition.
[0068] The amount of lubricating viscosity oil present may be the remainder remaining after subtracting 100% by weight from the sum of the amount of performance additives including the viscosity index improver(s) and/or depressant( es) pour point and/or other main treatment additives. For example, the lubricating viscosity oil that may be present in a finished fluid may 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%, greater than about 85% by weight, or greater than about 90% by weight.
[0069] The lubricating oil composition may comprise not more than 10% by weight of a Group IV base oil, a Group V base oil or a combination thereof. In each of the foregoing embodiments, the lubricating oil compositions comprise less than 5% by weight of a Group V base oil. The lubricating oil composition does not contain any Group IV base oil. The lubricating oil composition does not contain any Group V base oil. detergents
[0070] The lubricating oil composition comprises one or more alkaline detergents and one or more alkaline calcium-containing detergents and one or more magnesium-containing detergents. Suitable detergent substrates include phenates, sulfate-containing phenates, sulfates, calixarates, salixarates, salicylates, carboxylic acids, phosphorous acids, mono- and/or di-thiophosphoric acids, alkyl phenols, sulfur-coupled alkyl phenol compounds or bridged phenols. methylene. Suitable detergents and their methods of preparation are described in more detail in numerous patent publications, including US 7,732,390 and cited references. The detergent substrate may be salted with an alkali or alkaline earth metal such as, but not limited to, calcium, magnesium, potassium, sodium, lithium, barium or mixtures thereof. In some embodiments, the detergent is barium-free. A suitable detergent may include alkali or alkaline earth metal salts of petroleum sulfonic acids and long chain mono- or di-alkylarylsulfonic acids, the aryl benzyl group being tolyl and xylyl. Examples of suitable additional detergents include, but are not limited to, calcium phenates, calcium sulfur-containing phenates, calcium perfluorooctane sulfonates, calcium calixarates, calcium salixarates, calcium salicylates, calcium carboxylic acids, calcium phosphorus acids, calcium, calcium mono- and/or di-thiophosphoric acids, calcium alkyl phenols, calcium sulfur-coupled alkyl phenol compounds, calcium methylene bridged phenols, magnesium phenates, magnesium sulfur-containing phenates, magnesium sulfonates, magnesium calixarates, magnesium salixarates, magnesium salicylates, magnesium carboxylic acids, magnesium phosphorus acids, magnesium mono- and/or di-thiophosphoric acids, magnesium alkyl phenols, magnesium sulfur-coupled alkyl phenol compounds, methylene magnesium bridged phenols, sodium phenates, sodium-containing phenates, sodium sulfonates, sodium calixarates, sodium salixarates, sodium salicylates, acid sodium carboxylic acids, sodium phosphorous acids, sodium mono- and/or di-thiophosphoric acids, sodium alkyl phenols, alkyl phenol compounds coupled with sodium sulfur or sodium methylene bridged phenols.
[0071] Alkaline detergents are well known in the art and can be alkali metal or alkaline earth alkaline detergents. Alkaline detergent additives are well known in the art and can be alkali metal or alkaline earth alkaline 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, for example an acid such as an aliphatic substituted sulfonic acid, an aliphatic substituted carboxylic acid or an aliphatic substituted phenol.
[0072] The terminology "alkaline" refers to metal salts, such as metal salts of sulfonates, carboxylates and phenates, in which the amount of metal present exceeds the stoichiometric amount. These salts can have a conversion level greater than 100% (ie, they can comprise more than 100% of the theoretical amount of metal needed to convert the acid to its "normal", "neutral" salt). The term "metal ratio", often abbreviated as MR, is used to designate the ratio of total chemical equivalents of metal in the alkaline salt to chemical equivalents of the metal in a neutral salt according to known chemical reactivity and stoichiometry. In a normal or neutral salt, the metal ratio is one, and in an alkaline salt the MR is greater than one. They are commonly referred to as alkaline, hyperbasified, or superbasified salts and can be salts of sulfur organic acids, carboxylic acids, and phenols.
[0073] An alkaline detergent has a TBN of about 225 mg KOH/gram or greater, or as other examples, a TBN of about 250 mg KOH/gram or greater, or a TBN of about 300 mg KOH/gram or greater, or a TBN of about 350 mg KOH/gram or greater, or a TBN of about 375 mg KOH/gram or greater, or a TBN of about 400 mg KOH/gram or greater.
[0074] Examples of suitable alkaline detergents include, but are not limited to, alkaline calcium phenates, sulfur-containing excess calcium phenates, alkaline calcium sulfonates, alkaline calcium calixarates, alkaline calcium salixarates, alkaline calcium salicylates, acids alkaline calcium carboxylic acids, alkaline calcium phosphorus acids, alkaline mono- and/or di-thiophosphoric calcium acids, alkaline calcium alkyl phenols, alkaline calcium sulfur-coupled alkyl phenol compounds, alkaline calcium methylene bridged phenols , alkaline magnesium phenates, alkaline magnesium sulfate-containing phenates, alkaline magnesium sulfates, alkaline magnesium calixarates, alkaline magnesium salixarates, alkaline magnesium salicylates, alkaline magnesium carboxylic acids, alkaline magnesium phosphorus acids, alkaline magnesium alkaline mono- and di-thiophosphoric calcium, alkaline magnesium alkyl phenols, alkalin compounds alkaline magnesium sulfur-coupled alkyl phenols or alkaline magnesium methylene bridged phenols.
[0075] The alkaline detergent can have a metal to substrate ratio of 1.1:1, or 2:1, or 4:1, or 5:1, or 7:1, or 10:1 .
[0076] In some embodiments, a detergent is effective in reducing or preventing rust in an engine.
[0077] The total detergent may be present at up to 10% by weight, or about up to about 8% by weight, or up to about 4% by weight, or greater than about 4% by weight to about 8% by weight based on the total weight of the lubricating oil composition.
[0078] The total detergent may be present in an amount to provide from about 950 to about 3,500 ppm of metal to the finished fluid. In other embodiments, the detergent can provide from about 1100 to about 3000 ppm metal, or about 1150 to about 2500 ppm metal, or about 1200 to about 2400 ppm metal to the finished fluid.
[0079] The lubricating oil compositions of the present disclosure include at least one alkaline calcium-containing detergent having a TBN of greater than 225 mg KOH/gram and at least one magnesium-containing detergent. The present disclosure also includes methods of using such lubricating oil compositions in a method of lubricating an engine by lubricating the engine with the lubricating oil composition and operating the engine.
[0080] The lubricating oil composition of the disclosure has a total amount of calcium from the alkaline calcium-containing detergent that ranges from 900 ppm by weight to less than 2400 ppm by weight based on a total weight of the lubricating oil composition. The alkaline calcium-containing detergent may be selected from an alkaline calcium sulfonate detergent, an alkaline calcium phenate detergent and an alkaline calcium salicylate detergent. In certain embodiments, the alkaline calcium-containing detergent comprises an alkaline calcium sulfonate detergent. In certain embodiments, the alkaline detergent is one or more calcium-containing detergents. Preferably, the alkaline detergent is a calcium sulfonate detergent.
[0081] In certain embodiments, the one or more alkaline calcium-containing detergents provide from about 900 to about 2000 ppm calcium to the finished fluid. As a further example, one or more alkaline calcium-containing detergents may be present in an amount to provide from about 1000 to about 2000 ppm calcium, or from about 900 to about 1800 ppm calcium or from about 1050 to about 1050 to 1650 ppm calcium, or about 1200 to 1600 ppm calcium for the finished fluid.
[0082] The amount of magnesium-containing detergent may be sufficient to provide from about 100 ppm by weight to about 800 ppm by weight of magnesium to the lubricating oil composition, based on the total weight of the lubricating oil composition.
[0083] The one or more magnesium-containing detergents may be alkaline magnesium-containing detergents having a total base number greater than 225 mg KOH/g measured by the method of ASTM D-2896 and the one or more alkaline magnesium-containing detergents may be selected from an alkaline magnesium sulfonate detergent, an alkaline magnesium phenate detergent, an alkaline magnesium salicylate detergent and mixtures thereof. Alternatively, magnesium-containing detergents may include one or more of the above-described magnesium-containing detergents, including low-base/neutral magnesium-containing detergents.
[0084] In some embodiments, the lubricating oil composition has a ratio of total millimoles of metal (M) to TBN of the lubricating oil composition ranging from greater than 4.5 to about 10.0. In some embodiments, the ratio of total millimoles of metal (M) to TBN of the lubricating oil composition ranges from greater than 8 to less than 10.0 or from 8 to 9.5 or from 8.1 to 9.0.
[0085] The lubricating oil compositions of the present invention may optionally also contain one or more low base/neutral detergents. 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 can be selected from a calcium sulfonate detergent, a calcium phenate detergent and a calcium salicylate detergent. 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.
[0086] The low base/neutral detergent may comprise at least 0.2% by weight of the lubricating oil composition. In some embodiments, the low base/neutral detergent comprises at least 0.25% by weight, or at least 0.5% by weight, or at least 0.7% by weight, or at least 1.0% by weight or at least 1.2% by weight or at least 2.0% by weight of the lubricating oil composition. The low base/neutral detergent may optionally include one or more low base/neutral caloric containing detergents.
[0087] In certain embodiments, the one or more low base/neutral calcium containing detergents provide from about 50 to about 1000 ppm calcium by weight to the lubricating oil composition based on a total weight of the lubricating oil composition. In some embodiments, the one or more low base/neutral detergents provide from 75 to less than 800 ppm, or from 100 to 600 ppm, or from 125 to 500 ppm by weight of calcium for the lubricating oil composition based on a total weight of lubricating oil composition.
[0088] In some embodiments, the ratio of ppm of calcium by weight supplied to the lubricating oil composition by the low base/neutral detergent to the ppm of calcium by weight supplied to the lubricating oil composition by the alkaline calcium detergent is about 0.01 to about 1, or from about 0.03 to about 0.7, or from about 0.05 to about 0.5, or from about 0.08 to about 0.4.
[0089] The detergent containing alkaline calcium may be an alkaline calcium sulfonate detergent. The alkaline calcium-containing detergent may optionally exclude alkaline calcium salicylate detergents. The lubricating oil may optionally exclude any magnesium-containing detergents or be magnesium-free. In either embodiment of the disclosure, the amount of sodium in the lubricating composition may be limited to no more than 150 ppm sodium, based on a total weight of the lubricating oil composition.
[0090] The lubricating oil composition may also include one or more optional components selected from the various additives presented below. antioxidants
[0091] The lubricating oil compositions herein may also optionally contain one or more antioxidants. Antioxidant compounds are known and include, for example, phenates, phenate sulfates, sulfur olefins, phosphorosulfated terpenes, sulfated esters, aromatic amines, alkylated diphenylamines (e.g. nonyl diphenylamine, dinonyl diphenylamine, octyl diphenylamine, di-octyl diphenylamine ), phenyl-alpha-naphthylamines, alkylated phenyl-alpha-naphthylamines, hindered non-aromatic amines, phenols, hindered phenols, oil-soluble molybdenum compounds, macromolecular antioxidants or mixtures thereof. Antioxidant compounds can be used alone or in combination.
[0092] The hindered phenol antioxidant may contain a secondary butyl group and/or a tertiary butyl group as a sterically hindering group. The phenol group may be further substituted by a hydrocarbyl group and/or a linking group which links to a second aromatic group. Examples of suitable hindered phenol antioxidants include 2,6-di-tert-butylphenol, 4-methyl-2,6-di-tert-butylphenol, 4-ethyl-2,6-di-tert-butylphenol, 4-propyl- 2,6-di-tert-butylphenol or 4-butyl-2,6-di-tert-butylphenol, or 4-dodecyl-2,6-di-tert-butylphenol. In one embodiment, the hindered phenol antioxidant may be an ester and may include, for example, IRGANOX™ L-135 available from BASF or an adduct derived from 2,6-di-tert-butylphenol and an alkyl acrylate, in that 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™ 4716 available from Albemarle Corporation.
[0093] 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, such that each antioxidant may be present in an amount sufficient to provide up to about 5%, by weight, based on weight. end of the lubricating oil composition. In one embodiment, the antioxidant can be a mixture of about 0.3 to about 1.5% diarylamine and about 0.4 to about 2.5% high molecular weight phenol, by weight, based on in the final weight of the lubricating oil composition.
[0094] Examples of suitable olefins that can be sulfurized to form a sulfurized olefin 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 and their dimers, trimers and tetramers are especially 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 butylacrylate.
[0095] Another class of sulfur olefin includes sulfated fatty acids and their esters. Fatty acids are often obtained from vegetable oil or animal oil and typically contain about 4 to about 22 carbon atoms. Examples of suitable fatty acids and their esters include triglycerides, oleic acid, linoleic acid, palmitoleic acid or mixtures thereof. Fatty acids are often obtained from lard oil, tall oil, peanut oil, soybean oil, cottonseed oil, sunflower seed oil or mixtures thereof. Fatty acids and/or esters can be mixed with olefins, such as α-olefins.
[0096] One or more antioxidants may be present in ranges from about 0% by weight to about 20% by weight, or about 0.1% by weight to about 10% by weight, or about 1% by weight. weight to about 5% by weight of the lubricating oil composition. anti-wear agents
[0097] The lubricating oil compositions contained herein may also optionally contain one or more anti-wear agents. Examples of suitable anti-wear agents include, but are not limited to, a metal thiophosphate; a metal dialkyldiphophosphate; a phosphoric acid ester or a salt thereof; a phosphate ester(s); a phosphite; a phosphorus-containing ester, ether or carboxylic amide; a sulfur olefin; thiocarbamate-containing compounds including thiocarbamate esters, alkylene-coupled thiocarbamates and bis(S-alkyldithiocarbamyl) disulfides; and mixtures thereof. A suitable anti-wear agent may be a molybdenum dithiocarbamate. Phosphorus-containing anti-wear agents are more fully described in European Patent 612 839. The metal in the dialkyl dithiophosphate salts can be an alkali metal, alkaline earth metal, aluminum, lead, tin, molybdenum, manganese, nickel, copper, titanium or zinc. . A useful anti-wear agent may be zinc dialkylthiophosphate.
[0098] Other examples of suitable anti-wear agents include titanium compounds, tartrates, tartrimides, oil-soluble amine salts of phosphorus compounds, sulfur olefins, phosphites (such as dibutyl phosphite), phosphonates, thiocarbamate-containing compounds such as esters of thiocarbamate, thiocarbamate amides, thiocarbamic ethers, alkylene-coupled thiocarbamates and bis(S-alkyldithiocarbamyl) disulfides. The tartrate or tartrimide may contain alkyl ester groups, where the sum of carbon atoms in the alkyl groups may be at least 8. The anti-wear agent may, in one embodiment, include a citrate.
[0099] The anti-wear agent may be present in ranges including about 0% by weight to about 15% by weight, or about 0.01% by weight to about 10% by weight, or about 0.05% by weight to about 5% by weight, or about 0.1% by weight to about 3% by weight of the lubricating oil composition.
[00100] An anti-wear compound can be a zinc dihydrocarbyl dithiophosphate (ZDDP) having a P:Z ratio of from about 1:0.8 to about 1:1.7. boron-containing compounds
[00101] The lubricating oil compositions optionally contained herein may contain one or more boron-containing compounds.
[00102] Examples of boron-containing compounds include borate esters, borated fatty amines, borated epoxides, borated detergents, and borated dispersants, such as borated succinimide dispersants, as disclosed in U.S. Patent 5,883,057.
[00103] The boron-containing compound, if present, can be used in an amount sufficient to provide up to about 8% by weight, about 0.01% by weight to about 7% by weight, about 0.05% by weight. weight to about 5% by weight, or about 0.1% by weight, to about 3% by weight of the lubricating oil composition. dispersers
[00104] The lubricating oil composition may optionally further comprise one or more dispersants or mixtures thereof. Dispersants are often known as ashless type dispersants because, prior to mixing into a lubricating oil composition, they do not contain ash-forming metals and normally do not contribute any ash when added to a lubricant. Ashless type dispersants are characterized by a polar group attached to a relatively high molecular weight hydrocarbon chain. Typical ashless dispersants include N-substituted long chain alkenyl succinimides. Examples of N-substituted long chain alkenyl succinimides include polyisobutylene succinimide with number average molecular weight of the polyisobutylene substituent in the range of about 350 to about 50,000 or about 5000 or about 3,000. Succinimide dispersants and their preparation are disclosed, for example, in U.S. Pat. U.S. 7,897,696 or U.S. Pat. U.S. 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. Succinimide dispersants are typically the imide formed from a polyamine, typically a poly(ethylenamine).
[00105] 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. Polyisobutylene succinimide can be used alone or in combination with other dispersants.
[00106] In some embodiments, the polyisobutylene, when included, may be greater than 50% by mol, greater than 60% by mol, greater than 70% by mol, greater than 80% by mol, or greater than 90% by mol. moles of terminal double bonds. This GDP is also referred to as highly reactive GDP ("HR- GDP"). HR-PIB having a number average molecular weight ranging from about 800 to about 5000 is suitable for use in embodiments of the present disclosure. Conventional PIB typically has less than 50 mol%, less than 40 mol%, less than 30 mol%, less than 20 mol% or less than 10 mol% terminal double bonds.
[00107] An HR-PIB with a number average molecular weight ranging from about 900 to about 3000 may be suitable. Such HR-PIB is commercially available or can be synthesized by polymerizing isobutene in the presence of a non-chlorinated catalyst, such as boron trifluoride, as described in U.S. Patent 4,152,429 to Boerzel et al. and U.S. Patent 5,739,355 to Gateau, et al. When used in the aforementioned ene thermal reaction, HR-PIB can lead to higher conversion rates in the reaction, as well as lower amounts of sludge formation, due to increased reactivity. A suitable method is described in U.S. Patent 7,897,696.
[00108] In one embodiment, the present disclosure further comprises at least one dispersant derived from polyisobutylene succinic anhydride ("PIBSA"). PIBSA can average between about 1.0 and about 2.0 succinic acid fractions per polymer.
[00109] The active % of alkenyl or alkyl succinic anhydride can be determined using a chromatographic technique. This method is described in columns 5 and 6 in U.S. Pat. U.S. 5,334,321.
[00110] The percentage of polyolefin conversion is calculated from the % actives using the equation in columns 5 and 6 in U.S. Pat. U.S. 5,334,321.
[00111] Unless otherwise indicated, all percentages are weight percent and all molecular weights are number average molecular weights.
[00112] In one embodiment, the dispersant may be derived from a polyalphaolefin succinic anhydride (PAO).
[00113] In one embodiment, the dispersant may be derived from an olefin maleic anhydride copolymer. As an example, the dispersant can be described as a poly-PIBSA.
[00114] In one embodiment, the dispersant may be derived from an anhydride that is grafted to an ethylene-propylene copolymer.
[00115] A class of suitable dispersants may be Mannich bases. Mannich bases are materials that are formed by the condensation of a higher molecular weight alkyl substituted phenol, a polyalkylene polyamine and an aldehyde, such as formaldehyde. Mannich bases are described in more detail in U.S. Patent 3,634,515.
[00116] A suitable class of dispersants may be high molecular weight esters or half ester amides.
[00117] A suitable dispersant can also be post-treated by conventional methods by a reaction with any of a variety of agents. These include boron, urea, thiourea, dimercaptothiazoles, carbon disulfide, aldehydes, ketones, carboxylic acids, hydrocarbon-substituted succinic anhydrides, maleic anhydride, nitriles, epoxides, carbonates, cyclic carbonates , hindered phenolic esters and phosphorus compounds. U.S. 7,645,726; U.S. 7,214,649; and U.S. 8,048,831 are incorporated herein by reference in their entirety.
[00118] In addition to carbonate and boric acid post-treatments, both compounds can be post-treated or post-treatment, with a variety of post-treatments intended to enhance or diffuse different properties. Such aftertreatments include those summarized in columns 27-29 of U.S. Pat. U.S. 5,241,003, incorporated herein by reference. Such treatments include, treatment with: Inorganic phosphorus acids or anhydrates (e.g., U.S. Pat. 3,403,102 and 4,648,980); Organic phosphorus compounds (e.g., U.S. Pat. 3,502,677); Phosphorus pentasulfides; Boron compounds, as noted above (e.g., U.S. Pat. 3,178,663 and 4,652,387); Carboxylic acid, polycarboxylic acids, anhydrides and/or acid halides (e.g., U.S. Pat. No. 3,708,522 and 4,948,386); Epoxides, polyepoxides or thioexpoxides (for example, U.S. Pat. 3,859,318 and 5,026,495); Aldehyde or ketone (e.g., U.S. Pat. No. 3,458,530); carbon disulfide (e.g., U.S. Pat. 3,256,185); Glycidol (e.g., U.S. Pat. 4,617,137); Urea, bullure or guanidine (for example, U.S. Patent 3,312,619; 3,865,813; and British Patent GB 1,065,595); Organic sulfonic acid (for example, U.S. Pat. 3,189,544 and British Patent GB 2,140,811); Alkenyl cyanide (e.g., U.S. Pat. 3,278,550 and 3,366,569); Diketene (e.g., U.S. Pat. No. 3,546,243); A diisocyanate (e.g., U.S. Pat. 3,573,205); Alkane sultone (e.g., U.S. Pat. No. 3,749,695); 1,3-Dicycarbonyl compound (e.g., U.S. Pat. 4,579,675); Alkoxylated alcohol sulfate or phenol (e.g., U.S. Pat. 3,954,639); Cyclic lactone (e.g., U.S. Pat. 4,617,138; 4,645,515; 4,668,246; 4,963,275; and 4,971,711); Linear monocarbonate or polycarbonate of cyclic carbonate or thiocarbonate, or chloroformate (e.g., U.S. Pat. No. 4,612,132; 4,647,390; 4,648,886; 4,670,170); Nitrogen-containing carboxylic acid (for example, U.S. Pat. 4,971,598 and British Patent GB 2,140,811); A hydroxy-protected chlorodicarbonyloxy compound (e.g., U.S. Pat. 4,614,522); lactam, thiolactam, thiolactone or dithiolactone (e.g., U.S. Pat. 4,614,603 and 4,666,460); Linear monocarbonate or polycarbonate of cyclic carbonate or thiocarbonate, or chloroformate (e.g., U.S. Pat. No. 4,612,132; 4,647,390; 4,646,886; and 4,670,170); Nitrogen-containing carboxylic acid (for example, U.S. Pat. 4,971,598 and British Patent GB 2,440,811); A hydroxy-protected chlorodicarbonyloxy compound (e.g., U.S. Pat. 4,614,522); lactam, thiolactam, thiolactone or dithiolactone (e.g., U.S. Pat. 4,614,603 and 4,666,460); Cyclic carbamate, cyclic thiocarbamate or cyclic dithiocarbamate (e.g., U.S. Pat. 4,663,062 and 4,666,459); hydroxyaliphatic carboxylic acid (e.g., U.S. Pat. No. 4,482,464; 4,521,318; 4,713,189); Oxidizing agent (e.g., U.S. Pat. 4,379,064); Combination of phosphorus pentasulfide and a polyalkylene polyamine (e.g., U.S. Pat. 3,185,647); Combination of a carboxylic acid or an aldehyde or ketone and sulfur or sulfur chloride (e.g., U.S. Pat. 3,390,086; 3,470,098); Combination of a hydrazine and carbon disulfide (e.g., U.S. Pat. 3,519,564); Combination of an aldehyde and a phenol (e.g., U.S. Pat. 3,694,229; 5,030,249; 5,039,307); Combination of an aldehyde and an O-diester of dithiophosphoric acid (e.g., U.S. Pat. 3,865,740); Combination of a hydroxyaliphatic carboxylic acid and a boric acid (e.g., U.S. Pat. No. 4,554,086); Combination of a hydroxyaliphatic carboxylic acid, then formaldehyde and a phenol (e.g., U.S. Pat. No. 4,636,322); Combination of a hydroxyaliphatic carboxylic acid and then an aliphatic dicarboxylic acid (e.g., U.S. Pat. 4,663,064); Combination of formaldehyde and a phenol and then glycolic acid (e.g., U.S. Pat. 4,699,724); Combination of a hydroxyaliphatic carboxylic acid or oxalic acid and then a diisocyanate (e.g., U.S. Pat. 4,713,191); A combination of inorganic acid or phosphorus anhydride or a partial or total sulfur analogue thereof and a boron compound (e.g., U.S. Pat. No. 4,857,214); Combination of an organic dioxide, then an unsaturated fatty acid, and then a nitrosoaromatic amine, optionally followed by a boron compound and then a glycolizing agent (e.g., U.S. Pat. No. 4,973,412); Combination of an aldehyde and a triazole (e.g., U.S. Pat. 4,963,278); Combination of an aldehyde and a triazole, then a boron compound (e.g., U.S. Pat. 4,981,492); Combination of cyclic lactone and a boron compound (e.g., U.S. Pat. 4,963,275 and 4,971,711). The patents mentioned above are incorporated herein in their entirety.
[00119] The TBN of a suitable dispersant can be from about 10 to about 65 on an oil-free basis, which is comparable to about 5 to about 30 TBN if measured in a dispersant sample containing about 50% oil. diluent.
[00120] The dispersant, if present, may be used in an amount sufficient to provide up to about 20% by weight, based on the final weight of the lubricating oil composition. Another amount of the dispersant that can be used can be from about 0.1% by weight to about 15% by weight, or about 0.1% by weight to about 10% by weight, or about 3% by weight. weight to about 10% by weight, or about 1% by weight to about 6% by weight, or about 7% by weight to about 12% by weight, based on the final weight of the lubricating oil composition. In some embodiments, the lubricating oil composition utilizes a mixed dispersant system. A single type or a mixture of two or more types of dispersants may be used in any desired ratio. friction modifiers
[00121] The lubricating oil compositions herein may also optionally contain one or more friction modifiers. Suitable friction modifiers may comprise metal-containing and metal-free friction modifiers and may include, but are not limited to, imidazolines, amides, amines, succinimides, alkoxylated amines, alkoxylated ether amines, amine oxides, amidoamines, nitris, betaines, quaternary amines, imines, amine salts, amino guanadine, alkanolamides, phosphonates, metal-containing compounds, glycerol esters, sulfur fatty compounds and olefins, sunflower oil, other naturally occurring vegetable or animal oils, esters of dicarboxylic acids, esters or esters partials of a polyol and one or more aliphatic or aromatic carboxylic acids and the like.
[00122] Suitable friction modifiers may contain hydrocarbyl groups which are selected from straight, branched or aromatic chain hydrocarbyl groups or mixtures thereof, and may be saturated or unsaturated. Hydrocarbyl groups can be compounds of carbon and hydrogen or heteroatoms, such as sulfur or oxygen. Hydrocarbyl groups can range from about 12 to about 25 carbon atoms. In some embodiments, the friction modifier may be a long chain fatty acid ester. In another embodiment, the long-chain fatty acid ester can be a mono-ester, or a di-ester, or a (tri)glyceride. The friction modifier can be a long-chain fatty amide, a long-chain fatty ester, long-chain fatty epoxide derivatives, or a long-chain imidazoline.
[00123] Other suitable friction modifiers may include nitrogen-free, ash-free (metal-free), organic friction modifiers. Such friction modifiers may include esters formed by reacting carboxylic acids and anhydrides with alkanols and generally include a terminal polar group (e.g., carboxyl or hydroxyl) covalently bonded to an oleophilic hydrocarbon chain. An example of an organic nitrogen-free friction modifier is not commonly known as glycerol monooleate (GMO) which may contain mono-, diand tri-esters of oleic acid. Other suitable friction modifiers are described in U.S. Pat. U.S. 6,723,685, incorporated herein by reference in its entirety.
[00124] Amine friction modifiers may include amines or polyamines. Such compounds may have hydrocarbyl groups that are linear, saturated or unsaturated, or a mixture thereof and may contain from about 12 to about 25 carbon atoms. Other examples of suitable friction modifiers include alkoxylated amines and ether alkoxylated amines. Such compounds may have hydrocarbyl groups that are linear, saturated, unsaturated, or a mixture thereof. They can contain from about 12 to about 25 carbon atoms. Examples include ethoxylated amines and ethoxylated ether amines.
[00125] Amines and amides can be used as such or in the form of an adduction or reaction product with a boron compound, such as a boron oxide, boron halide, metaborate, boric acid or a mono-, di or tri-alkyl. Other suitable friction modifiers are described in U.S. Pat. U.S. 6,300,291, incorporated herein by reference in its entirety.
[00126] A friction modifier may optionally be present in ranges, such as about 0% by weight to about 10% by weight, or about 0.01% by weight to about 8% by weight, or about 0.1% by weight to about 4% by weight. Component containing molybdenum
[00127] The lubricating oil compositions herein may also optionally contain one or more molybdenum-containing compounds. An oil-soluble molybdenum compound may have the functional performance of an anti-wear agent, an antioxidant, a friction modifier, or mixtures thereof. An oil-soluble molybdenum compound may include molybdenum dithiocarbamates, molybdenum dialkyldithiophosphates, molybdenum dithiophosphates, amine salts of molybdenum compounds, molybdenum xanthates, molybdenum thioxanthates, molybdenum sulfides, molybdenum carboxylates, molybdenum alkoxides, a trinuclear organo-molybdenum compound and/or mixtures thereof. Molybdenum sulfides include molybdenum disulfide. Molybdenum disulfide may be in the form of a stable dispersion. In one embodiment, the oil-soluble molybdenum compound may be selected from the group consisting of molybdenum dithiocarbamates, molybdenum dialkyldithiophosphates, amine salts of molybdenum compounds, and mixtures thereof. In one embodiment, the oil-soluble molybdenum compound may be a molybdenum dithiocarbamate.
[00128] Suitable examples of molybdenum compounds that may be used include commercial materials sold under trade names such as Molyvan 822™, Molyvan™ A, Molyvan 2000TM and Molyvan 855TM from RT Vanderbilt Co., Ltd. and Sakura-Lube™ S-165, S-200, S-300, S-310G, S-525, S-600, S-700 and S-710 available from Adeka Corporation, and mixtures thereof. Suitable molybdenum components are described in US 5,650,381; U.S. RE 37,363 E1; US RE 38,929 E1; and US RE 40,595 E1, incorporated herein by reference in its entirety.
[00129] 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, e.g. sodium hydrogen molybdate, MoOCl4, MoO2Br2, Mo2O3Cl6, molybdenum trioxide or similar acidic molybdenum compounds. Alternatively, the compositions may be provided with molybdenum by molybdenum/sulfur complexes of basic nitrogen compounds as described, for example, in U.S. Pat. 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 U.S. Patent Publication 2002/0038525, incorporated herein by reference in its entirety.
[00130] Another class of suitable organo-molybdenum compounds are trinuclear molybdenum compounds, such as those of the formula Mo3SkLnQz and mixtures thereof, where S represents sulfur, L represents independently selected ligands having organic groups with a sufficient number of atoms of carbon to make the compound soluble or dispersible in oil, n is from 1 to 4, k ranges from 4 to 7, Q is selected from the group of neutral electron donating compounds such as water, amines, alcohols, phosphines and ethers , z ranges from 0 to 5 and includes non-stoichiometric values. At least 21 total carbon atoms may be present among all organic groups of the ligands, such as at least 25, at least 30 or at least 35 carbon atoms. Additional suitable molybdenum compounds are described in U.S. Pat. U.S. 6,723,685, incorporated herein by reference in its entirety.
[00131] The oil-soluble molybdenum compound may be present in an amount sufficient to provide about 0.5 ppm to about 2000 ppm, about 1 ppm to about 700 ppm, about 1 ppm to about 550 ppm, about 5 ppm to about 300 ppm, or about 20 ppm to about 250 ppm molybdenum. Compounds containing titanium
[00132] Another class of additives includes oil-soluble titanium compounds. Oil-soluble titanium compounds can function as anti-wear agents, friction modifiers, antioxidants, deposit control additives, or more than one of these functions. In one embodiment, the oil-soluble titanium compound can be a titanium (IV) alkoxide. Titanium alkoxide can be formed from a monohydric alcohol, a polyol or mixtures thereof. Monohydric alkoxides can have 2 to 16, or 3 to 10 carbon atoms. In one embodiment, the titanium alkoxide may be titanium (IV) isopropoxide. In one embodiment, the titanium alkoxide may be titanium (IV) 2-ethylhexoxide. In one embodiment, the titanium compound can be the alkoxide of a 1,2-diol or polyol. In one embodiment, the 1,2-diol comprises a glycerol fatty acid mono-ester, such as oleic acid. In one embodiment, the oil-soluble titanium compound can be a titanium carboxylate. In one embodiment, the titanium (IV) carboxylate may be titanium neodecanoate.
[00133] In one embodiment, the oil-soluble titanium compound can be present in the lubricating oil composition in an amount to provide from zero to about 1500 ppm titanium by weight or about 10 ppm to 500 ppm titanium by weight or about 25 ppm to about 150 ppm. Compounds containing transition metal
[00134] In another embodiment, the oil-soluble compound can be a transition metal-containing compound or a metalloid. Transition metals may include, but are not limited to, titanium, vanadium, copper, zinc, zirconium, molybdenum, tantalum, tungsten and the like. Suitable metalloids include, but are not limited to, boron, silicon, antimony, tellurium and the like.
[00135] In one embodiment, the oil-soluble compound that can be used in a Ca/M weight ratio ranging from about 0.8:1 to about 70:1 is a titanium-containing compound, where M is the total metal in the lubricant composition as described above. Titanium-containing compounds can function as anti-wear agents, friction modifiers, antioxidants, deposit control additives, or more than one of these functions. Among the titanium-containing compounds that can be used or can be used for the preparation of the oil-soluble materials of the disclosed technology are various Ti(IV) compounds, such as titanium(IV) oxide; titanium (IV) sulfide; titanium (IV) nitrate; titanium (IV) alkoxides such as titanium methoxide, titanium ethoxide, titanium propoxide, titanium isopropoxide, titanium butoxide, titanium 2-ethylhexoxide; and other titanium compounds or complexes, including, but not limited to, titanium phenates; titanium carboxylates such as titanium (IV) 2-ethyl-1-3-hexanedioate or titanium citrate or titanium oleate; and titanium (IV) isopropoxide (triethanolamine). Other forms of titanium covered by the described technology include titanium phosphates such as titanium dithiophosphates (e.g. dialkyldithiophosphates) and titanium sulfonates (e.g. alkylbenzenesulfonates) or, in general, the reaction product of titanium compounds with various materials. acids to form salts, such as oil-soluble salts. The titanium compounds can thus be derived from, inter alia, organic acids, alcohols and glycols. Ti compounds can also exist in dimeric or oligomeric form, containing Ti-O-Ti structures. Such titanium materials are commercially available or can be readily prepared by appropriate synthetic techniques which will be apparent to one skilled in the art. They can exist at room temperature as a solid or a liquid, depending on the particular compound. They can also be supplied as a solution in a suitable inert solvent.
[00136] In one embodiment, the titanium may be provided as a Ti-modified dispersant, such as a succinimide dispersant. Such materials can be prepared by forming a mixed titanium anhydride between a titanium alkoxide and a hydrocarbyl substituted succinic anhydride, such as an alkenyl-(or alkyl)succinic anhydride. The resulting titanate-succinate intermediate can be used directly or can be reacted with any of a variety of materials, such as (a) a free, condensable, NH-functional, NH-functional succinimide/amide dispersant; (b) the components of a polyamine-based succinimide/amide dispersant, i.e., an alkenyl-(or alkyl-)succinic anhydride and a polyamine; (c) a hydroxy-containing polyester dispersant, prepared by the reaction of a succinic anhydride substituted with a polyol, aminoalcohol, polyamine or mixtures thereof. Alternatively, the titanate-succinate intermediate can be reacted with other agents, such as alcohols, aminoalcohols, ether alcohols, polyether alcohols or polyols, or fatty acids, and the product used either directly to impart Ti to a lubricant, or else also react with the succinic dispersants as described above. As an example, 1 part (in mol) of tetraisopropyl titanate can be reacted with about 2 parts (in mol) of a polyisobutene substituted succinic anhydride at 140-150°C for 5 to 6 hours to provide a dispersant. or titanium-modified intermediate. The resulting material (30 g) can be further reacted with a succinimide dispersant from polyisobutene substituted succinic anhydride and a mixture of polyethylene polyamine (127 grams + diluent oil) at 150°C for 1.5 hours, to produce a titanium-modified succinimide dispersant.
[00137] Another titanium-containing compound may be a reaction product of titanium alkoxide and C6 to C25 carboxylic acid. The reaction product can be represented by the following 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 by the formula:
wherein each of R1 , R2 , R3 , and R4 are the same or different and are selected from a hydrocarbyl group containing from about 5 to about 25 carbon atoms. Suitable carboxylic acids may 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.
[00138] In one embodiment, the oil-soluble titanium compound can be present in the lubricating oil composition in an amount to provide from 0 to 3000 ppm of titanium by weight or 25 to about 1500 ppm of titanium by weight or about 35 ppm to 500 ppm titanium by weight or about 50 ppm to about 300 ppm. Viscosity Index Improvers
[00139] The lubricating oil compositions contained herein may also optionally contain one or more viscosity index improvers. Suitable viscosity index improvers may include polyolefins, olefin copolymers, ethylene/propylene copolymers, polyisobutenes, hydrogenated styrene-isoprene polymers, styrene/maleic ester copolymers, hydrogenated styrene/butadiene copolymers, hydrogenated isoprene polymers , alpha-olefin maleic anhydride copolymers, polymethacrylates, polyacrylates, polyalkylstyrenes, hydrogenated alkenyl aryl conjugated diene copolymers or mixtures thereof. Viscosity index improvers can include star polymers and suitable examples are described in U.S. Patent 8,999,905 B2.
[00140] The lubricating oil compositions herein may also optionally contain one or more viscosity index improvers of the dispersant in addition to a viscosity index improver or instead of a viscosity index improver. Suitable viscosity index improvers may include functionalized polyolefins, for example, ethylene-propylene copolymers that have been functionalized with the reaction product of an acylating agent (such as maleic anhydride) and an amine; amine-functionalized polymethacrylates or copolymers of esterified maleic anhydride and styrene reacted with an amine.
[00141] The total amount of viscosity index improver and/or viscosity index improver of the dispersant can be from about 0% by weight to about 20% by weight, about 0.1% by weight to about 15% by weight, about 0.1% by weight to about 12% by weight, or about 0.5% by weight to about 10% by weight, of the lubricating oil composition. Other optional additives
[00142] Other additives may be selected to perform one or more necessary functions of a lubricating fluid. Furthermore, one or more of the aforementioned additives may be multifunctional and provide additional or other functions than the function prescribed herein.
[00143] A lubricating oil composition according to the present disclosure may optionally include other performance additives. The other performance additives may be added to the specified additives of the present disclosure and/or may comprise one or more of the metal deactivators, viscosity index improvers, ashless TBN enhancers, friction modifiers, anti-wear agents, corrosion inhibitors, rust inhibitors, dispersants, viscosity index improving dispersants, extreme pressure agents, antioxidants, foam inhibitors, demulsifiers, emulsifiers, pour point depressants, seal swelling agents and mixtures thereof. Typically, fully formulated lubricating oil will contain one or more of these performance additives.
[00144] Suitable metal deactivators may include benzotriazole derivatives (typically tolyltriazole), dimercaptothiadiazole derivatives, 1,2,4-triazoles, benzimidazoles, 2-alkyldithio benzimidazoles or 2-alkyldithio benzothiazoles; foam inhibitors including copolymers of ethyl acrylate and 2-ethylhexylacrylate and optionally vinyl acetate; demulsifiers including trialkyl phosphates, polyethylene glycols, polyethylene oxides, polypropylene oxides and polymers of ethylene oxide and propylene oxide; pour point depressants, including maleic anhydride-styrene esters, polymethacrylates, polyacrylates or polyacrylamides.
[00145] Suitable foam inhibitors include silicon-based compounds such as siloxane.
[00146] Suitable pour point depressants may include polymethylmethacrylates or mixtures thereof. Pour point depressants may be present in an amount sufficient to provide from about 0% by weight to about 1% by weight, about 0.01% by weight to about 0.5% by weight, or about 0.02% by weight to about 0.04% by weight based on the final weight of the lubricating oil composition.
[00147] Suitable rust inhibitors may be a single compound or a mixture of compounds which have the property of inhibiting corrosion of ferrous metal surfaces. Non-limiting examples of rust inhibitors useful herein include oil-soluble high molecular weight organic acids such as 2-ethylhexanoic acid, lauric acid, myristic acid, palmitic acid, oleic acid, linoleic acid, linolenic acid, behenic acid and cerotic acid, as well as oil-soluble polycarboxylic acids, including dimer and trimer acids, such as those produced from tall oil fatty acids, oleic acid and linoleic acid. Other suitable corrosion inhibitors include long chain alpha, omega-dicarboxylic acids in the molecular weight range of about 600 to about 3000 and alkenylsuccinic acids in which the alkenyl group contains about 10 or more carbon atoms, such as tetrapropenylsuccinic acid. , tetradecenylsuccinic acid and hexadecenylsuccinic acid. Another useful type of acid corrosion inhibitors are alkenylsuccinic acid methylesters having from about 8 to about 24 carbon atoms in the alkenyl group with alcohols, such as polyglycols. Corresponding half amides of such alkenylsuccinic acids are also useful. A useful rust inhibitor is a high molecular weight organic acid. In some embodiments, an engine oil is devoid of a rust inhibitor.
[00148] The rust inhibitor, if present, may be used in an amount sufficient to provide from about 0% by weight to about 5% by weight, about 0.01% by weight to about 3% by weight, about from 0.1% by weight to about 2% by weight, based on the final weight of the lubricating oil composition.
[00149] In general terms, a suitable crankcase lubricant may include additive components in the ranges listed in the following table. Table 2

[00150] The percentages of each component above represent the percentage by weight of each component, based on the weight of the final lubricating oil composition. The remainder of the lubricating oil composition consists of one or more base oils.
[00151] The additives used in formulating the compositions described herein may be mixed into the base oil individually or in various sub-combinations. However, it may be suitable to mix all components simultaneously using an additive concentrate (i.e. additives plus a diluent such as a hydrocarbon solvent). The additives used in formulating the compositions described herein may be blended into the base oil individually or in various sub-combinations. However, it may be suitable to mix all components simultaneously using an additive concentrate (i.e. additives plus a diluent such as a hydrocarbon solvent).
[00152] The present disclosure provides novel lubricating oil blends specifically formulated for use as automobile engine lubricants. Embodiments of the present disclosure may provide lubricating oils suitable for engine applications that provide improvements in one or more of the following characteristics: low speed pre-ignition events, antioxidants, anti-wear performance, rust inhibition, fuel economy, water tolerance , air drag, seal protection, deposit reduction, i.e. pass TEOST 33 test and foam reduction properties.
[00153] Fully formulated lubricants conventionally contain an additive package, referred to herein as a dispersant/inhibitor package or DI package, which will provide the characteristics that are needed in the formulations. Suitable DI packages are described, for example, in US Patents 5,204,012 and 6,034,040, for example, Among the types of additives included in the additive package can be dispersants, signal swelling agents, antioxidants, foam inhibitors, lubricating agents, rust inhibitors, corrosion inhibitors, demulsifiers, viscosity index improvers and the like. Several of these components are well known to those skilled in the art and are generally used in amounts conventional with the additives and compositions described herein.
[00154] The following examples are illustrative, but not limiting, of the methods and compositions of the present disclosure. Other modifications and suitable adaptations of the variety of conditions and parameters commonly encountered in the field, and which are obvious to those skilled in the art, are within the spirit and scope of the disclosure. All patents and publications cited herein are fully incorporated by reference herein in their entirety. EXAMPLES
[00155] Fully formulated lubricating oil compositions containing conventional additives were made and tested in a powered internal combustion engine to determine their influence on low speed pre-ignition events. Each of the lubricating oil compositions contained a major amount of a base oil, a conventional DI package of base and one or more viscosity index improvers, where the DI package of base (minus the viscosity index improver) provided approx. from 8 to about 12 weight percent of the lubricating oil composition. The base DI package contained conventional amounts of dispersant(s), anti-wear additive(s), anti-foaming agent(s), and antioxidant(s), as set out in Table 3 below. Specifically, the base DI package contained a succinimide dispersant, a borate succinimide dispersant, a compound containing molybdenum in an amount sufficient to provide about 80 ppm of molybdenum to the lubricating oil composition, an organic friction modifier, one or more plus antioxidants and one or more anti-wear agents (unless otherwise noted). The base DI package and base oil were also blended with about 5 to about 10% by weight of one or more viscosity index improvers. A Group I base oil was used as a diluent for the viscosity index improvers. The largest amount of base oil (about 78 to about 87% by weight) was from a Group III base oil. The components that were varied are specified in the Tables and in the discussion of Examples below. All values listed are given as a percentage by weight of the component in the lubricating oil composition (ie active ingredient plus thinner oil, if any), unless otherwise specified. Table 3 - Composition of the base DI Package
* The amount and type of detergent are varied in the following experiments, therefore, for the purposes of the base formulation, the amount of detergent is set to zero in Table 3.
[00156] Low Speed Pre-Ignition (LSPI) events were measured on a GM Ecotec 4-cylinder, 2.0-liter Turbocharged Gasoline Direct Injection (TGDi) engine. A complete LSPI driven motor test consisted of 4 test cycles. Within a single test cycle, two operational stages or segments are repeated to generate LSPI events. In stage A, when LSPI is most likely, the engine is operated at approximately 2000 rpm and about 18,000 kPa mean brake effective pressure (BMEP). In stage B, when LSPI is not likely to occur, the engine is operated at about 1500 rpm and about 17,000 kPa BMEP. For each stage, data is collected on over 25,000 engine cycles. The structure of a test cycle is as follows: stage A - stage A - stage B - stage B - stage A - stage A. Each stage is separated by an idle period. As the LSPI is statistically significant during stage A, the LSPI event data that was considered in the present examples only included LSPI events generated during stage A operation. Thus, for a full LSPI-driven motor test, the data were generally generated in a total of 16 stages and were used to evaluate the performance of comparative and inventive oils.
[00157] LSPI events were determined by monitoring the maximum cylinder pressure (PP) and when 2% of the combustible material in the combustion chamber burns (MFB02). The limit for maximum cylinder pressure is calculated for each cylinder and for each stage and is generally 65,000 to 85,000 kPa. The limit for MFB02 is calculated for each cylinder and for each stage and typically ranges from about 3.0 to about 7.5 Degree Crank Angle (CAD) After Neutral (ATDC). An LSPI was recorded when both the PP and MFB02 thresholds were exceeded in a single engine cycle. LSPI events can be reported in several ways. To remove the ambiguity involved with counting reports per engine cycle, where different engine driven tests may be conducted with a different number of engine cycles, the relative number of LSPI events from comparative and inventive oils were reported as " LSPI reason". In this way, the improvement over some standard response is clearly demonstrated.
[00158] All reference oils are commercially available engine oils that meet all ILSAC GF-5 performance requirements, including passing the TEOST-33 test discussed below.
[00159] In the following examples, the LSPI Ratio was reported as a ratio of the LSPI events of a test oil to the LSPI events of the reference oil "R-1". Reference oil R-1 was formulated from about 80.7% by weight of a Group III base oil, 12.1% by weight of HiTEC® 11150 PCMO Additive Pack available from Afton Chemical Corporation and 7, 2% by weight of an SSI 35 ethylene/propylene copolymer viscosity index improver. The HiTEC® 11150 Passenger Car Engine Oil Additive Package is a DI, API SN, ILSAC-GF-5 and ACEA A5/B5 qualified package. R-1 also showed the following properties and partial elemental analysis. R-1 Reference Oil

[00160] Considerable improvement in LSPI is recognized when there is more than a 50% reduction in LSPI events relative to R-1 (an LSPI ratio less than 0.5). A greater improvement in LSPI is recognized when there is a greater than 70% reduction in LSPI events (an LSPI ratio of less than 0.3), an even greater improvement in LSPI is recognized when there is a greater than 75% reduction in LSPI events. LSPI (an LSPI ratio of less than 0.25) and an even greater improvement in LSPI is recognized when there is a greater than 80% reduction in LSPI events relative to R-1 (an LSPI ratio of less than 0, 20) and an even greater improvement in LSPI is recognized when there is a greater than 90% reduction in LSPI events relative to R-1 (an LSPI ratio of less than 0.10). The ratio of LSPI to R-1 reference oil is therefore assumed to be 1.00.
[00161] The TEOST-33 test is a bench-top test that can be used to assess the oxidative degradation and/or thermal cooking of motor oil. According to the test, about 100 mL of test oil is used in a 12 cycle/2 hour test. The test results in crude oxidation of the oil (about 100 grams) in a hollow heated rod (TEOST depository rod) which will accumulate deposits during the test period. The test oil flows over the rod at about 0.5 grams per minute while the test piece is cycled 12 times through a temperature ranging from 200 to 480°C. Total deposit is the measured performance parameter. The total deposit is the sum of the deposit on the rod and the deposit on the oil that is removed by filtration. The more deposit measured indicates a poorer performance of the additive composition. Specifically, a test oil having a weight gain of 30 mg or less passes the TEOST 33 test.
[00162] The TBN measurements given in the tables below were determined using the method of ASTM D2896. TBN measurements were used to report the total TBN of the fully formulated example fluids in Table 5 below. Example 1
[00163] In the following examples, the impact of incorporating magnesium in varying amounts on the LSPI Ratio was determined. A combination of an alkaline calcium detergent, a low base/neutral calcium detergent, and an alkaline magnesium detergent was formulated in the same R-1 lubricating oil formulation as indicated above, replacing the alkaline calcium sulfonate detergent of R -1 for the detergent combinations listed in the tables below. R-2 is a commercial product that contains a calcium detergent and a magnesium compound. It was determined by ICP analysis that R-2 contained about 1240 ppmw of Ca and about 730 ppmw of Mg, based on the total weight of the lubricating oil composition.
[00164] Two samples were tested to compare the impact of an alkaline calcium sulfonate detergent on the LSPI Ratio as measured at R-1. C-1 contained an alkaline calcium sulfonate detergent which provided 1600 ppmw of Ca to the lubricating oil and C-2 contained an alkaline calcium sulfonate detergent which provided 1100 ppmw of Ca to the lubricating oil.
[00165] In I-3, C-3, I-1 and I-2, alkaline calcium sulfonate and alkaline magnesium sulfonate detergents were present in varying amounts. In addition, formulations I-1 and I-2 contained a low base/neutral calcium sulfonate detergent in an amount sufficient to provide 125 ppmw of Ca to the lubricating oil. Formulation I-3 contained a low base calcium phenate detergent in an amount sufficient to provide 125 ppmw of Ca to the lubricating oil composition. The composition and results of these test formulations are summarized in Table 4. Table 4

[00166] Commercial oils, R-1 and R-2, are included as reference oils to demonstrate the current state of the art. The R-1 oil contained an alkaline calcium-containing detergent and had a high calcium content. The R-2 oil contained a calcium-containing detergent and has a relatively low calcium content and a high magnesium content. R-1 and R-2 meet all performance requirements for ILSAC GF-5 and as such would demonstrate pass performance in the TEOST-33 benchtop oxidation test. Comparative Examples C-1, C-2 and C-3 are not commercially available fluids but are designed to demonstrate technical problems experienced by one of skill in the art when the detergent system is modified to meet the performance needs of LSPI.
[00167] In Table 4, formulations R-1, C-1 and C-2 demonstrate that decreasing the total calcium content in the lubricating oil composition reduces the LSPI Ratio. When the Ca content in the lubricating oil was decreased from 2400 ppmw to 1600 ppmw to 1100 ppmw, the LSPI Ratio also decreased to a minimum of 0.05. Although C-1 and C-2 provide significantly reduced LSPI Ratios, both failed the TEOST-33 test.
[00168] In Table 4, formulations C-2 and C-3 demonstrate that a combination of only an alkaline calcium sulfonate detergent and an alkaline magnesium sulfonate detergent is not sufficient to provide an LSPI Ratio that is reduced to desired level while still being able to pass the TEOST-33 test. In formulation C-3, the addition of alkaline magnesium sulfonate to the lubricating oil had no effect on the LSPI Ratio compared to formulation C-2 and both formulations C-2 and C-3 failed the TEOST-33 test. Since both of these examples contain reduced levels of alkaline calcium sulfonate detergent, it is evident that an additional additive in addition to the combination of an alkaline calcium sulfonate and an alkaline magnesium sulfonate detergent is required to obtain the desired LSPI Ratio, while still passing the EOST-33 test.
[00169] Inventive Formulations I-1 and I-2 demonstrate that the combination of an alkaline calcium sulfonate detergent, a low base/neutral calcium sulfonate detergent and an alkaline magnesium sulfonate detergent provides lubricating oils that reduce significantly improve the LSPI Ratio and pass the TEOST-33 test. A comparison of formulations I-1 and I-2 indicates that lower levels of magnesium are desirable to reduce the LSPI Ratio. A comparison of formulations I3 and I-2 demonstrates that different types of low base/neutral calcium detergents can be used to provide similar results for LSPI Ratio and TEOST-33 test pass when combined with a calcium sulfonate detergent alkaline and an alkaline magnesium sulfonate detergent. Example 2
[00170] In Example 2, the impact of incorporating a sodium sulfonate detergent, an alkaline calcium phenate detergent6 and a higher concentration of molybdenum on the LSPI Ratio was determined. TABLE 5

[00171] Commercial oils, R-1 and R-2, were again included as reference oils to demonstrate the current state of the art. The formulations of comparative examples C-4, C-5 and C-6 are not commercially available fluids but are designed to demonstrate technical problems experienced by one of skill in the art when the detergent system is modified to meet the performance needs of LSPI .
[00172] In Table 5, formulations C-4 and C-5 demonstrate that a sodium detergent provides a minor reduction in the LSPI Ratio relative to magnesium detergent use in the exemplified magnesium-containing compositions. Inventive Examples I-1 and I-4 demonstrate that when the molybdenum concentration is tripled in the presence of a magnesium-containing component, the LSPI Ratio is only slightly reduced.
[00173] Comparative Example C-3 and Inventive Example I-5 demonstrate that the combination of an alkaline calcium sulfonate detergent, an alkaline calcium phenate detergent and an alkaline magnesium sulfonate detergent provides the greatest reduction in the Ratio of LSPI, as well as passing the TEOST-33 Test. Furthermore, these examples also show that alkaline calcium phenate can significantly contribute to reducing the LSPI Ratio. Formulation C-6 demonstrated that a lubricating oil composition comprising only an alkaline calcium phenate detergent and a low base/neutral calcium detergent does not provide as large a reduction in the LSPI Ratio as the inventive combination of detergents, although still passing the TEOST-33 test. Example 3
[00174] In the following example, the impact of incorporating an alkaline calcium detergent and a magnesium sulfonate detergent on the temperature in the turbocharger coolant outlet stream (TCO temperature) was determined. Turbocharger Coking Test
[00175] Turbocharger coking test events were completed on a 2012 1.4L Chevy Cruze calibration engine with 3 liters of test oil charge and a qualified test fuel. A complete turbocharger tank test consisted of 2,000 cycles for approximately 536 hours. Each cycle consists of two stages. The first stage consists of the engine idling for 30 seconds, followed by an increase to 3,000 RPM for six and a half minutes. After this period, the engine speed is decreased to 2000 RPM for a period of 50 seconds, until the engine comes to a complete stop and the second stage starts. The second stage consists of a period of seven and a half minutes of the engine in the immersion period.
[00176] The temperature at the turbocharger coolant outlet stream (TCO temperature) is measured every 30 seconds. The initial baseline temperature is measured after the initial 100 cycles are complete to warm up the engine. After the test has been carried out for 1800 cycles, the TCO temperature is measured again. A pass-through performance is defined as a less than 13% increase in TCO temperature from the baseline TCO temperature and engine operation without measured boost pressure of less than 5 kPa lasting for a duration of 10 consecutive seconds during the entire 2000 cycle test.
[00177] To determine an additional performance parameter of this test, the ASTM Manual 20 Non-Rubbing Carbon Method is used to analyze different areas of the turbocharger upon completion of the Turbocharger Coking Test. After 2000 cycles or after operating to failure, an Average Merit Rating is determined by averaging the merit ratings assigned to each of the six different turbocharger areas, i.e. A) Turbine Shaft Area, B) Shaft Area of Turbine, C) Center Housing Turbine End Orifice, D) Center Housing Turbine Inlet Orifice, E) Center Housing Turbine Outlet Orifice, and F) Inlet Pipe. The Average Merit Rating is reported as a range of 0-10 merits. A rating of 10 merit is the highest and best rating and a rating of 0 merit is the lowest and lowest merit rating. The composition and test result of the formulation are summarized in Table 6. Table 6


[00178] In Table 6, the I-6 formulation demonstrates acceptable results for the TCO temperature rise and relatively high Average Merit Rating tests.
[00179] At various places throughout this specification, reference has been made to a number of U.S. Patents and other documents. All such cited documents are expressly incorporated in their entirety in this disclosure as if fully set forth herein.
[00180] Other embodiments of the present disclosure will be apparent to those skilled in the art from a consideration of the specification and practice of the embodiments described herein. As used throughout the specification and claims, "a" and/or "an" may refer to one or more than one. Unless otherwise indicated, all numbers expressing amounts of ingredients, properties such as molecular weight, percentage, ratio, reaction conditions, and so on used in the specification and claims are to be understood to be modified in all cases by the term "fence" whether or not the term "fence" is present. Therefore, unless otherwise indicated, the numerical parameters set forth in the specification and claims are approximations which may vary depending upon the desired properties sought to be achieved by the present disclosure. In the end, and not as an attempt to limit the application of the doctrine of equivalents to the scope of the claims, each numerical parameter should at least be interpreted in light of the number of significant digits reported and by the application of ordinary rounding techniques. While the numerical ranges and parameters that define the broad scope of the disclosure are approximations, the numerical values set forth in the specific examples are reported as accurately as possible. Any numerical value, however, inherently contains certain errors that necessarily result from the standard deviation found in its respective test measures. The specification and examples are intended to be considered exemplary only, with the true scope and spirit of the disclosure being indicated by the following claims.
[00181] The foregoing modalities are susceptible to considerable variation in practice. Accordingly, the embodiments are not intended to be limited to the specific exemplifications described herein. Rather, the foregoing modalities are within the spirit and scope of the appended claims, including their equivalents available as a matter of law.
[00182] Patent holders do not intend to dedicate any modality disclosed to the public and, insofar as any disclosed modifications or alterations do not literally fall within the scope of the claims, they are considered part of the same under the doctrine of equivalents.
[00183] It is to be understood that each component, compound, substituent or parameter disclosed herein is to be interpreted as being disclosed for use alone or in combination with one or more of each of the other components, compounds, substituents or parameters described herein.
[00184] It is also to be understood that each amount/value or range of amounts/values for each component, compound, substituent or parameter disclosed herein shall be interpreted as also being disclosed in combination with each amount/value or range of amounts/values disclosed for any other component(s), compound(s), substituent(s) or parameter(s) disclosed herein and that any combination of amounts/values or ranges of amounts/values for two or more component(s), compound(s) )), the substituent(s) or parameters described herein are thus also disclosed in combination with each other for the purposes of this description.
[00185] It is further understood that each range disclosed herein shall be interpreted as a disclosure of each specific value within the disclosed range that has the same number of significant digits. Thus, a range of 1-4 is to be interpreted as an express disclosure of the values 1, 2, 3 and 4.
[00186] It is further understood that each lower limit of each range disclosed herein shall be interpreted as disclosed in combination with each upper limit of each range and each specific value within each range disclosed herein for the same component, compounds, substituent or parameter. Thus, this disclosure should be interpreted as an all-range disclosure 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 of each track.
[00187] In addition, specific amounts/values of a component, compound, substituent or parameter disclosed in the description or in an example should be interpreted as a disclosure of a lower or upper limit of a range and therefore may be combined with any other lower or upper limit of a range or specific amount/value for the same component, compound, substituent or parameter described elsewhere in the application to form a range for that component, compound, substituent or parameter.

权利要求:
Claims (18)
[0001]
1. A lubricating oil composition comprising: greater than 50% by weight of a lubricating viscosity base oil; and an additive composition having: an alkaline calcium sulfonate detergent having a total base number greater than 225 mg KOH/g measured by ASTM method D-2896, one or more magnesium-containing detergents, and one of: (a) a calcium phenate or alkaline calcium salicylate detergent with a total base number greater than 225 mg KOH/g as measured by ASTM method D-2896, and (b) at least one low base detergent containing calcium, with a total base number of up to 175 mg KOH/g, measured by ASTM method D-2896 in an amount that provides at least 50 ppm by weight of calcium to the lubricating oil composition, based on the total weight of the lubricating composition in which the lubricating oil composition includes an amount of the alkaline calcium-containing detergents that provides 900 ppm by weight to less than 1800 ppm by weight of calcium for the lubricating oil composition, an amount of the magnesium-containing detergent that provides 50 ppm by weight to 1000 ppm in p magnesium eso for the lubricating oil composition, both amounts being based on a total weight of the lubricating oil composition based on a total weight of the lubricating oil composition; and the total calcium in the lubricating composition is 1800 ppm, based on the total weight of the lubricating composition.
[0002]
2. Lubricating oil composition according to claim 1, characterized in that an alkaline calcium phenate detergent is present in the lubricating oil composition.
[0003]
3. Lubricating oil composition according to claim 1, characterized in that the one or more magnesium-containing detergents are alkaline magnesium-containing detergents having a total base number greater than 225 mg KOH/g measured by the ASTM D- 2896 and the one or more alkaline magnesium containing detergents are selected from an alkaline magnesium sulfonate detergent, an alkaline magnesium phenate detergent, an alkaline magnesium salicylate detergent and mixtures thereof.
[0004]
4. Lubricating oil composition according to claim 1, characterized in that the amount of the magnesium-containing detergent is sufficient to provide from 100 ppm by weight to 800 ppm by weight of magnesium for the lubricating oil composition on a weight basis. total lubricating oil composition.
[0005]
5. The lubricating oil composition of claim 1, characterized in that the one or more alkaline calcium-containing detergents provide from 1000 to 1650 ppm by weight of calcium for the lubricating oil composition based on a total weight of the oil composition. lubricant.
[0006]
6. Lubricating oil composition according to claim 1, characterized in that the lubricating oil composition has a ratio of a total mmol of metal in the lubricating oil composition to a total base number of the lubricating oil composition varying from greater than 4.5 to 10.0.
[0007]
7. Lubricating oil composition according to claim 1, characterized in that the total base number of the lubricating oil composition is at least 7.5 mg KOH/g.
[0008]
8. Lubricating oil composition according to claim 1, characterized in that (b) the at least one low base/neutral calcium-containing detergent is present in the lubricating oil composition.
[0009]
A lubricating oil composition according to claim 8, characterized in that the at least one low base/neutral calcium containing detergent comprises a compound selected from a low base calcium sulfonate detergent, a calcium phenate detergent low base calcium, a low base calcium salicylate detergent and mixtures thereof.
[0010]
10. Lubricating oil composition according to claim 1, characterized in that the total calcium in the lubricating oil composition varies from 1,000 ppm to 1,800 ppm.
[0011]
11. Lubricating oil composition according to claim 1, characterized in that total calcium in the lubricating oil composition varies from 1,050 ppm to 1,650 ppm
[0012]
12. Lubricating oil composition according to claim 1, characterized in that one or more components selected from the group consisting of friction modifiers, anti-wear agents, dispersants, antioxidants and viscosity index improvers are present in the lubricating oil composition .
[0013]
13. Lubricating oil composition according to claim 1, characterized in that more than 50% of base oil is selected from the group consisting of Group II, Group III, Group IV, Group V base oils and a combination of two or more of the foregoing and wherein more than 50% by weight of the base oil is different from diluent oils which result from the provision of additive or viscosity index improver components in the composition.
[0014]
14. Method for operating a powered internal combustion engine, characterized in that it comprises: lubricating a powered internal combustion engine with a lubricating oil composition as defined in claim 1, comprising: more than 50% by weight of an oil lubricating viscosity base and an additive composition comprising: an alkaline calcium sulfonate detergent having a total base number greater than 225 mg KOH/g measured by the method of ASTM D-2896, an amount of one or more detergents containing sufficient magnesium to provide 50 ppm by weight to 1000 ppm by weight of magnesium for the lubricating oil composition based on a total weight of the lubricating oil composition, and one of: (a) a calcium phenate or alkaline calcium salicylate detergent with a total base number greater than 225 mg KOH/g, as measured by ASTM method D-2896, and (b) at least one low base detergent containing calcium, with a total base number of up to 175 mg KOH/g, measured by ASTM method D-2896 in an amount that provides at least 50 ppm by weight of calcium to the lubricating oil composition, based on the total weight of the lubricating composition, wherein the lubricating oil composition includes an amount of the alkaline calcium-containing detergent that provides 900 ppm by weight to less than 1800 ppm by weight of calcium for the lubricating oil composition, based on a total weight of the lubricating oil composition and the total calcium in the lubricating composition is 1800 ppm, with based on the total weight of the lubricating composition, and operating the engine lubricated with the lubricating oil composition.
[0015]
A method as claimed in claim 14, characterized in that the amount of the magnesium-containing detergent is sufficient to provide from 100 ppm by weight to 800 ppm by weight of magnesium to the lubricating oil composition based on the total weight of the composition. of lubricating oil.
[0016]
16. Method according to claim 14, characterized in that the total calcium in the lubricating oil composition varies from 1,000 ppm to 1,800 ppm.
[0017]
17. Method according to claim 14, characterized in that the lubrication step lubricates a combustion chamber or cylinder walls of a spark-driven direct injection engine or fuel injection internal combustion engine in the hole provided with a turbocharger or a supercharger.
[0018]
18. Method according to claim 14, characterized in that it includes a step of measuring low-speed pre-ignition events of the internal combustion engine lubricated with lubricating oil.

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同族专利:

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公开号 | 公开日

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KR20180048598A|2018-05-10|

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MX2018000133A|2018-03-23|

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CA2991787A1|2017-01-19|

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US10421922B2|2019-09-24|

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EP3322782A1|2018-05-23|

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RU2018104083A3|2019-12-24|

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RU2722017C2|2020-05-26|

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BR112018000615A2|2018-09-18|

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WO2017011687A1|2017-01-19|

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CN107922874A|2018-04-17|

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CN107922874B|2021-02-26|

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KR102271650B1|2021-06-30|

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RU2018104083A|2019-08-05|

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JP2018520244A|2018-07-26|

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US20170015927A1|2017-01-19|

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法律状态:
2020-02-27| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|

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2021-07-06| B06A| Patent application procedure suspended [chapter 6.1 patent gazette]|

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2021-11-30| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|

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2022-01-18| B16A| Patent or certificate of addition of invention granted [chapter 16.1 patent gazette]|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 14/07/2016, OBSERVADAS AS CONDICOES LEGAIS. |

优先权:

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申请号 | 申请日 | 专利标题

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US201562193297P| true| 2015-07-16|2015-07-16|

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US62/193297|2015-07-16|

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US15/147375|2016-05-05|

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US15/147,375|US10421922B2|2015-07-16|2016-05-05|Lubricants with magnesium and their use for improving low speed pre-ignition|

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PCT/US2016/042332|WO2017011687A1|2015-07-16|2016-07-14|Lubricants with magnesium and their use for improving low speed pre-ignition|

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