METHOD TO REDUCE LOW SPEED PRE-IGNITION EVENTS IN A REINFORCED INTERNAL COMBUSTION ENGINE

专利摘要:
a lubricating oil composition and a method of operation of a reinforced internal combustion engine. the lubricating oil composition has no more than 150 ppm sodium and includes a larger amount of a base oil and an additive composition that includes one or more detergents containing super-basified calcium with a total base number greater than 225 mg koh/ gram, in an amount sufficient to provide more than 1100 ppm by weight less than 2400 ppm by weight of calcium for the lubricating oil composition and one or more molybdenum-containing compounds in an amount sufficient to provide at least about 80 ppm by weight of molybdenum to the lubricating oil composition, all based on the total weight of the lubricating composition. the oil and method can reduce low-speed pre-ignition events in the reinforced internal combustion engine relative to a series of low-speed pre-ignition events in the same engine lubricated with a reference lube oil.
公开号:BR112018000657B1
申请号:R112018000657-2
申请日:2016-07-14
公开日:2021-08-10
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 additives and the use of such lubricating oil compositions to improve low-speed pre-ignition. BACKGROUND
[002] Reinforced internal combustion engines, such as turbocharged or supercharged 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, premature combustion during an inappropriate crank angle, and knocking. All of these, individually and in combination, have the potential to cause serious engine degradation and/or damage. However, as LSPI events occur sporadically and in an uncontrolled manner, 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 prior to the desired ignition of the air-fuel mixture by the detonator. 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 hot-spot pre-ignition.
[004] More recently, abnormal intermittent combustion has been observed in reinforced internal combustion engines at low speeds and medium to high loads. For example, when running the engine at 3,000 rpm or less, under load, with a mean effective brake pressure (BMEP) of at least 10,000 kPa, low speed pre-ignition (LSPI) may occur randomly and stochastic. During low speed engine operation, the compression stroke time is the longest.
[005] Several published studies have demonstrated that turbocharger use, engine design, engine coatings, piston shape, choice of fuel and/or engine oil additives can contribute to an increase in LSPI events . Consequently, there is a need for engine oil components and/or additive combinations that are effective to reduce or eliminate LSPI in heavy-duty internal combustion engines. SUMMARY AND TERMS
[006] The present disclosure relates to a lubricating oil composition and method of operation of a reinforced internal combustion engine. The lubricating oil composition includes greater than 50% by weight of a base oil of lubricating viscosity, one or more calcium-containing overbassified detergents having a total base number greater than 225 mg KOH/g in an amount sufficient to provide more than 1100 ppm by weight to less than 2400 ppm by weight of calcium for the lubricating oil composition based on a total weight of the lubricating oil composition, and one or more compounds containing molybdenum in an amount sufficient to provide at least about 80 ppm by weight of molybdenum for the lubricating oil composition based on the total weight of the lubricating composition. The lubricating oil composition contains no more than 150 ppm sodium, based on the total weight of the lubricating oil composition. In some embodiments, the lube oil composition can be effective to reduce low speed pre-ignition events in a reinforced internal combustion engine lubricated with the lube oil composition in relation to a series of low-speed pre-ignition events. low speed on the same engine lubricated with R-1 reference lube oil.
[007] In another embodiment, the disclosure provides a method to reduce low-speed pre-ignition events in a reinforced internal combustion engine. The method includes lubricating a reinforced internal combustion engine with a lubricating oil composition that includes greater than 50% by weight of a base oil of lubricating viscosity and an additive composition that includes one or more calcium-containing overbasing detergents having a number. of total base greater than 225 mg KOH/g in an amount that provides greater than 1100 ppm by weight to less than 2400 ppm by weight of calcium for the lubricating oil composition based on a total weight of the lubricating oil composition, and one or more compounds containing molybdenum in an amount sufficient to provide at least about 80 ppm by weight of molybdenum to the lubricating oil composition based on the total weight of the lubricating composition. The lubricating oil composition contains no more than 150 ppm sodium, based on the total weight of the lubricating oil composition. The engine is operated and lubricated with the lubricating oil composition. In some embodiments, the method of the invention reduces a number of low-speed pre-ignition events in the lubricated reinforced internal combustion engine relative to a series of low-speed pre-ignition events in the same engine lubricated with the lubricating oil. reference R-1.
[008] In each of the foregoing embodiments, one or more overbasic calcium-containing detergents may be selected from an overbasic calcium sulphonate detergent, an overbasic calcium phenate detergent, and an overbasic calcium salicylate detergent. In each of the above embodiments, one or more overbasing calcium-containing detergents can provide from about 1200 to about 2000 ppm, or from 1400 to 1800 ppm by weight of calcium to the lubricating oil composition based on a total weight of the composition. of lubricating oil.
[009] In each of the above embodiments, the one or more molybdenum-containing compounds may comprise a sulphur-free amine/molybdenum complex, molybdenum dithiocarbamate, molybdenum dithiophosphate and mixtures thereof.
[0010] In each of the above embodiments, the one or more molybdenum-containing compounds may be present in an amount that provides up to about 1000 ppm by weight of molybdenum based on the total weight of the lubricating composition.
[0011] In each of the above embodiments, the lubricating oil composition may include one or more components selected from friction modifiers, antiwear agents, dispersants, antioxidants and viscosity index improvers. In each of the above embodiments, a weight ratio of sulfur supplied to the lubricating oil composition from the additive composition to the weight of molybdenum in the lubricating oil composition is less than about 18:1. In each of the above examples, the lubricating oil composition can have a SASH of less than about 1% by weight.
[0012] In each of the aforementioned modalities, the reduction of one of the LSPI events is a reduction of 50% or 75% or greater and the LSPI events are LSPI counts for 25,000 cycles, in which the engine is operated at 2000 revolutions per minute with an average effective brake pressure of 18,000 kPa.
[0013] In each of the above modalities, the base oil can be selected from the base oils of Group I, Group II, Group III, Group IV or Group V, and a combination of two or more of the above. In each of the above embodiments, more than 50% by weight of base oil can be 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 above in that more than 50% by weight of base oil is different from the extender oils that arise from the provision of additive components or viscosity index improvers for the lubricating oil composition.
[0014] In each of the foregoing embodiments, the reinforced internal combustion engine may be a turbocharger or supercharger internal combustion engine and/or the reinforced internal combustion engine may be a reinforced spark ignition engine and/or a powered engine. reinforced gasoline. In each of the above embodiments, the reinforced internal combustion engine may be a spark-ignition turbocharged gasoline internal combustion engine.
[0015] In each of the above embodiments, the lubricating oil composition may comprise no more than 10% by weight of a Group IV base oil, a Group V base oil or a combination thereof. In each of the above embodiments, the lubricating oil compositions comprise less than 5% by weight of a Group V base oil.
[0016] In each of the foregoing embodiments, the overbasing calcium-containing detergent may be an overbasing calcium sulfonate detergent.
[0017] In each of the above embodiments, the overbasified calcium-containing detergent may optionally exclude overbasified calcium salicylate detergents.
[0018] In each of the above embodiments, the lubricating oil composition may optionally exclude any detergents containing magnesium or the lubricating oil composition may be magnesium free.
[0019] In each of the above embodiments, the lubricating oil composition may not contain any Group IV base oils.
[0020] In each of the above embodiments, the lubricating oil composition may not contain any Group V base oils.
[0021] The following definitions of terms are provided to clarify the meanings of certain terms as used herein.
[0022] The terms "oil composition", "lubrication composition", "lubricating oil composition", "lubricating oil", "lubricating composition", "lubrication composition", "fully formulated lubricating composition", "lubricant" , "crankcase oil", "crankcase lubricant", "engine oil", "engine lubricant", "engine oil" and "engine lubricant" are considered to be fully interchangeable and synonymous terminologies referring to the finished lubrication product comprising greater than 50% by weight base oil plus a minor amount of an additive composition.
[0023] As used herein, the terms "additive package", "additive concentrate", "additive composition", "engine oil additive package", "engine oil additive concentrate", "engine oil additive package" crankcase additives", "crankcase additive concentrate", "engine oil additive package", "engine oil concentrate" are considered to be fully interchangeable and synonymous terminologies referring to the portion of the lubricating oil composition, excluding more than 50% by weight base oil stock blend. The additive package may or may not include the viscosity index improver or pour point depressant.
[0024] The term "superbasified" 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 in excess of 100% (that is, 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 metal chemical equivalents in the overbasified salt to metal chemical equivalents 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 overbasified salt, MR, it is greater than one. They are commonly called overbassified, overbassified or overbassified salts and can be salts of sulfur organic acids, carboxylic acids, salicylates and/or phenols. In some examples, an over-basic detergent may have a TBN greater than 225 mg KOH/g. In some examples, a low/neutral detergent may have a TBN of less than 175 mg KOH/g. In some cases, “overbasified” can be abbreviated as “OB”. And in some cases, “Low Grade/Neutral” can be abbreviated as “LB/N”.
[0025] The term "total metal" refers to the total metal, metalloid or transition metal in the lubricating oil composition including the metal contributed by the detergent component(s) of the lubricating oil composition.
[0026] 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 hydrocarbon in character. Examples of hydrocarbyl groups include: (a) hydrocarbon substituents, i.e., aliphatic substituents (eg, alkyl or alkenyl), alicyclic substituents (eg, cycloalkyl, cycloalkenyl), and aromatic substituents substituted with aromatic, aliphatic and alicyclic groups, as well as cyclic substituents 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., non-hydrocarbon groups containing substituents which, in the context of this disclosure, do not change the predominantly hydrocarbon substituent (e.g., halo (especially chloro and fluoro), hydroxy, alkoxy, mercapto, alkylmercapto, nitro, nitroso, amino, alkyalamino and sulfoxy); and (c) hetero substituents, that is, substituents which, although predominantly hydrocarbon in 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, no more than two, for example, no 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.
[0027] As used herein, the term "percentage by weight", unless expressly stated otherwise, means the percentage that the recited component represents to the weight of the entire composition.
[0028] The terms "soluble", "oil soluble", or "dispersible" used herein may, but not necessarily, indicate that the compounds or additives are soluble, dissolvable, miscible, or capable of being suspended in oil at all times. proportions. The above terms mean, however, that they are, for example, soluble, susceptible to suspension, dissolvable or stably dispersible in oil to a level sufficient to exert their intended effect on the environment in which the oil is used. Furthermore, the addition of additional additives may also allow for the incorporation of higher levels of a particular additive, if desired.
[0029] The term "TBN", as used herein, is used to designate the Total Base Number in mg KOH/g as measured by the method of ASTM D2896.
The term "alkyl", as used herein, refers to substituted straight, branched, cyclic and/or saturated chain moieties of about 1 to about 100 carbon atoms.
The term "alkenyl", as used herein, refers to substituted straight-chain, branched, cyclic and/or unsaturated moieties of about 3 to 10 carbon atoms.
The term "aryl" as used herein refers to individual compounds and multiple aromatic rings which may include alkyl, alkenyl, alkylaryl, amino, hydroxyl, alkoxy, halo substituents, and/or heteroatoms, including, but not limited to, nitrogen, oxygen and sulfur.
[0033] The lubricants, combinations of components, or individual components of this description may be suitable for use in various types of internal combustion engines. Suitable engine types may include, but are not limited to heavy duty diesel, passenger car, light duty diesel, medium speed diesel, marine engines or motorcycle engines. An internal combustion engine can be a diesel engine, a gasoline engine, a natural gas engine, a biofuel engine, a blended diesel/biofuel engine, a blended gasoline/biofuel engine, a alcohol powered engine, an engine powered by mixed gasoline/alcohol, engine powered by compressed natural gas (CNG), or mixtures thereof. A diesel engine can be a compression ignition mechanism. A diesel engine can be a compression ignition engine with spark ignition assistance. A gasoline engine can be a spark-ignition engine. An internal combustion engine can also be used in combination with an electrical or battery power source. An engine configured in this way 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 inboard marine engines), aviation piston engines, low-load diesel engines, and motorcycle engines, automobiles, locomotives, and trucks.
[0034] The internal combustion engine may contain components of one or more than an aluminum alloy, lead, tin, copper, cast iron, magnesium, ceramic, 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 can 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 on a microscopic or near-microscopic level, regardless of the detailed structure of the same. This includes any conventional alloys with metals other than aluminum, as well as composite or alloy-type structures with non-metallic elements or compounds with ceramic-like materials.
[0035] The lubricating oil composition for an internal combustion engine can be suitable for any engine regardless of sulfur, phosphorus or sulphated ash content (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 wt% to about 0.5 wt%, or about 0.01 wt% to about 0.3 wt%. The phosphorus content can 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, 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 50ppm to about 1000ppm, or about 325ppm to about 850ppm. The total content of sulfated ash can be about 2 wt% or less, or about 1.5 wt% or less, or about 1.1 wt% or less, or about 1 wt% or less, or about 0.8% by weight or less, or about 0.5% by weight or less. In one embodiment, the content of sulfated ash can be from about 0.05 wt% to about 0.9 wt%, or about 0.1 wt%, or about 0.2 wt% to about of 0.45% by weight. In another 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 that of sulfated ash is about 1% in weight or less. In yet another embodiment, the sulfur content can be about 0.3 wt% or less, the phosphorus content is about 0.05 wt% or less, and the sulfated ash content can be about 0.8% by weight or less.
[0036] In one embodiment, the lubricating oil composition is a motor 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.
[0037] 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 about 0.0015% sulfur). The lubricating oil composition is suitable for use with heavy-duty internal combustion engines, including turbocharger or supercharger internal combustion engines.
[0038] 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, or original equipment manufacturer 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, WSS-M2C930 -A, WSS-M2C945-A, WSS-M2C913A, WSS-M2C913-B, WSS-M2C913-C, GM 6094-M, 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.
[0039] Other hardware may not be suitable for use with the described lubricant. 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, some gear oils, power steering fluids, fluids used in wind turbines, compressors, some industrial fluids and fluids related to power train components. It should be noted that within each of these fluids, eg 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.
[0040] With regard to tractor hydraulic fluids, for example, these fluids are general purpose products used for all lubricant applications on a tractor, except for lubricating the engine. These lubrication applications can include lubrication of gearboxes, power take-off and clutches, rear axles, reduction gears, wet brakes and hydraulic accessories.
[0041] When the functional fluid is an automatic transmission fluid, the automatic transmission fluids must have sufficient friction for the clutch plates to transfer power. However, the coefficient of friction of fluids tends to decrease due to temperature effects as the fluid heats up during operation. It is important that tractor hydraulic fluid or automatic transmission fluid maintain its high coefficient of friction at elevated temperatures, otherwise brake systems or automatic transmissions can fail. This is not a function of an engine oil.
[0042] Tractor fluids and, for example, Universal Super Tractor Oils (STUOs) or Universal Tractor Transmission Oils (UTTOs), can match the performance of engine oils with transmissions, differentials, planetary drive gears end, wet brakes and hydraulic performance. Although many of the additives used to formulate a UTTO or STUO fluid are of similar 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 quiet wet brake noise 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.
[0043] The present disclosure provides novel lubricating oil blends formulated for use as automotive crankcase lubricants. The modalities of the present disclosure can provide lubricating oils suitable for crankcase applications and with improvements in the following characteristics: air entrainment, alcohol fuel compatibility, antioxidant, anti-wear performance, biofuel compatibility, foam reduction properties, friction reduction, economy fuel, pre-ignition prevention, rust inhibition, sludge and/or soot dispersibility, piston cleanliness, deposit formation and water tolerance.
[0044] 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, can be combined individually with a base oil (or a mixture of both). Fully formulated engine oil may exhibit improved performance properties based on the additives added and their respective proportions.
[0045] Additional details and advantages of disclosure will be presented in part in the description that follows, and/or may be learned by practicing disclosure. The details and advantages of the disclosure can be realized and attained by means of the elements and combinations particularly pointed out in the appended claims. It is to be understood that both the above general description and the detailed description below are illustrative and explanatory only and are not restrictive of the disclosure as claimed. DETAILED DESCRIPTION
[0046] Various embodiments of the disclosure provide a lubricating oil composition and methods for reducing low speed pre-ignition events (LSPI) in a reinforced internal combustion engine. In particular, the ruggedized internal combustion engines of the present disclosure include turbocharger and supercharger internal combustion engines. Heavy duty internal combustion engines include ignition injection, direct injection and/or port fuel injection engines. Spark-ignition internal combustion engines may be gasoline engines.
[0047] In one embodiment, the description provides a lubricating oil composition and a method for operating a reinforced internal combustion engine. The lubricating oil composition includes greater than 50% by weight of a base oil of lubricating viscosity and an additive composition that includes one or more calcium-containing overbassified detergents having a total base number greater than 225 mg KOH/g in a amount sufficient to provide more than 1100 ppm by weight to less than 2400 ppm by weight of calcium for the lubricating oil composition based on a total weight of the lubricating oil composition and one or more molybdenum-containing compounds in an amount sufficient to provide fur minus about 80 ppm by weight of molybdenum for the lubricating oil composition based on the total weight of the lubricating composition. The lubricating oil composition contains no more than 150 ppm sodium, based on the total weight of the lubricating oil composition.
[0048] The additive composition includes at least one overbasified detergent and at least one molybdenum-containing compound. As described in more detail below, the lubricating oil composition can be effective for use in reducing low-speed pre-ignition events in a reinforced internal combustion engine, such as a turbocharger gasoline engine lubricated with the oil composition. lubricant.
[0049] In another embodiment, the disclosure provides a method for reducing low-speed pre-ignition events in a reinforced internal combustion engine. In another embodiment, the disclosure provides a method for reducing low-speed pre-ignition events in a reinforced internal combustion engine. The method includes lubricating a reinforced internal combustion engine with a lubricating oil composition that includes greater than 50% by weight of a base oil of lubricating viscosity and an additive composition that includes one or more calcium-containing overbasing detergents having a number. of total base greater than 225 mg KOH/g in an amount that provides greater than 1100 ppm by weight to less than 2400 ppm by weight of calcium for the lubricating oil composition based on a total weight of the lubricating oil composition, and one or more compounds containing molybdenum in an amount sufficient to provide at least about 80 ppm by weight of molybdenum to the lubricating oil composition based on the total weight of the lubricating composition. The lubricating oil composition contains no more than 150 ppm sodium, based on the total weight of the lubricating oil composition. The engine is operated and lubricated with the lubricating oil composition. The reinforced internal combustion engine is operated and lubricated with the lube oil composition, so low speed pre-ignition events in the engine lubricated with the lube oil composition can be reduced.
[0050] In some embodiments, the combustion chamber or cylinder walls of a spark-ignition direct injection engine or internal combustion engine with port fuel injection provided with a turbocharger or a supercharger is 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.
[0051] 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, in 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 LSPI counts over 25,000 cycles of the engine, in which the engine is operated at 2000 revolutions per minute with an average effective brake pressure of 18,000 kPa.
[0052] As described in more detail below, the embodiments of the disclosure can provide a significant and unexpected improvement in reducing LSPI events by maintaining a relatively high calcium detergent concentration in the lubricating oil composition. base oil
[0053] The base oil used in the lubricating oil composition herein may be selected from any of the base oils in Groups IV as specified in the Base Oil Interchangeability Guidelines of the American Petroleum Institute (API). The five groups of oil are as follows: Table 1

[0054] 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 synthetics and can include diesters, polyol esters, polyalkylene glycols, alkylated aromatics, polyphosphate esters, polyvinyl ethers and/or polyphenyl ethers, and the like, but they can also be oils that naturally occur, such as vegetable oils. It should be noted that although 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 can be called synthetic fluids in industry.
[0055] 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 can be derived from hydrocracking, hydrogenation, hydrofinishing, unrefined, refined, and re-refined oils, and mixtures thereof.
[0056] Unrefined oils are those derived from a natural, mineral, or synthetic source, with no or little additional purification treatment. Refined oils are similar to unrefined oils except that they have been treated in one or more purification steps, which can 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. Refined oils for qualifying an edible product may or may not be useful. Edible oils can also be called white oils. In some embodiments, the oil lubricating compositions are free of edible or white oils.
[0057] 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 spent additives and oil degradation products.
[0058] 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 such as liquid petroleum oils and lubricating oils of acid treated or solvent treated minerals of paraffinic, naphthenic or mixed paraffinic and naphthenic types. Such oils can be partially or fully hydrogenated, if desired. Oils obtained from coal or shale may also be useful.
Useful synthetic lubricating oils may include hydrocarbon oils such as polymerized, oligomerized, or interpolymerized olefins (for example, polybutylenes, polypropylenes, propylene/isobutylene copolymers); poly(1-hexenes), poly(1-octenes), trimers or oligomers of 1-decene, e.g., poly(1-decene), such materials often being called α-olefins, and mixtures thereof; alkylbenzenes (for example, dodecyl benzenes, tetradecyl benzenes, dinonyl benzenes, di-(2-ethyl hexyl)benzenes); polyphenyls (for example biphenyls, terphenyls, alkylated polyphenyls); diphenyl alkanes, alkylated diphenyl alkanes, alkylated diphenyl ethers and alkylated diphenyl sulfides and the derivatives, analogues and homologues thereof or mixtures thereof. Polyalphaolefins are typically hydrogenated materials.
[0060] Other synthetic lubricating oils include polyol esters, diesters, liquid esters of phosphorus-containing acids (eg, tricresyl phosphate, trioctyl phosphate, and the phosphonic acid diethyl ester decane), or polymeric tetrahydrofurans. Synthetic oils can be produced through Fischer-Tropsch reactions and typically can be hydroisomerized hydrocarbons or Fischer-Tropsch waxes. In one embodiment the oils can be prepared by a Fischer-Tropsch gas-to-liquid synthesis process, as well as other gas-to-liquid oils.
[0061] More than 50% by weight of base oil included in a lubricant composition can 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 in which more than 50% by weight of base oil is different from base oils arising from the provision of additive components or viscosity index improvers in the composition. In another embodiment, greater than 50% by weight of base oil included in a lubricant composition may be selected from the groups consisting of Group II, Group III, Group IV, Group V, and a combination of two or more of the above, and in that more than 50% by weight of base oil are different from the extender oils that arise from the provision of additive components or viscosity index improvers in the composition.
[0062] The amount of lubricating viscosity oil present can be the balance remaining after subtracting from 100% by weight the sum of the amount of performance additives, including viscosity index improver(s) and/or depressant(s) pour point and/or other major treatment additives. For example, the lubricating viscosity oil that can be present in a finished fluid can be one with greater than 50% by weight, such as greater than about 50% by weight, greater than about 60% by weight, greater than about 50% by weight. 70% by weight, more than about 80% by weight, more than about 85% by weight, or more than about 90% by weight.
[0063] The lubricating oil composition may comprise no more than 10% by weight of a Group IV base oil, a Group V base oil, or a combination thereof. In each of the above 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 oils. The lubricating oil composition does not contain any Group V base oils. Detergent
[0064] The lubricating oil composition comprises one or more over-basic detergents. Suitable detergent substrates include phenates, sulfur-containing phenates, sulfonates, calixarates, salixarates, salicylates, carboxylic acids, phosphorous acids, mono and/or dithiophosphoric acids, alkyl phenols, sulfur-coupled alkyl phenol compounds, or in bridged phenols. methylene. Suitable detergents and their methods of preparation are described in greater detail in numerous patent publications, including US 7,732,390 and the references cited therein. The detergent substrate can be salinized with an alkali or alkaline earth metal, such as, but not limited to, calcium, magnesium, potassium, sodium, lithium, barium or mixtures thereof. In some modalities, the detergent is barium-free. A suitable detergent can include alkali metal or alkaline earth salts of petroleum sulfonic acids and long chain mono or dialkyl aryl sulfonic acids with the aryl group being benzyl, tolyl and xylyl. Examples of suitable additional detergents include, but are not limited to, calcium phenates, calcium sulfur containing phenates, calcium sulfonate, calcium calixarates, calcium salixarates, calcium salicylates, calcium carboxylic acids, phosphorus acids, mono acids - and/or calcium dithiophosphoric acids, calcium alkyl phenols, alkyl phenol compounds coupled with sulfur and calcium, phenols bridged with methylene and calcium, magnesium phenates, phenates containing sulfur and magnesium, magnesium sulfonates, magnesium calixarates, salixarates of magnesium, magnesium salicylates, magnesium carboxylic acids, phosphorus and magnesium acids, magnesium mono and/or dithiophosphoric acids, magnesium alkyl phenols, sulfur, alkyl phenol compounds coupled with magnesium, phenols bridged with methylene and magnesium, sodium phenates, sodium sulphur-containing phenates, sodium sulfonates, sodium calixarates, sodium salixarates, sodium salicylates, sodium carboxylic acids, water phosphorus and sodium acids, sodium mono- and/or dithiophosphoric acids, sodium alkyl phenols, alkyl phenol compounds coupled with sulfur and sodium, or phenols bridged with methylene and sodium.
[0065] Overbassified detergent additives are well known in the art and can be alkaline earth metal or alkali overbase detergent additives. Such detergent additives can be prepared by reacting a metal oxide or metal hydroxide with a carbon dioxide gas and a substrate. 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.
[0066] The terminology "overbasified" 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 in excess of 100% (that is, 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 metal chemical equivalents in the overbasified salt to metal chemical equivalents 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 overbasified salt, MR, it is greater than one. They are commonly called overbassified, hyperbasified, or overbassified salts and can be salts of organic sulfur acids, carboxylic acids, or phenols.
[0067] A super-bassified detergent has a TBN of greater than 225 mg KOH/gram, 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.
[0068] Examples of suitable overbassified detergents include, but are not limited to, overbassified calcium phenates, overbassified calcium and sulfur-containing phenates, overbassified calcium sulfonate, overbassified calcium calixarates, overbassified calcium salixarates, overbassified calcium salicylates, carboxylic acids of superbasified calcium, superbasified phosphorus and calcium acids, superbasified calcium mono- and/or dithiophosphoric acids, superbasified alkyl phenols calcium, alkyl phenol compounds coupled with superbasified sulfur and calcium, bridged phenols with superbasified methylene and calcium, magnesium phenates super-bassified, super-basic sulfur and magnesium-containing phenates, super-basic magnesium sulfonates, super-basic magnesium calixarates, super-basic magnesium salixarates, super-basic magnesium salicylates, super-basic magnesium carboxylic acids, super-basic phosphorus and magnesium acids rbasified, overbasified magnesium mono- and/or dithiophosphoric acids, overbasified magnesium alkyl phenols, overbasified alkyl phenol compounds with sulfur and overbasified magnesium, or overbasified magnesium and methylene bridged phenols.
[0069] The over-basic detergent may 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 .
[0070] In some embodiments, a detergent is effective in reducing or preventing oxidation in an engine.
[0071] Detergent may include other detergents in addition to one or more over-based detergents. The total detergent may be present at up to 10% by weight, or about up to 8% by weight, or up to about 4% by weight, or greater than about 4% by weight to about 8% by weight based in a total weight of the lubricating oil composition.
[0072] The total detergent may be present in an amount sufficient to provide from about 1100 to about 3500 ppm of metal to the finished fluid. In other embodiments, the total 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.
[0073] The composition of additives used in the compositions and methods of the present disclosure include at least one overbasified detergent having a TBN greater than 225 mg KOH/gram. The lubricating oil composition of the disclosure including the additive composition has a total amount of calcium from the overbased detergent ranging from more than 1100 ppm by weight to less than 2400 ppm by weight, based on the total weight of the lubricating oil composition. .
[0074] The super-bassified detergent may be a super-basic calcium-containing detergent. The overbasified calcium-containing detergent can be selected from an overbassified calcium sulphonate detergent, an overbassified calcium phenate detergent and an overbassified calcium salicylate detergent. In certain embodiments, the overbasing calcium-containing detergent comprises an overbasing calcium sulfonate detergent. In certain embodiments, the overbasing detergent is one or more calcium containing detergents, preferably the overbasing detergent is a calcium sulphonate detergent.
In certain embodiments, the overbasified calcium-containing detergent delivers from about 1100 to about 2200 ppm of calcium to the finished fluid. As a further example, the one or more over-basic calcium detergents can be present in an amount sufficient to provide from about 1200 to about 2000 ppm of calcium to the finished fluid. As a further example, the one or more over-basic calcium detergents can be present in an amount sufficient to provide from about 1200 to 1800 ppm of calcium, or from about 1400 to 1800 ppm of calcium to the finished fluid.
[0076] The overbasified calcium-containing detergent may be an overbasified calcium sulphonate detergent. The overbasified calcium-containing detergent may optionally exclude overbasified calcium salicylate detergents. The lubricating oil can optionally exclude any detergents containing magnesium or be magnesium free. Component containing molybdenum
[0077] The lubricating oil compositions herein contain one or more oil-soluble molybdenum-containing compounds. An oil-soluble molybdenum compound may have the functional performance of an antiwear agent, an antioxidant, a friction modifier, or mixtures thereof. The oil-soluble molybdenum compound can be any one of molybdenum dithiocarbamates, molybdenum dialkyldithiophosphates, molybdenum sulfides, molybdenum disulfides, molybdenum dithiophosphinates, amine salts of molybdenum compounds, molybdenum xanthates, molybdenum sulfides, molybdenum thioxantates molybdenum, molybdenum carboxylates, molybdenum alkoxides, a trinuclear organo-molybdenum compound and/or mixtures thereof. Molybdenum-containing compounds can be sulfur-containing or sulfur-free compounds. Molybdenum disulfide can be in the form of a stable dispersion.
[0078] In one embodiment the oil-soluble molybdenum compound can be selected from the group consisting of molybdenum dithiocarbamates, molybdenum dialkyldithiophosphates, sulfur-free organomolybdenum complexes of organic amides and mixtures thereof. In one embodiment the oil-soluble molybdenum compound can be a molybdenum dithiocarbamate. Exemplary sulfur-free organomolybdenum complexes of organic amides are disclosed in US Patent No. 5,137,647 and Molyvan® 855T filed with R.T. Vanderbilt Co., Ltd. is one such complex.
Suitable examples of molybdenum compounds that can be used include commercial materials sold under the trade names such as Molyvan® 822, Molyvan® A, Molyvan® 2000. Molyvan® 807 and Molyvan® 855T 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 blends of the same. Suitable molybdenum components are described in US 5,650,381; US RE 37,363 E1; US RE 38,929 E1; and US RE 40,595 E1, incorporated herein by reference in their entirety.
[0080] 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, for example, hydrogenated sodium molybdate, MoOCl4, MoO2Br2, Mo2O3Cl6, molybdenum trioxide or compounds of similar acid molybdenum. Alternatively, lubricating oil compositions can be supplied with molybdenum by molybdenum/sulfur complexes of basic nitrogen compounds, as described, for example, in US Patent Nos. 4,263,152; 4,285,822; 4,283,295; 4,272,387; 4,265,773; 4,261,843; 4,259,195 and 4,259,194; and US Patent Publication No. 2002/0038525, incorporated herein by reference in its entirety.
[0081] Another class of suitable organo-molybdenum compounds are trinuclear molybdenum compounds, such as those of formula Mo3SkLnQz and mixtures thereof, wherein S represents sulfur, L represents independently selected ligands having organo groups with a number of carbon atoms sufficient 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 donor compounds such as water, amines, alcohols, phosphines, and ethers, and z ranges from 0 to 5 and includes non-stoichiometric values. At least 21 carbon atoms in total can be present in all organo groups of the linkers, such as at least 25, at least 30, or at least 35 carbon atoms. Additional suitable molybdenum compounds are described in US Patent No. 6,723,685, incorporated herein by reference in its entirety.
[0082] The oil-soluble molybdenum compound may be present in an amount sufficient to provide about 80 ppm to about 2000 ppm, from about 80 ppm to about 1000 ppm, about 80 ppm to about 700 ppm, about 120ppm to about 500ppm, or from about 150ppm to about 300ppm molybdenum.
[0083] The lubricating oil composition may also include one or more optional components selected from the various additives set forth below. Antioxidants
[0084] The lubricating oil compositions of this invention may also optionally contain one or more antioxidants. Antioxidant compounds are known and include, for example, phenates, phenate sulfides, sulfur olefins, phosphosulfurized terpenes, sulfur esters, aromatic amines, alkylated diphenylamines (e.g., nonyl diphenylamine, di-nonyl diphenylamine, octyl diphenylamine, di-octyl- diphenylamine), phenyl-alpha-naphthylamines, alkylated phenyl-alpha-naphthylamines, non-aromatic hindered amines, phenols, hindered phenols, macromolecular antioxidants, or mixtures thereof. Antioxidant compounds can be used alone or in combination.
[0085] The hindered phenol antioxidant may contain a secondary butyl and/or a tertiary butyl group as a steric hindering group. The phenol group may be additionally substituted with a hydrocarbyl group and/or a bridging group which attaches to a second aromatic group. Examples of suitable hindered phenolic 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 a acrylate. alkyl, where the alkyl group can 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 atoms of carbon. Another commercially available hindered phenol antioxidant may be an ester and may include ETHANOXTM 4716 available from Albemarle Corporation.
Useful antioxidants can include high molecular weight diarylamines and phenols. In one embodiment, the lubricating oil composition can contain a mixture of a diarylamine and a high molecular weight phenol such that each antioxidant can be present in an amount sufficient to provide up to about 5% by weight, based on the final weight of the lubricating oil composition. In one embodiment, the antioxidant 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 in the final weight of the lubricating oil composition.
[0087] 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 butyl acrylate.
[0088] Another class of sulfur olefin includes sulfur fatty acids and their esters. Fatty acids are generally 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.
The one or more antioxidants may be present in ranges from about 0 wt% to about 20 wt%, or about 0.1 wt% to about 10 wt%, or about 1 wt%. by weight to about 5% by weight of the lubricating oil composition. Anti-wear agents
The lubricating oil compositions of this invention may also optionally contain one or more antiwear agents. Examples of suitable antiwear agents include, but are not limited to, a metal thiophosphate; a metal dialkyldithiophosphate; an ester of phosphoric acid or a salt thereof; a phosphate ester(s); a phosphite; a carboxylic ester containing phosphorus, ether, or amide; a sulfurized olefin; thiocarbamate-containing compounds including, thiocarbamate esters, alkylene-coupled thiocarbamates, and bis(S-alkyldithiocarbamyl) disulfides; and mixtures thereof. Phosphorus-containing antiwear 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, manganese, nickel, copper, titanium, or zinc. A useful antiwear agent may be zinc dialkyl thiophosphate.
[0091] Other examples of suitable antiwear agents include titanium compounds, tartrates, tartrimides, oil-soluble amine salts of phosphorus compounds, sulfur olefins, phosphites (eg, dibutyl phosphite), phosphonates, thiocarbamate-containing compounds such as thiocarbamate esters, 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 antiwear agent may, in one embodiment, include a citrate.
The antiwear 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. by weight to about 5% by weight, or about 0.1% by weight to about 3% by weight of the lubricating oil composition.
[0093] An antiwear compound may be a zinc dihydrocarbyl dithiophosphate (ZDDP) having a P:Zn ratio of from about 1:0.8 to about 1:1.7. Boron-Containing Compounds
[0094] The lubricating oil compositions herein may optionally contain one or more boron-containing compounds.
[0095] Examples of borate-containing compounds include borate esters, borate fatty amines, borate epoxides, borate detergents, and borate dispersants, such as borate succinimide dispersants, as disclosed in US Pat. 5,883,057.
[0096] 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 to about 5% by weight, or about 0.1% by weight to about 3% by weight of the lubricating oil composition. Additional Optional Detergents
[0097] The lubricating oil composition may comprise one or more low base and/or neutral detergents, as well as over base detergents that do not contain calcium and mixtures thereof. Suitable detergent substrates include phenates, sulfur-containing phenates, sulfonates, calixarates, salixarates, salicylates, carboxylic acids, phosphorous acids, mono and/or dithiophosphoric acids, alkyl phenols, sulfur-coupled alkyl phenol compounds, or in bridged phenols. methylene. Suitable detergents and their methods of preparation are described in greater detail in numerous patent publications, including US 7,732,390 and the references cited therein. The detergent substrate can be salinized with an alkali or alkaline earth metal, such as, but not limited to, calcium, magnesium, potassium, sodium, lithium, barium or mixtures thereof. In some modalities, the detergent is barium-free. A suitable detergent can include alkali metal or alkaline earth salts of petroleum sulfonic acids and long chain mono or dialkyl aryl sulfonic acids with the aryl group being benzyl, tolyl and xylyl. Examples of suitable detergents include, but are not limited to, calcium phenates, sulfur and calcium containing phenates, calcium sulfonates, calcium calixarates, calcium salixarates, calcium salicylates, calcium carboxylic acids, phosphorus and calcium acids, acids calcium mono and/or dithiophosphoric acids, calcium alkyl phenols, alkyl phenol compounds coupled to sulfur and calcium, phenols bridged with methylene and calcium, magnesium phenates, phenates containing sulfur and magnesium, magnesium sulfonates, magnesium calixarates, salixarates of magnesium, magnesium salicylates, magnesium carboxylic acids, phosphorus and magnesium acids, magnesium mono- and/or dithiophosphoric acids, magnesium alkyl phenols, alkyl phenol compounds coupled with sulfur and magnesium, phenols bridged with methylene and magnesium , sodium phenates, sodium sulphur-containing phenates, sodium sulfonates, sodium calixarates, sodium salixarates, sodium salicylates, sodium carboxylic acids, acid sodium mono- and/or dithiophosphorics, sodium alkyl phenols, alkyl phenol compounds coupled with sulfur and sodium, or phenols bridged with methylene and sodium.
[0098] Overbassified detergent additives are well known in the art and can be alkaline earth metal or alkali overbase detergent additives. Such detergent additives can be prepared by reacting a metal oxide or metal hydroxide with a carbon dioxide gas and a substrate. 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.
[0099] The terminology "overbasified" 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 in excess of 100% (that is, 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 metal chemical equivalents in the overbasified salt to metal chemical equivalents 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 overbasified salt, MR, it is greater than one. They are commonly called overbassified, hyperbasified, or overbassified salts and can be salts of organic sulfur acids, carboxylic acids, or phenols.
[00100] An over-basified detergent of the lubricating oil composition may have a total base number (TBN) greater than 225 mg KOH/gram, or as other examples, about 250 mg KOH/gram or greater, or about 350 mg of KOH/gram or greater, or about 375 mg of KOH/gram or greater, or about 400 mg of KOH/gram or greater.
[00101] Examples of suitable overbassified detergents include, but are not limited to, overbassified magnesium phenates, overbassified magnesium sulphur-containing phenates, overbassified magnesium sulphonates, overbassified magnesium calixarates, overbassified magnesium salixarates, overbassified magnesium salicylates, carboxylic acids of superbasified magnesium, superbasified phosphorus and magnesium acids, superbasified magnesium mono- and/or dithiophosphoric acids, superbasified alkyl magnesium phenols, alkyl phenol compounds coupled with superbasified sulfur and magnesium, or bridged phenols with superbasified methylene and magnesium.
[00102] The over-basic detergent may 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 .
[00103] Low base/neutral detergent has a TBN of up to 175 mg KOH/g, or up to 150 mg KOH/g. Poorly based or neutral detergent may include a detergent containing calcium. The low-basified-neutral calcium containing detergent can be selected from a calcium sulphonate detergent, a calcium phenate detergent and a calcium salicylate detergent. In some embodiments, the weakly basified or neutral detergent is a calcium-containing detergent or a mixture of calcium-containing detergents. In some embodiments, the weakly basified or neutral detergent is a calcium sulfonate detergent or a calcium phenate detergent.
The low-basified/neutral detergent may comprise at least 2.5% by weight of the total detergent of the lubricating oil composition. In some embodiments, at least 4% by weight, or at least 6% by weight, or at least 8% by weight, or at least 10% by weight or at least 12% by weight or at least 20% by weight of the detergent The total lubricating oil composition is a low-basified or neutral detergent which may optionally be a low-basified or neutral detergent containing calcium.
[00105] In certain embodiments, the one or more low base/neutral 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-basified or neutral detergents containing calcium provide from 75 to less than 800 ppm, or from 100 to 600 ppm, or 125 to 500 ppm by weight of calcium to the lubricating oil composition on a weight basis. total lubricating oil composition.
[00106] In some embodiments, a detergent is effective in reducing or preventing oxidation in an engine. Dispersants
[00107] The lubricating oil composition may optionally additionally comprise one or more dispersants or mixtures thereof. Dispersants are often known as ashless type dispersants because prior to blending into a lubricating oil composition, they do not contain ash-forming metals and they normally do not contribute any ash when added to a lubricant. Ashless type dispersants are characterized by a polar group attached to a hydrocarbon chain of relatively high molecular weight. Typical ashless dispersants include N-substituted long chain alkenyl succinimides. Examples of N-substituted long chain alkenyl succinimides include polyisobutylene succinimide having the number average molecular weight of the polyisobutylene substituent in the range of 350 to about 50,000, or to about 5,000, or to about 3,000. Succinimide dispersants and their preparation are disclosed, for example, in US patent no. 7,897,696 or US Patent No. 4,234,435. The polyolefin can be prepared from polymerizable monomers containing about 2 to about 16, or about 2 to about 8, or about 2 to about 6 carbon atoms. Succinimide dispersants are typically the imide formed from a polyamine, typically a poly(ethyleneamine).
[00108] In one embodiment the present disclosure further comprises at least one polyisobutylene-derived polyisobutylene succinimide dispersant having a number average molecular weight in the range of about 350 to about 50,000, or about 5000, or of about 3000. Polyisobutylene succinimide can be used alone or in combination with other dispersants.
[00109] In some embodiments, polyisobutylene, when included, may have greater than 50 mol%, greater than 60 mol%, greater than 70 mol%, greater than 80 mol%, or greater than 90 mol% content of double terminal connections. Such GDP is also called highly reactive GDP (“HR-PIB”). HR-PIB having a number average molecular weight ranging from about 800 to about 5000 is suitable for use in the embodiments of the present disclosure. Conventional PIB is typically less than 50 mol%, less than 40 mol%, less than 30 mol%, less than 20 mol%, or less than 10 mol% terminal double bond content.
[00110] An HR-PIB having 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 US Pat. 4,152,499 of Boerzel, et al. and US Patent no. 5,7393.55 to Gateau, et al. When used in the aforementioned enothermal reaction, HR-PIB can lead to higher conversion rates in the reaction, as well as lower amounts of sediment formation, due to increased reactivity. A suitable method is described in US Patent no. 7,897,696.
[00111] 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 parts of succinic acid per polymer.
[00112] The % active substances of alkenyl or alkyl succinic anhydride can be determined using a chromatographic technique. This method is described in columns 5 and 6 of US Patent No. 5,334,321.
[00113] The percentage of polyolefin conversion is calculated from the % of active substances using the equation of columns 5 and 6 in US patent No. 5,334,321.
[00114] Unless otherwise noted, all percentages are in percent by weight and all molecular weights are number average molecular weights.
[00115] In one embodiment, the dispersant may be derived from a polyalphaolefin succinic anhydride (PAO).
[00116] In one embodiment, the dispersant can be derived from copolymer of maleic anhydride and olefins. As an example, the dispersant can be described as a poly-PIBSA.
[00117] In one embodiment, the dispersant can be derived from an anhydride, which is grafted with an ethylene-propylene copolymer.
[00118] 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 US Patent no. 3,634,515.
[00119] A suitable class of dispersing agents may be high molecular weight esters or half-ester amides.
[00120] A suitable dispersant may also be post-treated by conventional methods via a reaction with any of a variety of agents. These include boron, urea, thiourea, dimercaptothiadiazoles, carbon disulfide, aldehydes, ketones, carboxylic acids, hydrocarbon substituted succinic anhydrides, maleic anhydride, nitriles, epoxides, carbonates, cyclic carbonates, hindered phenolic esters, and phosphorus compounds. Documents US 7,645,726; US 7,214,649; and US 8,048,831 are hereby incorporated by reference in their entirety.
[00121] In addition to post-treatments of carbonates and boric acids both compounds can be post-treated, or subjected to additional post-treatment, with a variety of post-treatments designed to improve or impart different properties. Such post-treatments include those summarized in columns 27-29 of US Patent No. 5,241,003, incorporated herein by reference. Such treatments include, treatment with: Inorganic phosphorus anhydrates or acids (for example, US Patent Nos. 3,403,102 and 4,648,980); Organic phosphorus compounds (eg, US Patent No. 3,502,677); Phosphorus pentasulfides; Boron compounds as already mentioned above (for example, US Patent Nos. 3,178,663 and 4,652,387); Carboxylic acid, polycarboxylic acids, anhydrides and/or acid halides (for example, US Patent Nos. 3,708,522 and 4,948,386); Epoxides, polyepoxides, or thioexpoxides (for example, US Patent Nos. 3,859,318 and 5,026,495); Aldehyde or ketone (for example, US Patent No. 3,458,530); carbon disulfide (eg, US Patent No. 3,256,185); Glycidol (for example, US Patent No. 4,617,137); Urea, thiourea or guanidine (for example, US Patent Nos. 3,312,619; 3,865,813; and British Patent GB 1,065,595); Organic sulfonic acid (eg, US Patent No. 3,189,544 and British Patent GB 2,140,811); Alkenyl cyanide (for example, US Patent Nos. 3,278,550 and 3,366,569); Diketene (eg, US Patent No. 3,546,243); A diisocyanate (for example, US Patent No. 3,573,205); Alkane sultone (eg, US Patent No. 3,749,695); 1,3-Dicarbonyl Compound (eg, US Patent No. 4,579,675); Alcohol sulfate or alkoxylated phenol (eg, US Patent No. 3,954,639); Cyclic lactone (e.g., US Patent Nos. 4,617,138; 4,645,515; 4,668,246; 4,963,275; and 4,971,711); Cyclic carbonate or thiocarbonate, linear polycarbonate or monocarbonate, or chloroformate (for example, US Patent Nos. 4,612,132; 4,647,390; 4,648,886; 4,670,170); Nitrogen-containing carboxylic acid (eg, US Patent 4,971,598 and British Patent GB 2,140,811); Hydroxy-protected chlorodicarbonyloxy compound (eg, US Patent No. 4,614,522); lactam, thiolactam, thiolactone or dithiolactone (for example, US Patent Nos. 4,614,603 and 4,666,460); Cyclic or linear carbonate or thiocarbonate, polycarbonate or monocarbonate or linear, or chloroformate (for example, US Patent Nos. 4,612,132; 4,647,390; 4,646,886; and 4,670,170); Nitrogen-containing carboxylic acid (eg, US Patent No. 4,971,598 and British Patent GB 2,440,811); Hydroxy-protected chlorodicarbonyloxy compound (eg, US Patent No. 4,614,522); lactam, thiolactam, thiolactone or dithiolactone (for example, US Patent Nos. 4,614,603, and 4,666,460); Cyclic carbamate, cyclic thiocarbamate, or cyclic dithiocarbamate (for example, US Patent Nos. 4,663,062 and 4,666,459); Aliphatic hydroxy carboxylic acid (e.g., US Patent Nos. 4,482,464; 4,521,318; 4,713,189); Oxidizing agent (eg, US Patent No. 4,379,064); Combination of phosphorus pentasulfide and a polyalkylene polyamine (eg, US Patent No. 3,185,647); Combination of carboxylic acid or an aldehyde or ketone and sulfur or sulfur chloride (eg, US Patent Nos. 3,390,086; 3,470,098); Combination of a hydrazine and carbon disulfide (eg, US Patent No. 3,519,564); Combination of an aldehyde and a phenol (eg, US Patent Nos. 3,649,229; 5,030,249; 5,039,307); Combination of an Aldehyde and a Dithiophosphoric Acid O-Diester (eg, US Patent No. 3,865,740); Combination of an aliphatic hydroxy carboxylic acid and a boric acid (eg, US Patent No. 4,554,086); Combination of an aliphatic hydroxy carboxylic acid, then formaldehyde and a phenol (eg, US Patent No. 4,636,322); Combination of an aliphatic hydroxy carboxylic acid and then an aliphatic dicarboxylic acid (eg, US Patent No. 4,663,064); Combination of formaldehyde and a phenol and glycolic acid, then (eg, US Patent No. 4,699,724); Combination of an aliphatic hydroxy carboxylic acid or oxalic acid and then a diisocyanate (eg, US Patent No. 4,713,191); Combination of inorganic acid or phosphorus anhydride or a partial or total sulfur analogue thereof and a boron compound (eg, US Patent No. 4,857,214); Combination of an organic diacid, then an unsaturated fatty acid, then a nitrosoaromatic amine optionally followed by a boron compound and then a glycolating agent (eg, US Patent No. 4,973,412) ; Combination of an Aldehyde and a Triazole (eg, US Patent No. 4,963,278); Combination of an aldehyde and a triazole, then a boron compound (eg, US Patent No. 4,981,492); Combination of cyclic lactone and a boron compound (eg, US Patent Nos. 4,963,275 and 4,971,711). The aforementioned patents are hereby incorporated in their entirety.
[00122] The TBN of a suitable dispersant can be from about 10 to about 65 in an oil-free base, which is comparable to about 5 to about 30 TBN if measured in a dispersant sample containing about 50% of thinner oil.
[00123] The dispersing agent, if present, can 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 wt% to about 15 wt%, or about 0.1 wt% to about 10 wt%, 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 uses a mixed dispersant system. A single type or a mixture of two or more types of dispersants can be used in any desired ratio. Friction Modifiers
[00124] The lubricating oil compositions of this invention 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, nitriles, betaines , quaternary amines, imines, amine salts, amino guanidine, alkanolamides, phosphonates, metal-containing compounds, glycerol esters, sulfurized fatty compounds and olefins, sunflower oil, other naturally occurring oils from plants or animals, dicarboxylic acid esters, esters or partial esters of a polyol and one or more aliphatic or aromatic carboxylic acids, and the like.
[00125] Suitable friction modifiers may contain hydrocarbyl groups which are selected from straight-chain, branched-chain, or aromatic hydrocarbyl groups or mixtures thereof, and may be saturated or unsaturated. Hydrocarbyl groups can be composed of carbon and hydrogen atoms or heteroatoms such as oxygen or sulfur. Hydrocarbyl groups can range from about 12 to about 25 carbon atoms. In some embodiments the friction modifier can be a long chain fatty acid ester. In another embodiment the long chain fatty acid ester can be a monoester, or a diester, or a (tri)glyceride. The friction modifier can be a long-chain fatty amide, a long-chain fatty ester, a long-chain fatty epoxide derivative, or a long-chain imidazoline.
[00126] Other suitable friction modifiers may include organic friction modifiers, ash free (metal free), free of organic nitrogen. Such friction modifiers can include esters formed by the reaction of carboxylic acids and anhydrides with alkanols and generally include a polar end group (e.g., carboxyl or hydroxyl) covalently linked to an oleophilic hydrocarbon chain. An example of an ashless nitrogen-free organic friction modifier is commonly known as glycerol monooleate (GMO) which may contain mono-, di-, and triesters of oleic acid. Other suitable friction modifiers are described in US Patent No. 6,723,685, incorporated herein by reference in its entirety.
[00127] Amine friction modifiers can include amines or polyamines. Such compounds can have hydrocarbyl groups that are linear, saturated or unsaturated, or a mixture thereof and can contain from about 12 to about 25 carbon atoms. Other examples of suitable friction modifiers include alkoxylated amines and ether alkoxylated amines. Such compounds can have hydrocarbyl groups that are linear, either 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.
[00128] Amines and amides can be used as such or in the form of an adduct product or reaction with a boron compound, such as a boric oxide, boron halide, metaborate, boric acid or a mono-borate, di- or tri-alkyl. Other suitable friction modifiers are described in US Patent No. 6,300,291, incorporated herein by reference in its entirety.
[00129] A friction modifier may optionally be present in ranges such as about 0 wt% to about 10 wt%, or about 0.01 wt% to about 8 wt%, or about 0 0.1% by weight to about 4% by weight. Titanium containing compounds
[00130] Another class of additives includes oil-soluble titanium compounds. Oil-soluble titanium compounds can function as antiwear 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 can be titanium(IV) isopropoxide. In one embodiment, the titanium alkoxide can be titanium(IV) 2-ethylhexoxide. In one embodiment, the titanium compound can be the alkoxide of a polyol or 1,2-diol. In one embodiment, the 1,2-diol comprises a glycerol fatty acid monoester, such as oleic acid. In one embodiment, the oil-soluble titanium compound can be a titanium carboxylate. In one embodiment the titanium(IV) carboxylate can be titanium neodecanoate.
[00131] In one embodiment the oil-soluble titanium compound may be present in the lubricating oil composition in an amount sufficient to provide from zero to about 1500 ppm by weight of titanium or about 10 ppm to 500 ppm by weight of titanium or about 25 ppm to about 150 ppm. Transition metal-containing compounds
[00132] In another embodiment, the oil-soluble compound may be a transition metal-containing compound or a metalloid. Transition metals can 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.
[00133] 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, wherein M is the total metal in the lubricating composition as described above. Titanium-containing compounds can function as antiwear agents, friction modifiers, antioxidants, deposit control additives, or more than one of these functions. Among the titanium-containing compounds that can be used in, or that 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) (triethanolaminate) isopropoxide. Other forms of titanium encompassed within the disclosed technology include titanium phosphates such as titanium dithiophosphate (eg dialkyldithiophosphates) and titanium sulfonates (eg alkylbenzenesulfonates), or, in general, the reaction product of titanium compounds with various acidic materials to form salts, such as oil-soluble salts. Titanium compounds can thus be derived from, inter alia, organic acids, alcohols and glycols. The compounds can also exist in dimeric or oligomeric form, containing Ti--O--Ti structures. Such titanium materials are either commercially available or can be readily prepared by suitable synthetic techniques that will be apparent to one of ordinary skill 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 an appropriate inert solvent.
[00134] In one embodiment, titanium can 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)-substituted succinic anhydride. The resulting titanate-succinate intermediate can be used directly or can be reacted with any of a number of materials, such as (a) a polyamine-based succinimide/amide dispersant having free condensable -NH functionality; (b) the components of a polyamine-based succinimide/amide dispersant, i.e., an alkenyl- (or alkyl)-substituted succinic anhydride and a polyamine, (c) a hydroxyl-containing polyester dispersant prepared by the reaction of an anhydride succinic substituted with a polyol, amino alcohol, polyamine, or mixtures thereof. Alternatively, the intermediate titanate succinate can be reacted with other agents, such as alcohols, amino alcohols, ether alcohols, polyether alcohols or polyols, or fatty acids, and the product thereof used directly to impart Ti to a lubricant, or then further reacted with the succinic dispersants as described above. As an example, one part (by mole) of tetraisopropyl titanate can be reacted with about 2 parts (by moles) of a polyisobutene substituted succinic anhydride at 140-150°C for 5 to 6 hours to provide an intermediate or titanium modified dispersant. The resulting material (30 g) can be further reacted with a succinimide dispersant from polyisobutene substituted succinic anhydride and a polyethylene polyamine mixture (127 grams + oil extender) at 150°C for 1.5 hours to produce a titanium-modified succinimide dispersant.
[00135] Another titanium containing compound can be a reaction product of titanium alkoxide and C6 to C25 carboxylic acid. The product of the reaction 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 can 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.
[00136] In one embodiment the oil-soluble titanium compound may be present in the lubricating oil composition in an amount to provide from 0 to 3000 ppm by weight of titanium, or 25 to about 1500 ppm by weight of titanium or about 35 ppm to 500 ppm by weight of titanium or about 50 ppm to about 300 ppm. Viscosity Index Improvers
[00137] The lubricating oil compositions of this invention may also optionally contain one or more viscosity index improvers. Suitable viscosity index improvers can include polyolefins, olefin copolymers, ethylene/propylene copolymers, polyisobutenes, hydrogenated styrene-isoprene polymers, styrene/maleic ester copolymers, hydrogenated styrene/butadiene copolymers, hydrogenated isoprene polymers, maleic anhydride and alpha-olefin copolymers, polymethacrylates, polyacrylates, polyalkyl styrenes, hydrogenated aryl alkenyl-conjugated diene copolymers, or mixtures thereof. Viscosity index improvers can include star polymers, and suitable examples are described in US patent no. 8,999,905 B2.
[00138] The lubricating oil compositions of this invention may also optionally contain one or more dispersant viscosity index improvers in addition to a viscosity index improver or instead of a viscosity index improver. Suitable viscosity index improvers can 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 esterified styrene-maleic anhydride copolymers reacted with an amine.
[00139] The total amount of viscosity index improver and/or dispersant viscosity index improver can be about 0% by weight to about 20% by weight, from about 0.1% by weight to about 15 % by weight, from about 0.1% by weight to about 12% by weight, or from about 0.5% by weight to about 10% by weight, of the lubricating oil composition. Other Optional Additives
[00140] Other additives can be selected to perform one or more functions required of a lubricating fluid. Furthermore, one or more of the mentioned additives may be multifunctional and provide functions in addition to, or different from, the function prescribed herein.
[00141] A lubricating oil composition according to the present invention may optionally comprise other performance additives. The other performance additives may be in addition to the specified additives of the present disclosure and/or may comprise one or more of metal deactivators, viscosity index improvers, detergents, ashless TBN enhancers, friction modifiers, antiwear agents, inhibitors corrosion inhibitors, rust inhibitors, dispersants, dispersant viscosity index improvers, extreme pressure agents, antioxidants, foam inhibitors, demulsifiers, emulsifiers, pour point depressants, seal blowing agents and mixtures thereof. Typically, fully formulated lubricating oil will contain one or more of these performance additives.
Suitable metal deactivators may include benzotriazole derivatives (typically tolyltriazole), dimercaptothiadiazole derivatives, 1,2,4-triazoles, benzimidazoles, 2-alkyldithiobenzimidazoles, or 2-alkyldithiobenzothiazoles; foam inhibitors, including copolymers of acrylate and ethyl 2-ethylhexyl acrylate and optionally vinyl acetate; demulsifiers, including trialkyl phosphates, polyethylene glycols, polyethylene oxides, polypropylene oxides and polymers (ethylene oxide-propylene oxide); pour point depressants, including styrene maleic anhydride esters, polymethacrylates, polyacrylates or polyacrylamides.
Suitable foam inhibitors include silicon-based compounds such as siloxane.
[00144] Suitable pour point depressants may include polymethylmethacrylates or mixtures thereof. The pour point depressants can be present in an amount sufficient to provide from about 0% by weight to about 1% by weight, from 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.
[00145] Suitable rust inhibitors can be a single compound or a mixture of compounds having the property of inhibiting corrosion of ferrous metal surfaces. Non-limiting examples of rust inhibitors useful in this invention include oil-soluble high molecular weight organic acids such as 2-ethyl-hexanoic acid, lauric acid, myristic acid, palmitic acid, oleic acid, linoleic acid, linolenic acid, acid behenic and cerotic acid, as well as oil-soluble polycarboxylic acids, including dimer and trimer acids, such as those produced from tall oil fatty acids, oleic acid and linoleic acid. Other suitable corrosion inhibitors include long-chain alpha, omega-dicarboxylic acids, in the molecular weight range of about 600 to about 3000, and alkenyl succinic acids where the alkenyl group contains about 10 or more carbon atoms, such as , tetrapropenyl succinic acid, tetradecenyl succinic acid, and hexadecenyl succinic acid. Other types of useful acid corrosion inhibitors are alkenyl succinic acid half-esters having about 8 to about 24 carbon atoms in the alkenyl group with alcohols, such as polyglycols. Corresponding half-amides of such alkenyl succinic 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.
The rust inhibitor, if present, can be used in an amount sufficient to provide about 0% by weight to about 5% by weight, from about 0.01% by weight to about 3% by weight from about 0.1% by weight to about 2% by weight, based on the final weight of the lubricating oil composition.
[00147] Generally speaking, a suitable crankcase lubricant may include additive components in the ranges listed in the table below. Table 2


[00148] The percentages of each of the above components 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.
[00149] The additives used in the formulation of the compositions described herein can be mixed with the base oil individually or in various sub-combinations. However, it may be appropriate to mix all components together using an additive concentrate (ie additives in addition to a diluent such as a hydrocarbon solvent). The additives used in formulating the compositions described herein can be blended with the base oil individually or in various sub-combinations. However, it may be appropriate to mix all components together using an additive concentrate (ie additives in addition to a diluent such as a hydrocarbon solvent).
[00150] The present disclosure provides new blends of lubricating oils specifically formulated to be used as lubricants for automobile engines. The embodiments of the present disclosure can provide lubricating oils suitable for engine applications that provide improvements in one or more of the following characteristics: low speed pre-ignition events, anti-oxidation, anti-wear performance, rust inhibition, fuel economy, water tolerance , air entrainment, sealing protection, and foam reduction properties.
[00151] Conventionally fully formulated lubricants contain a set of additives, referred to here as a dispersant/inhibitor pack or DI pack, which will provide the characteristics that are needed in the formulations. Suitable ID packages are described, for example, in US Patent Nos. 5,204,012 and 6,034,040, for example. Among the types of additives included in the additive package may be dispersants, seal blowing 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 conventional amounts with the additives and compositions described herein.
[00152] The following examples are illustrative, but not limiting, of the methods and compositions of the present disclosure. Other suitable modifications and adaptations of the variety of conditions and parameters normally found 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 in their entirety. EXAMPLES
[00153] The fully formulated lubricating oil compositions containing conventional additives were prepared and the low speed pre-ignition events of the lubricating oil compositions were measured. Each of the lubricating oil compositions contained a larger amount of a base oil, a conventional base DI package plus a viscosity index improver(s), where the base DI package (minus the viscosity index improver) viscosity) of about 8 to 12 percent by weight of the lubricating oil composition. The base DI package contained conventional amounts of dispersant(s), antiwear additive(s), an antifoam agent(s) and antioxidant(s) as provided in Table 3 below. Specifically, the base DI package contained a succinimide dispersant, a borate succinimide dispersant, an organic friction modifier, an antioxidant(s), and an antiwear agent(s) (unless otherwise specified). Comparative oil C-1 did not contain a compound containing molybdenum. The base DI package was also blended with about 5 to about 10% by weight of the viscosity index improver(s). Group I base oil was used as a diluent. The largest amount of base oil (about 78 to about 87% by weight) was Group III. The components that have been varied are specified in the Tables and discussion of Examples below. All stated values are given as a percentage by weight of the component in the lubricating oil composition (ie, active ingredient plus oil thinner, if applicable) unless otherwise specified. base, the amount of detergent is set to zero.

[00154] Low-speed pre-ignition events were measured on a 2.0 Liter GM 4-cylinder Ecotec gasoline direct injection (GDI) engine. A complete LSPI detonated engine test consisted of 4 test cycles. Within a single test cycle, two stages or operating segments are repeated in order to generate LSPI. In Stage A, when LSPI is most likely to occur, the engine is operated at about 2,000 rpm and about 18,000 kPa of mean effective brake pressure (BMEP). In stage B, when LSPI is unlikely to occur, the engine is operated at about 1,500 rpm and about 17,000 kPa of BMEP. For each stage, data is collected 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 a rest period. Because LSPI is statistically significant during stage A, the LSPI event data considered only included the LSPI generated during stage A of operation. Thus, for a complete LSPI blast engine test, data was typically generated over a total of 16 steps and was used to evaluate the performance of comparative and inventive oils.
[00155] The LSPI events were determined by monitoring the peak cylinder pressure (PP) and when 2% of the combustible material in the combustion chamber burns (MFB02). The threshold for peak cylinder pressure is calculated for each cylinder and for each stage and is typically 65,000 to 85,000 kPa. The threshold for MFB02 is calculated for each of the cylinders and for each stage and typically ranges from about 3.0 to about 7.5 degrees crank angle (CAD) After Top Dead Point (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 many ways. In order to eliminate the ambiguity involved with engine cycle reporting counts, where tests of different detonated engines can be performed with a different number of engine cycles, the relative LSPI events of comparative and inventive oils have been reported (" LSPI reason”). In this way, the relative improvement for some standard response is clearly demonstrated.
[00156] All reference oils are commercially available engine oils that meet all ILSAC GF-5 performance requirements.
[00157] In the following examples, the LSPI ratio has been classified as a ratio of LSPI events from a test oil to the LSPI events from the “R-1” reference oil. R-1 was a lubricating oil composition formulated with the base DI package and an overbased calcium detergent in an amount to provide about 2400 ppm Ca to the lubricating oil composition. More detailed formulation information for the R-1 reference oil is given below. Considerable improvement in LSPI is recognized when there is a greater than 50% reduction in LSPI events relative to R-1 (an LSPI Ratio of less than 0.5). A further improvement in LSPI is recognized when there is a greater than 70% reduction in LSPI events (an LSPI Ratio of less than 0.3), yet a further improvement in LSPI is recognized when there is more than a 75% reduction in events of LSPI (an LSPI Ratio of less than 0.25), and further improvement in LSPI is recognized when there is more than 80% reduction in LSPI events relative to R-1 (an LSPI Ratio of less than 0.20, and further improvement in LSPI is recognized when there is no more 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 thus considered to be 1.00. A combination of an overbasing calcium detergent and a molybdenum-containing compound was tested with the base formulation. R-1 also contained a sulphur-free amine/molybdenum complex to provide about 80 ppm Mo for the lubricating oil composition.
[00158] Sulphated ash (SASH) was calculated for the total metallic elements that contribute to SASH in the lubricant composition, according to the following factors that were multiplied by the amount of each metallic element in the lubricant composition, according to: http: //konnaris.com/portals/0/search/calculations.htm.
Examples 1-9
[00159] In the following examples, the impact on LSPI of molybdenum, in different amounts and from different sources was tested. In R-1, I-1, I-2 and I-3, a sulphur-free amine/molybdenum complex was used. In R-2, the molybdenum compound is unknown as it is a commercial product. However, the amount of molybdenum present in the lubricant composition was measured to be about 280 ppm by weight of molybdenum by ICP analysis. Two different types of molybdenum dithiocarbamate were tested. In I-4 and I-5, a molybdenum dithiocarbamate was used. In I-6 and I-7, a molybdenum dithiocarbamate was used. In I-8 and I-9 a molybdenum dithiophosphate was used. The results are shown in the table below. Table 4
* Elements measured by ICP (ASTM D5185 and/or D4951) and SASH was calculated as described above. No annotation - sulfur free organomolybdenum complex of an organic amide $ - molybdenum dithiocarbamate # - molybdenum dithiocarbamate ** - molybdenum dithiophosphate
[00160] Commercial oils, R-1 and R-2, are included as reference oils to demonstrate the current state of the art. The R-1 reference oil 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 ethylene/propylene copolymer viscosity index improver at 35 SSI. The HiTEC® 11150 passenger car engine oil additive package is a DI package qualified as API SN, ILSAC-GF-5, and ACEA A5/B5. R-1 also showed the following properties and partial elemental analysis:

[00161] R-2 contains only calcium-containing detergents at a higher calcium loading than the inventive oils. R-1 and R-2 meet all performance requirements for ILSAC GF-5. Comparative Example C-1 is not a commercially available oil, but was designed as a comparative oil to demonstrate performance on LSPI when molybdenum is excluded from the lubricating oil composition.
[00162] In Table 4, R-1 and R-2 demonstrate that using a similar Ca treatment and merely increasing the amount of molybdenum does not improve LSPI. I-1, I-2, and I-3 compared to C-1 demonstrated that decreasing the amount of Ca while increasing the amount of molybdenum has a positive effect on LSPI. I-4, I-5, I-6, and I7 used molybdenum dithiocarbamate in place of the sulfur-free amine/molybdenum complex. An improvement in LSPI is observed both as the amount of molybdenum is increased, as well as in relation to the increase in sulfur content. I-8 and I-9 used molybdenum dithiophosphate in place of the sulphur-free amine/molybdenum complex. An improvement in LSPI is seen as molybdenum and sulfur are increased. Furthermore, as molybdenum dithiophosphate additionally includes phosphorus, the added amount of phosphorus appears to have a positive impact on LSPI.
[00163] An unexpected improvement in LSPI can be obtained by reducing the amount of overbasified calcium detergent and varying the amount and type of a molybdenum-containing compound. A further improvement is seen when the molybdenum-containing compound additionally contains sulfur and/or phosphorus. Greater than about 50% or about 75% improvement in LSPI can be obtained when using the claimed combination as compared to a fluid containing calcium in an amount of 2400 ppm by weight of Ca from an overbasified calcium detergent .
[00164] The present data show that maintaining a ratio of sulfur from additive package or dispersant inhibitor (DI) package to molybdenum from molybdenum compound of less than 18:1 is beneficial in improving LSPI . In addition, keeping SASH less than about 1.0% by weight is also beneficial for LSPI. Examples 10-12
[00165] Examples 10-12 demonstrate the effect of the compositions of the present invention on the temperature on the refrigerant flow (TCO) of a turbocharger and on the average merit rating for turbocharger deposits. Turbocharger Coking Test
[00166] A turbocharger coking test was performed on a 1.4L Chevy Cruze 2012 calibration engine, with a 3 liter test oil charge and a qualified test fuel. A complete turbocharger deposit test consisted of 2000 cycles over approximately 536 hours. Each cycle consists of two steps. The first stage consists of the engine idling for 30 seconds, followed by an increase to 3000 RPM for six and a half minutes. After this period, the engine speed is reduced to 2000 RPM for a second period of 50, until the engine is completely stopped and the second stage starts. The second stage consists of a seven and a half minute period of the engine in the stabilization stage.
[00167] The temperature in the turbocharger refrigerant flow (TCO temperature) is measured every 30 seconds. The baseline initial temperature is measured after the initial 100 cycle period has been completed 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 TCO temperature rise of less than 13% from the baseline TCO temperature and engine running without measured boost pressure of less than 5 kPa, lasting for 10 seconds in duration consecutively, throughout the 2000 cycle test.
[00168] To determine an additional performance parameter of the present test, the manual ASTM Scrub Carbon Method 20 is used to analyze different areas of the turbocharger after completion of the turbocharger coking test. After 2000 cycles or after the race fails, an average merit rating is determined by averaging the merit ratings assigned to each of the six different turbocharger areas, namely, A) Turbine Shaft Area, B) Axle Area of Turbine, C) Central Housing Turbine End Bore, D) Central Housing Turbine Entrance Hole, E) Central Housing Turbine Output Hole, and F) Inlet Pipe. The Average Merit Rating is reported as a range of 0-10 merit. A 10 merit rating is the highest and best rating, and a 0 merit rating is the lowest and worst merit rating.
[00169] In the following examples 10-12, the effect of incorporating an overbasic calcium sulphonate detergent and molybdenum in varying amounts on TCO temperature increase and Mean Merit Rating was determined. The compositions and test results of each of these formulations are summarized in Table 5. Table 5

[00170] In Table 5, the formulations of C-2, I-10, I-11 and I-12 demonstrate that adjusting the total calcium and molybdenum content and the amount of borate dispersant can provide a significant reduction in the increased TCO temperature and an improved Average Merit Rating, as particularly evidenced by Inventive Examples I-12.
[00171] At various places throughout this specification, reference has been made to a number of US patents. All documents cited herein are expressly incorporated in their entirety into this specification as if they were fully set out herein.
[00172] Other embodiments of the present description will be apparent to those skilled in the art from consideration of the descriptive report and practice of the embodiments disclosed herein. As used throughout the specification and claims, “o, a” and/or “an, 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 shall be understood to be modified in all cases by the term “about”, whether or not the term “about” is present. Therefore, unless otherwise indicated, the numerical parameters presented in the specification and claims are approximations which may vary depending on the properties sought after which it is desired to obtain by the present disclosure. At the very least, and not as an attempt to limit the application of the equivalents doctrine to the scope of the claims, each numerical parameter should at least be interpreted in light of the number of significant figures described and by applying common rounding techniques. Notwithstanding the fact that the numerical ranges and parameters establishing the broad scope of the disclosure are approximations, the numerical values presented in the specific examples are presented as accurately as possible. Any numerical value, however, inherently contains certain errors necessarily resulting from the standard deviation found in their respective test measurements. It is intended that the descriptive report and the examples be regarded as illustrative only, with the true scope and spirit of the disclosure being indicated by the following claims.
[00173] The above modalities are susceptible to considerable variation in practice. Therefore, the modalities are not intended to be limited to the specific examples set forth above. Rather, the foregoing modalities are within the spirit and scope of the appended claims, including their equivalents available as a matter of Law.
[00174] The inventors do not intend to engage in any modalities presented to the public, and to the extent any modifications or alterations disclosed cannot literally fall within the scope of the claims which are considered to be part thereof under the doctrine of equivalents.
[00175] It is to be understood that each component, compound, substituent or parameter described herein is to be interpreted as being described for use alone or in combination with one or more of each and every other component, compound, substituent or parameter herein disclosed.
[00176] It should also be understood that each quantity/value or range of quantities/values for each component, compound, substituent or parameter described herein should be interpreted as also being disclosed in combination with each quantity/value or range of quantities/values disclosed for any other component(s), compound(s), substituent(s) or parameter(s) disclosed herein and that any combination of quantities/values or ranges of quantities/values for two or more component(s), compound(s) ), substituent(s) or parameters disclosed herein are, therefore, also disclosed in combination with each other for the purposes of the present disclosure.
[00177] It is further understood that each range disclosed herein is to be interpreted as a disclosure of each specific value within the range disclosed that has the same number of significant digits. Thus, a range of 1-4 should be interpreted as an express disclosure of values 1, 2, 3 and 4.
[00178] 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, compound, substituent or parameter. Thus, this disclosure should be interpreted as a disclosure of all derivative bands by combining each lower limit of each band with each upper limit of each band or with each specific value within each band, or by combining each limit top of each range with each specific value within each range.
[00179] In addition, the specific amounts/values of a component, compound, substituent or parameter disclosed in the description or an example shall be interpreted as a disclosure of any upper or lower limit of a range and therefore may be combined with any another lower or upper limit of a specific range or quantity/value for the same component, compound, or substitutent parameter disclosed elsewhere in the order, to form a range for that component, compound, substitutent or parameter.

权利要求:
Claims (9)
[0001]
1. A method for reducing low speed pre-ignition events in a reinforced internal combustion engine, comprising: lubricating a reinforced internal combustion engine with a lubricating oil composition comprising: more than 50% by weight of a base oil of lubricating viscosity and an additive composition, characterized by the fact that: one or more detergents containing overbasified calcium with a total base number greater than 250 mg KOH/gram, measured by the method of ASTM D-2896, in an amount sufficient to provide more than 1200 ppmw to less than 1800 ppmw calcium for the lubricating oil composition, based on a total weight of the lubricating oil composition and one or more oil-soluble molybdenum containing compounds in an amount sufficient to provide 80 ppm by weight to 1000 ppm by weight of molybdenum for the lubricating oil composition, based on the total weight of the lubricating composition and where the lubricating oil composition does not o contains more than 150 ppm sodium, 0.05% by weight to 0.9% by weight sulfated ash and 50 ppm by weight to 2000 ppm by weight phosphorus, based on the total weight of the lubricating oil composition and the The lubricating oil composition has a weight ratio of sulfur supplied to the lubricating oil composition by the additive composition, to the molybdenum in the lubricating oil composition of less than 18:1.
[0002]
2. Method according to claim 1, characterized in that the reinforced internal combustion engine is a gasoline engine with spark ignition turbocharger.
[0003]
3. Method according to claim 1, characterized in that the lubrication step lubricates a combustion chamber or cylinder walls of a spark-ignition direct injection engine or provided port fuel injection internal combustion engine of a turbocharger or a supercharger.
[0004]
4. Method according to claim 1, characterized in that it includes a step of measuring pre-ignition events at low speed of the internal combustion engine lubricated with the lubricating oil.
[0005]
5. The method according to claim 1, characterized in that the one or more super-bassified calcium-containing detergents comprise a compound selected from: a super-bassified calcium sulfonate detergent, a super-bassified calcium phenate detergent and a super-basic calcium sulfonate detergent and a salicylate detergent. superbasified calcium.
[0006]
6. Method according to claim 1, characterized in that the one or more oil-soluble molybdenum-containing compounds comprise one or more compounds selected from sulfur-free organomolybdenum complexes of organic amides, a molybdenum dithiocarbamate, a dithiophosphate of molybdenum and mixtures thereof or the one or more oil-soluble molybdenum-containing compounds comprise a sulfur-free organomolybdenum complex of an organic amide or the one or more oil-soluble molybdenum-containing compounds comprise a molybdenum dithiocarbamate or the one or more compounds containing oil-soluble molybdenum comprise a molybdenum dithiophosphate.
[0007]
7. The method according to claim 1, characterized in that one or more detergents containing over-basic calcium in the lubricating oil composition provide from 1400 to less than 1800 ppm by weight of calcium to the lubricating oil composition based on a total weight of lubricating oil composition.
[0008]
8. Method according to claim 1, characterized in that one or more components selected from the group consisting of friction modifiers, antiwear agents, dispersants, antioxidants and viscosity index improvers are in the additive composition.
[0009]
9. Method according to claim 1, characterized in that more than 50% by weight of base oil is selected from the group consisting of base oils from Group II, Group III, Group IV, Group V and a combination of two or more of the above, and by more than 50% by weight of base oil is different from the extender oils that result from the provision of additive or viscosity index improver components to the lubricating oil composition.

类似技术:

---

公开号 | 公开日 | 专利标题

---

BR112018000657B1|2021-08-10|METHOD TO REDUCE LOW SPEED PRE-IGNITION EVENTS IN A REINFORCED INTERNAL COMBUSTION ENGINE

---

BR112018000615B1|2022-01-18|COMPOSITION OF LUBRICANT OIL, AND METHOD FOR OPERATION IN AN PUSHED INTERNAL COMBUSTION ENGINE

---

JP6691957B2|2020-05-13|Lubricants with zinc dialkyldithiophosphates and their use in boosted internal combustion engines

---

US10336959B2|2019-07-02|Lubricants with calcium-containing detergent and their use for improving low speed pre-ignition

---

CN107820514B|2021-06-01|Lubricant containing titanium and/or tungsten and use thereof for improving low speed pre-ignition

---

JP6726366B2|2020-07-22|Lubricating oils with overbased calcium and magnesium overbased detergents and methods for improving slow preignition

---

CA3050432C|2020-08-18|Lubricants with calcium and magnesium-containing detergents and their use for improving low-speed pre-ignition and for corrosion resistance

---

JP6708831B2|2020-06-10|Lubricants containing calcium-containing detergents and their use for improving slow pre-ignition

---

JP6726365B2|2020-07-22|Lubricants containing calcium-containing detergents and their use for improving low-speed preignition

---

BR112017028384B1|2021-11-16|LUBRICANT OIL COMPOSITION, AND METHOD TO REDUCE PRE-IGNITION EVENTS AT LOW SPEED

同族专利:

---

公开号 | 公开日

---

RU2721712C2|2020-05-21|

---

RU2018103729A|2019-07-31|

---

EP3322783B1|2020-09-02|

---

CA2991782A1|2017-01-19|

---

CN107949629A|2018-04-20|

---

MX2018000138A|2018-03-23|

---

US10280383B2|2019-05-07|

---

KR20180048597A|2018-05-10|

---

WO2017011683A1|2017-01-19|

---

JP2018520246A|2018-07-26|

---

BR112018000657A2|2018-09-18|

---

RU2018103729A3|2019-12-26|

---

US20170015929A1|2017-01-19|

---

EP3322783A1|2018-05-23|

引用文献:

---

公开号 | 申请日 | 公开日 | 申请人 | 专利标题

---

---

US3366569A|1959-03-30|1968-01-30|Lubrizol Corp|Lubricating compositions containing the reaction product of a substituted succinic acid-producing compound, an amino compound, and an alkenyl cyanide|

---

DE1248643B|1959-03-30|1967-08-31|The Lubrizol Corporation, Cleveland, Ohio |Process for the preparation of oil-soluble aylated amines|

---

US3256185A|1961-06-12|1966-06-14|Lubrizol Corp|Lubricant containing acylated aminecarbon disulfide product|

---

US3185647A|1962-09-28|1965-05-25|California Research Corp|Lubricant composition|

---

US3458530A|1962-11-21|1969-07-29|Exxon Research Engineering Co|Multi-purpose polyalkenyl succinic acid derivative|

---

NL302077A|1962-12-19|

---

GB1054276A|1963-05-17|

---

GB1054093A|1963-06-17|

---

GB1065595A|1963-07-22|1967-04-19|Monsanto Co|Imidazolines and imidazolidines and oil compositions containing the same|

---

US3312619A|1963-10-14|1967-04-04|Monsanto Co|2-substituted imidazolidines and their lubricant compositions|

---

US3390086A|1964-12-29|1968-06-25|Exxon Research Engineering Co|Sulfur containing ashless disperant|

---

GB1162175A|1966-10-01|1969-08-20|Orobis Ltd|Novel Compounds and their use as Lubricant Additives|

---

US3519564A|1967-08-25|1970-07-07|Lubrizol Corp|Heterocyclic nitrogen-sulfur compositions and lubricants containing them|

---

US3718663A|1967-11-24|1973-02-27|Standard Oil Co|Preparation of oil-soluble boron derivatives of an alkylene polyamine-urea or thiourea-succinic anhydride addition product|

---

US3865813A|1968-01-08|1975-02-11|Lubrizol Corp|Thiourea-acylated polyamine reaction product|

---

US3634515A|1968-11-08|1972-01-11|Standard Oil Co| alkylene polyamide formaldehyde|

---

US3573205A|1968-12-17|1971-03-30|Chevron Res|Diisocyanate modified polyisobutenyl-succinimides as lubricating oil detergents|

---

US3859318A|1969-05-19|1975-01-07|Lubrizol Corp|Products produced by post-treating oil-soluble esters of mono- or polycarboxylic acids and polyhydric alcohols with epoxides|

---

US3649229A|1969-12-17|1972-03-14|Mobil Oil Corp|Liquid hydrocarbon fuels containing high molecular weight mannich bases|

---

US3708522A|1969-12-29|1973-01-02|Lubrizol Corp|Reaction products of high molecular weight carboxylic acid esters and certain carboxylic acid acylating reactants|

---

US3749695A|1971-08-30|1973-07-31|Chevron Res|Lubricating oil additives|

---

US3865740A|1972-05-22|1975-02-11|Chevron Res|Multifunctional lubricating oil additive|

---

US3954639A|1974-03-14|1976-05-04|Chevron Research Company|Lubricating oil composition containing sulfate rust inhibitors|

---

DE2702604C2|1977-01-22|1984-08-30|Basf Ag, 6700 Ludwigshafen|Polyisobutenes|

---

US4234435A|1979-02-23|1980-11-18|The Lubrizol Corporation|Novel carboxylic acid acylating agents, derivatives thereof, concentrate and lubricant compositions containing the same, and processes for their preparation|

---

US4259195A|1979-06-28|1981-03-31|Chevron Research Company|Reaction product of acidic molybdenum compound with basic nitrogen compound and lubricants containing same|

---

US4261843A|1979-06-28|1981-04-14|Chevron Research Company|Reaction product of acidic molybdenum compound with basic nitrogen compound and lubricants containing same|

---

US4272387A|1979-06-28|1981-06-09|Chevron Research Company|Process of preparing molybdenum complexes, the complexes so-produced and lubricants containing same|

---

US4283295A|1979-06-28|1981-08-11|Chevron Research Company|Process for preparing a sulfurized molybdenum-containing composition and lubricating oil containing said composition|

---

US4263152A|1979-06-28|1981-04-21|Chevron Research Company|Process of preparing molybdenum complexes, the complexes so-produced and lubricants containing same|

---

US4265773A|1979-06-28|1981-05-05|Chevron Research Company|Process of preparing molybdenum complexes, the complexes so-produced and lubricants containing same|

---

US4259194A|1979-06-28|1981-03-31|Chevron Research Company|Reaction product of ammonium tetrathiomolybdate with basic nitrogen compounds and lubricants containing same|

---

US4285822A|1979-06-28|1981-08-25|Chevron Research Company|Process for preparing a sulfurized molybdenum-containing composition and lubricating oil containing the composition|

---

US4338205A|1980-08-25|1982-07-06|Exxon Research & Engineering Co.|Lubricating oil with improved diesel dispersancy|

---

US4379064A|1981-03-20|1983-04-05|Standard Oil Company |Oxidative passivation of polyamine-dispersants|

---

US4482464A|1983-02-14|1984-11-13|Texaco Inc.|Hydrocarbyl-substituted mono- and bis-succinimide having polyamine chain linked hydroxyacyl radicals and mineral oil compositions containing same|

---

US4648980A|1983-09-22|1987-03-10|Chevron Research Company|Hydrocarbon soluble nitrogen containing dispersant - fluorophosphoric acid adducts|

---

US4579675A|1983-11-09|1986-04-01|Texaco Inc.|N-substituted enaminones and oleaginous compositions containing same|

---

US4521318A|1983-11-14|1985-06-04|Texaco Inc.|Lubricant compositions containing both hydrocarbyl substituted mono and bissuccinimide having polyamine chain linked hydroxacyl radicals, and neopentyl derivative|

---

US4554086A|1984-04-26|1985-11-19|Texaco Inc.|Borate esters of hydrocarbyl-substituted mono- and bis-succinimides containing polyamine chain linked hydroxyacyl groups and lubricating oil compositions containing same|

---

US4612132A|1984-07-20|1986-09-16|Chevron Research Company|Modified succinimides|

---

US4617137A|1984-11-21|1986-10-14|Chevron Research Company|Glycidol modified succinimides|

---

US4614603A|1985-04-12|1986-09-30|Chevron Research Company|Modified succinimides |

---

US4645515A|1985-04-12|1987-02-24|Chevron Research Company|Modified succinimides |

---

US4663062A|1985-04-12|1987-05-05|Chevron Research Company|Lubricating oil compositions containing modified succinimides |

---

US4668246A|1985-04-12|1987-05-26|Chevron Research Company|Modified succinimides |

---

US4666460A|1985-04-12|1987-05-19|Chevron Research Company|Modified succinimides |

---

US4670170A|1985-04-12|1987-06-02|Chevron Research Company|Modified succinimides |

---

US4617138A|1985-04-12|1986-10-14|Chevron Research Company|Modified succinimides |

---

US4647390A|1985-04-12|1987-03-03|Chevron Research Company|Lubricating oil compositions containing modified succinimides |

---

US4648886A|1985-04-12|1987-03-10|Chevron Research Company|Modified succinimides |

---

US4614522A|1985-04-12|1986-09-30|Chevron Research Company|Fuel compositions containing modified succinimides |

---

US4636322A|1985-11-04|1987-01-13|Texaco Inc.|Lubricating oil dispersant and viton seal additives|

---

US4663064A|1986-03-28|1987-05-05|Texaco Inc.|Dibaisic acid lubricating oil dispersant and viton seal additives|

---

US4652387A|1986-07-30|1987-03-24|Mobil Oil Corporation|Borated reaction products of succinic compounds as lubricant dispersants and antioxidants|

---

US4699724A|1986-08-20|1987-10-13|Texaco Inc.|Post-coupled mono-succinimide lubricating oil dispersant and viton seal additives|

---

US4713189A|1986-08-20|1987-12-15|Texaco, Inc.|Precoupled mono-succinimide lubricating oil dispersants and viton seal additives|

---

US4963275A|1986-10-07|1990-10-16|Exxon Chemical Patents Inc.|Dispersant additives derived from lactone modified amido-amine adducts|

---

US4713191A|1986-12-29|1987-12-15|Texaco Inc.|Diiscyanate acid lubricating oil dispersant and viton seal additives|

---

US4971711A|1987-07-24|1990-11-20|Exxon Chemical Patents, Inc.|Lactone-modified, mannich base dispersant additives useful in oleaginous compositions|

---

US5026495A|1987-11-19|1991-06-25|Exxon Chemical Patents Inc.|Oil soluble dispersant additives useful in oleaginous compositions|

---

CA1337293C|1987-11-20|1995-10-10|Emil Joseph Meny|Lubricant compositions for low-temperature internal combustion engines|

---

CA2011367C|1988-08-30|1997-07-08|Henry Ashjian|Reaction products of alkenyl succinimides with ethylenediamine carboxy acids as fuel detergents|

---

US4857214A|1988-09-16|1989-08-15|Ethylk Petroleum Additives, Inc.|Oil-soluble phosphorus antiwear additives for lubricants|

---

US4948386A|1988-11-07|1990-08-14|Texaco Inc.|Middle distillate containing storage stability additive|

---

US4963278A|1988-12-29|1990-10-16|Mobil Oil Corporation|Lubricant and fuel compositions containing reaction products of polyalkenyl succinimides, aldehydes, and triazoles|

---

US5204012A|1989-01-31|1993-04-20|Ethyl Corporation|Supplemental rust inhibitors and rust inhibition in internal combustion engines|

---

US4981492A|1989-12-13|1991-01-01|Mobil Oil Corporation|Borated triazole-substituted polyalkenyl succinimides as multifunctional lubricant and fuel additives|

---

JP2617807B2|1990-03-16|1997-06-04|日本石油株式会社|Engine oil composition|

---

US4973412A|1990-05-07|1990-11-27|Texaco Inc.|Multifunctional lubricant additive with Viton seal capability|

---

US5241003A|1990-05-17|1993-08-31|Ethyl Petroleum Additives, Inc.|Ashless dispersants formed from substituted acylating agents and their production and use|

---

US5030249A|1990-10-01|1991-07-09|Texaco Inc.|Gasoline detergent additive|

---

US5039307A|1990-10-01|1991-08-13|Texaco Inc.|Diesel fuel detergent additive|

---

US5137647A|1991-12-09|1992-08-11|R. T. Vanderbilt Company, Inc.|Organic molybdenum complexes|

---

EP0616635B1|1992-09-11|1999-01-07|Chevron Chemical Company LLC|Fuel composition for two-cycle engines|

---

BR9400270A|1993-02-18|1994-11-01|Lubrizol Corp|Liquid composition and method for lubricating a compressor|

---

US5334321A|1993-03-09|1994-08-02|Chevron Research And Technology Company, A Division Of Chevron U.S.A. Inc.|Modified high molecular weight succinimides|

---

GB2280907B|1993-08-13|1997-04-30|Ethyl Petroleum Additives Ltd|Motor oil compositions,additive concentrates for producing such motor oils,and the use thereof|

---

US6004910A|1994-04-28|1999-12-21|Exxon Chemical Patents Inc.|Crankcase lubricant for modern heavy duty diesel and gasoline fueled engines|

---

US5498355A|1994-09-20|1996-03-12|Ethyl Corporation|Lubricant compositions of enhanced performance capabilities|

---

CA2207676A1|1994-12-20|1996-06-27|Elisavet P. Vrahopoulou|Engine oil with improved fuel economy properties|

---

FR2730496B1|1995-02-15|1997-04-25|Inst Francais Du Petrole|PROCESS FOR THE MANUFACTURE OF ALKENYLS OR POLYALKENYLSUCCINIC ANHYDRIDES WITHOUT RESIN FORMATION|

---

USRE38929E1|1995-11-20|2006-01-03|Afton Chemical Intangibles Llc|Lubricant containing molybdenum compound and secondary diarylamine|

---

US5650381A|1995-11-20|1997-07-22|Ethyl Corporation|Lubricant containing molybdenum compound and secondary diarylamine|

---

ZA97222B|1996-01-16|1998-02-18|Lubrizol Corp|Lubricating compositions.|

---

US5804537A|1997-11-21|1998-09-08|Exxon Chemical Patents, Inc.|Crankcase lubricant compositions and method of improving engine deposit performance|

---

US6034040A|1998-08-03|2000-03-07|Ethyl Corporation|Lubricating oil formulations|

---

US6300291B1|1999-05-19|2001-10-09|Infineum Usa L.P.|Lubricating oil composition|

---

US6140282A|1999-12-15|2000-10-31|Exxonmobil Research And Engineering Company|Long life lubricating oil composition using particular detergent mixture|

---

US6569818B2|2000-06-02|2003-05-27|Chevron Oronite Company, Llc|Lubricating oil composition|

---

JP4185307B2|2001-09-20|2008-11-26|新日本石油株式会社|Lubricating oil composition for internal combustion engines|

---

US6723685B2|2002-04-05|2004-04-20|Infineum International Ltd.|Lubricating oil composition|

---

US7214649B2|2003-12-31|2007-05-08|Afton Chemical Corporation|Hydrocarbyl dispersants including pendant polar functional groups|

---

WO2006035716A1|2004-09-27|2006-04-06|Nippon Oil Corporation|Lubricant composition|

---

WO2006043606A1|2004-10-19|2006-04-27|Nippon Oil Corporation|Lubricant composition and antioxidant composition|

---

US7732390B2|2004-11-24|2010-06-08|Afton Chemical Corporation|Phenolic dimers, the process of preparing same and the use thereof|

---

ES2380938T3|2004-11-30|2012-05-21|Infineum International Limited|Lubricating oil compositions|

---

US7645726B2|2004-12-10|2010-01-12|Afton Chemical Corporation|Dispersant reaction product with antioxidant capability|

---

US7550415B2|2004-12-10|2009-06-23|Shell Oil Company|Lubricating oil composition|

---

CA2602378C|2005-03-28|2014-01-28|The Lubrizol Corporation|Titanium compounds and complexes as additives in lubricants|

---

US7482312B2|2005-04-01|2009-01-27|Shell Oil Company|Engine oils for racing applications and method of making same|

---

JP5513703B2|2005-05-27|2014-06-04|出光興産株式会社|Lubricating oil composition|

---

US7820602B2|2005-07-12|2010-10-26|King Industries, Inc.|Amine tungstates and lubricant compositions|

---

US20070119390A1|2005-11-30|2007-05-31|Herrmann Mark L|System and method for operating an internal combustion engine|

---

US7776800B2|2005-12-09|2010-08-17|Afton Chemical Corporation|Titanium-containing lubricating oil composition|

---

US20080110797A1|2006-10-27|2008-05-15|Fyfe Kim E|Formulated lubricants meeting 0W and 5W low temperature performance specifications made from a mixture of base stocks obtained by different final wax processing routes|

---

US7897696B2|2007-02-01|2011-03-01|Afton Chemical Corporation|Process for the preparation of polyalkenyl succinic anhydrides|

---

US7897548B2|2007-03-15|2011-03-01|Afton Chemical Corporation|Additives and lubricant formulations for improved antiwear properties|

---

US7867957B2|2007-03-30|2011-01-11|Nippon Oil Corporation|Lubricating oil composition|

---

US8048834B2|2007-05-08|2011-11-01|Afton Chemical Corporation|Additives and lubricant formulations for improved catalyst performance|

---

US8008237B2|2008-06-18|2011-08-30|Afton Chemical Corporation|Method for making a titanium-containing lubricant additive|

---

EP2154230A1|2008-08-08|2010-02-17|Afton Chemical Corporation|Lubricant additive compositions having improved viscosity index increasing properties|

---

JP5432493B2|2008-10-09|2014-03-05|出光興産株式会社|Lubricating oil composition for internal combustion engines|

---

EP2371934B1|2010-03-31|2017-03-15|Infineum International Limited|Lubricating oil composition|

---

US8999905B2|2010-10-25|2015-04-07|Afton Chemical Corporation|Lubricant additive|

---

CN103459359A|2011-02-04|2013-12-18|洛德公司|Polyols and their use in hydrocarbon lubricating and drilling fluids|

---

WO2013132613A1|2012-03-07|2013-09-12|トヨタ自動車株式会社|Control device for internal combustion engine|

---

US9677024B2|2012-06-06|2017-06-13|Vanderbilt Chemicals, Llc|Fuel efficient lubricating oils|

---

JP2014152301A|2013-02-13|2014-08-25|Idemitsu Kosan Co Ltd|Lubricant composition for direct-injection turbo mechanism-loaded engine|

---

WO2015023559A1|2013-08-12|2015-02-19|Shell Oil Company|Methods for modifying auto-ignition properties of a base oil or lubricant composition|

---

MX2016003611A|2013-09-19|2016-06-02|Lubrizol Corp|Lubricant compositions for direct injection engines.|

---

CN106062157B|2013-09-19|2021-12-21|路博润公司|Lubricant composition for direct injection engines|

---

SG11201602046PA|2013-09-19|2016-04-28|Lubrizol Corp|Lubricant compositions for direct injection engines|

---

DE102013112454A1|2013-11-13|2015-05-28|Pantere Gmbh & Co. Kg|lubricant composition|

---

US20150175924A1|2013-12-23|2015-06-25|Exxonmobil Research And Engineering Company|Method for improving engine fuel efficiency|

---

JP6300686B2|2014-01-31|2018-03-28|Ｅｍｇルブリカンツ合同会社|Lubricating oil composition|

---

JP6420964B2|2014-03-31|2018-11-07|出光興産株式会社|Lubricating oil composition for internal combustion engines|

---

US11034912B2|2014-04-29|2021-06-15|Infineum International Limited|Lubricating oil compositions|

---

US20150322369A1|2014-05-09|2015-11-12|Exxonmobil Research And Engineering Company|Method for preventing or reducing low speed pre-ignition|

---

US20150322368A1|2014-05-09|2015-11-12|Exxonmobil Research And Engineering Company|Method for preventing or reducing low speed pre-ignition|

---

US20150322367A1|2014-05-09|2015-11-12|Exxonmobil Research And Engineering Company|Method for preventing or reducing low speed pre-ignition|

---

EP3196278A4|2014-09-19|2018-04-25|Idemitsu Kosan Co., Ltd|Lubricating oil composition and method for manufacturing said lubricating oil composition|

---

US9528074B2|2015-02-13|2016-12-27|Chevron Oronite Technology B.V.|Lubricating oil compositions with enhanced piston cleanliness|

---

EP3275978A4|2015-03-24|2019-01-16|Idemitsu Kosan Co.,Ltd.|Lubricant composition for gasoline engines and method for producing same|

---

US10800992B2|2015-03-25|2020-10-13|The Lubrizol Corporation|Lubricant compositions for direct injection engine|

---

JP6149168B2|2015-03-31|2017-06-14|出光興産株式会社|Lubricating oil composition and internal combustion engine friction reducing method|

---

US10421922B2|2015-07-16|2019-09-24|Afton Chemical Corporation|Lubricants with magnesium and their use for improving low speed pre-ignition|US20160272915A1|2015-03-18|2016-09-22|The Lubrizol Corporation|Lubricant compositions for direct injection engines|

---

US11155764B2|2016-05-05|2021-10-26|Afton Chemical Corporation|Lubricants for use in boosted engines|

---

US10377963B2|2016-02-25|2019-08-13|Afton Chemical Corporation|Lubricants for use in boosted engines|

---

US10421922B2|2015-07-16|2019-09-24|Afton Chemical Corporation|Lubricants with magnesium and their use for improving low speed pre-ignition|

---

US10550349B2|2015-07-16|2020-02-04|Afton Chemical Corporation|Lubricants with titanium and/or tungsten and their use for improving low speed pre-ignition|

---

FR3039836B1|2015-08-06|2017-09-15|Total Marketing Services|LUBRICATING COMPOSITIONS FOR PREVENTING OR REDUCING PRE-IGNITION IN AN ENGINE|

---

CA3015620A1|2016-02-24|2017-08-31|The Lubrizol Corporation|Lubricant compositions for direct injection engines|

---

US10443011B2|2017-01-18|2019-10-15|Afton Chemical Corporation|Lubricants with overbased calcium and overbased magnesium detergents and method for improving low-speed pre-ignition|

---

US10370615B2|2017-01-18|2019-08-06|Afton Chemical Corporation|Lubricants with calcium-containing detergents and their use for improving low-speed pre-ignition|

---

US10443558B2|2017-01-18|2019-10-15|Afton Chemical Corporation|Lubricants with calcium and magnesium-containing detergents and their use for improving low-speed pre-ignition and for corrosion resistance|

---

EP3369802B1|2017-03-01|2019-07-10|Infineum International Limited|Improvements in and relating to lubricating compositions|

---

CN111051479A|2017-07-14|2020-04-21|雪佛龙奥伦耐有限责任公司|Zirconium-containing lubricating oil composition and method for preventing or reducing low speed pre-ignition in a direct injection spark ignition engine|

---

EP3461877B1|2017-09-27|2019-09-11|Infineum International Limited|Improvements in and relating to lubricating compositions08877119.1|

---

CN108102767A|2017-12-08|2018-06-01|锦州新兴石油添加剂有限责任公司|A kind of high-performance GF-5, SN, SM gasoline engine oil composite compound and its preparation method and application|

---

CN111100737A|2018-10-29|2020-05-05|中国石油化工股份有限公司|Low-viscosity energy-saving gasoline engine oil compatible with low-speed pre-ignition prevention performance|

---

CN112280609A|2019-07-23|2021-01-29|上汽通用汽车有限公司|Lubricating oil composition|

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]|

---

2021-07-06| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|

---

2021-08-10| 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:

---

申请号 | 申请日 | 专利标题

---

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

---

US62/193,297|2015-07-16|

---

US201615053617A| true| 2016-02-25|2016-02-25|

---

US15/053,617|2016-02-25|

---

US15/147,330|US10280383B2|2015-07-16|2016-05-05|Lubricants with molybdenum and their use for improving low speed pre-ignition|

---

US15/147,330|2016-05-05|

---

PCT/US2016/042328|WO2017011683A1|2015-07-16|2016-07-14|Lubricants with molybdenum and their use for improving low speed pre-ignition|

---