Lubricants with zinc dialkyl dithiophosphate and their use in boosted internal combustion engines

0001The present disclosure relates to lubricant compositions containing one or more oil-soluble additives, and such lubricant compositions to provide an acceptable number of improved slow pre-ignition events in a boosted internal combustion engine. Regarding the use of.

0002Turbocharged or supercharged engines (ie, boosted internal combustion engines) may exhibit anomalous combustion phenomena known as stochastic pre-ignition or slow pre-ignition (or "LSPI"). LSPI is a pre-ignition event that can include ultra-high pressure spikes, premature combustion between improper crank angles, and knocks. All of these, individually or in combination, can cause engine deterioration and / or serious damage. However, since LSPI events occur only in sporadic and uncontrolled manners, it is difficult to identify the cause of this phenomenon and develop solutions to suppress it.

0003Pre-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 igniter. Pre-ignition is typically a problem during high-speed engine operation, as heat from engine operation can heat parts of the combustion chamber to a temperature sufficient to ignite the air-fuel mixture on contact. It has become. This type of pre-ignition is sometimes referred to as hotspot pre-ignition.

0004More recently, intermittent anomalous combustion has been observed in low speed and medium to high load boosted internal combustion engines. For example, low speed pre-ignition (LSPI) may occur in a random and stochastic manner during engine operation below 3,000 rpm under load with a net mean effective pressure (BMEP) of at least 10 bar. The compression stroke time is the longest while the low-speed engine is operating.

0005Several published studies have demonstrated that turbocharger use, engine design, engine coating, piston geometry, fuel selection, and / or engine oil additives can contribute to the increase in LSPI events. One theory suggests that the automatic ignition of engine oil droplets entering the engine combustion chamber through the piston clearance (the space between the piston ring pack and the cylinder liner) can be one cause of the LSPI event. Therefore, there is a need for engine oil additive components and / or combinations that are effective in reducing or eliminating LSPI in boosted internal combustion engines.

0006The present disclosure relates to lubricating oil compositions and methods for providing an acceptable number of slow pre-ignition events in a boosted internal combustion engine. In one embodiment, the lubricating oil composition comprises a base oil having a lubricating viscosity of greater than 50% by weight and an additive composition, wherein the additive composition has a total base value (TBN) greater than 225 mgKOH / g. The perbasic calcium-containing cleaning agent containing the above and one or more zinc dialkyl thiophosphate compounds are contained, and one or more zinc dialkyl thiophosphate compounds are contained in a secondary alcohol of about 20: 100 to about 100: 0. Derived from the molar ratio to primary alcohols and having an average total carbon content of more than 10 carbon atoms per mole of phosphorus, the lubricating oil composition contains more than 900 wt ppm and less than 2400 wt ppm of calcium. It comprises an amount of a hyperbasic calcium-containing cleaning agent provided and at least 0.01% by weight of zinc dialkyldithiophosphate, both of which are based on the total weight of the lubricating oil composition.

0007In another embodiment, the present disclosure provides a method for providing an acceptable number of slow pre-ignition events in a boosted internal combustion engine. The method is a lubricating oil composition comprising a base oil having a lubricating viscosity and an additive composition, wherein the additive composition is a hyperbasic calcium-containing cleaning agent having a TBN of more than 225 mgKOH / g. And one or more zinc dialkylthiophosphate compounds, including the step of lubricating an internal combustion engine boosted with a lubricating oil composition, one or more zinc dialkylthiophosphate compounds from about 20: 100 to about. It is derived from the molar ratio of secondary alcohols of 100: 0 to primary alcohols and has an average total carbon content of more than 10 carbon atoms per mole of phosphorus. The perbasic calcium-containing cleaning agent is contained in the lubricating oil composition in an amount that provides more than 900% by weight ppm and less than 2400% by weight ppm of calcium based on the total weight of the lubricating oil composition, and the lubricating oil composition is lubricated. It contains at least 0.01% by weight of one or more zinc dialkyldithiophosphate compounds based on the total weight of the oil composition. The boosted internal combustion engine is lubricated and operated with a lubricating oil composition.

0008In any of the aforementioned embodiments, the perbasic calcium-containing detergent can be selected from a superbasic calcium sulfonate cleaning agent and a perbasic calcium phenate cleaning agent. In some embodiments, the total calcium from one or more hyperbasic calcium-containing detergents (s) is about 900 to about 2000 ppm by weight of calcium based on the total weight of the lubricating oil composition. Can be provided in the composition.

0009In each of the aforementioned embodiments, the zinc dialkyldithiophosphate compound is relative to the primary alcohol of a secondary alcohol of about 20: 100 to about 100: 0, or about 25: 100 to about 100: 0. It can be derived from the molar ratio. In some embodiments, the zinc dialkyldithiophosphate compound can be derived from a molar ratio of a secondary alcohol of about 35: 100 to about 100: 0 to a primary alcohol.

0010In each of the aforementioned embodiments, one or more zinc dialkyldithiophosphate compounds can have a total average carbon content of more than 10 and up to about 15 carbon atoms per mole of phosphorus. In any of the aforementioned embodiments, one or more zinc dialkyldithiophosphate compounds may be present in an amount of about 0.01% to about 15% by weight based on the total weight of the lubricating oil composition. In some embodiments, one or more zinc dialkyldithiophosphate compounds may be present in an amount of about 0.1% to about 3% by weight based on the total weight of the lubricating oil composition.

0011In each of the aforementioned embodiments, the lubricating oil composition is compared to a number of low speed ligation events in the engine lubricated with the reference lubricant R-1, low speed ligation in the same engine lubricated with the present lubricant. (LSPI) May be effective in reducing events. In some embodiments, the reduction of LSPI events is a reduction of 75% or more, the LSPI events are the number of LSPIs during the 25,000 engine cycle, and the engine is at 18,000 kPa net mean effective pressure (BMEP). It operates at 2000 rpm (RPM) per minute.

0012In each of the above embodiments, the lubricating oil composition may comprise 10% by weight or less of Group IV base oil, Group V base oil, or a combination thereof. In each of the aforementioned embodiments, the lubricating oil composition comprises less than 5% by weight of Group V base oil.

0013In each of the aforementioned embodiments, the base oil greater than 50% by weight can be selected from the base oils of Group II, Group III, or Group IV, and the group consisting of two or more combinations described above, with 50% by weight. The base oils that exceed are other than diluting oils resulting from the provision of additive components or viscosity index improvers in the composition.

0014In each of the aforementioned embodiments, the lubricating oil composition may contain one or more components selected from a friction modifier, an abrasion resistant agent, a dispersant, an antioxidant, and a viscosity index improver.

0015In each of the above embodiments, the superbasic calcium-containing cleaning agent can be a superbasic calcium sulfonate cleaning agent.

0016In each of the above embodiments, the superbasic calcium-containing cleaning agent may optionally exclude the superbasic calcium salicylate cleaning agent.

0017In each of the above embodiments, the lubricating oil composition may optionally exclude the magnesium-containing detergent, and the lubricating oil composition may not contain magnesium.

0018In each of the above embodiments, the lubricating oil composition may not contain a Group IV base oil.

0019In each of the above embodiments, the lubricating oil composition may not contain a Group V base oil.

0020Definitions of the following terms are provided to clarify the meaning of certain terms used herein.

0021"Oil composition", "lubrication composition", "lubricating oil composition", "lubricating oil", "lubricating composition", "lubricating composition", "completely blended lubricant" The terms "composition", "lubricate", "crank case oil", "crank case lubricant", "engine oil", "engine lubricant", "motor oil", and "motor lubricant" are 50 weights. It is considered to be a synonymous, fully compatible term that refers to the final lubrication product containing a small amount of additive composition in addition to the base oil in excess of%.

0022As used herein, "additive package", "additive concentrate", "additive composition", "engine oil additive package", "engine oil additive concentrate", "crank case addition" The terms "agent package," "crankcase additive concentrate," "motor oil additive package," and "motor oil concentrate" are part of a lubricating oil composition that excludes base oil stock mixtures in excess of 50% by weight. Is considered to be a synonymous, fully compatible technical term. The additive package may or may not contain a viscosity index improver or a pour point lowering agent.

0023The term "hyperbasic" is associated with metal salts such as sulfonate, carboxylate, salicylate, and metal salts of phenate, and the amount of metal present exceeds stoichiometry. Such salts can have conversion levels greater than 100% (ie, they are 100 of the theoretical amount of metal required to convert an acid to its "positive", "neutral" salt. Can contain more than%). The expression "metal ratio", often abbreviated as MR, refers to the ratio of the total chemical equivalent of a metal in a perbasic salt to the chemical equivalent of a metal in a neutral salt according to known stoichiometry and stoichiometry. Used for. In normal or neutral salts, the metal ratio is 1, and in hyperbasic salts, MR is greater than 1. They are commonly referred to as hyperbasic salts, hyperbasic salts, or superbasic salts and can be salts of organic sulfur acids, carboxylic acids, salicylates, and / or phenols. In the present disclosure, the hyperbasic detergent has a TBN of greater than 225 mgKOH / g. The superbasic cleaner can be a combination of two or more superbasic cleaners, each with a TBN greater than 225 mgKOH / g.

0024In the present disclosure, the low basic / neutral cleaner has a TBN of up to 175 mgKOH / g. The low basic / neutral cleaner can be a combination of two or more low basic and / or neutral cleaners each having a TBN of up to 175 mgKOH / g. In some examples, "hyperbasic" may be abbreviated as "OB". Also, in some examples, "low basic / neutral" may be abbreviated as "LB / N".

0025The term "total metal" refers to the entire metal, semi-metal, or transition metal in the lubricating oil composition, including the metal provided by the cleaning agent component (s) of the lubricating oil composition. ..

0026As used herein, the term "hydrocarbyl substituent" or "hydrocarbyl group" is used in its usual sense and is well known to those of skill in the art. Specifically, it refers to a group that has a carbon atom attached directly to the rest of the molecule and has predominantly hydrocarbon properties. An example of a hydrocarbyl group is (a) Hydrocarbon substituents, i.e. aliphatic (eg, alkyl or alkenyl), alicyclic (eg, cycloalkyl, cycloalkenyl) substituents, and aromatic, aliphatic, and alicyclic substituted aromatic substitutions. A cyclic substituent, in which the group, as well as the ring, is completed by another portion of the molecule (eg, the two substituents together form an alicyclic moiety). (b) Substituent Hydrocarbon Substituents, i.e., non-hydrocarbon groups (eg, halos (particularly chloro and fluoro), hydroxy, alkoxy, mercapto, alkyl mercapto, which do not primarily alter hydrocarbon substituents in the context of the present disclosure. Substituents containing (nitro, nitroso, amino, alkylamino, and alkoxy), and (c) Heterosubstituted groups, i.e., substituents, which, in the context of the present disclosure, which have predominantly hydrocarbon properties but which otherwise contain a non-carbon in a ring or chain composed of carbon atoms. Be done. Heteroatoms include sulfur, oxygen, and nitrogen and may cover substituents such as pyridyl, frills, thienyl, and imidazolyl. Generally, for every 10 carbon atoms in a hydrocarbyl group, there are no more than two, for example, one or less non-hydrocarbon substituents, typically no non-hydrocarbon substituents in the hydrocarbyl group. do not.

0027As used herein, the term "weight percent" means the percentage by which the cited ingredients represent the weight of the entire composition, unless explicitly stated otherwise.

0028As used herein, the terms "soluble," "oil-soluble," or "dispersible" mean that a compound or additive is soluble, soluble, miscible, or suspended in oil in all proportions. It can be shown that it can be turbid, but it does not have to be. However, the terms mentioned above are soluble, suspendable, soluble, or stable in oils, for example, to the extent that they exert their intended effects in the environment in which the oil is used. It means that it is decentralized. In addition, additional incorporation of other additives may also allow the incorporation of higher levels of specific additives, if desired.

0029As used herein, the term "TBN" is used to describe the total base value in a mgKOH / g composition as measured by the method of ASTM D2896.

0030As used herein, the term "alkyl" refers to the linear, branched, cyclic, and / or substituted saturated chain moieties of about 1 to about 100 carbon atoms.

0031As used herein, the term "alkenyl" refers to the linear, branched, cyclic, and / or substituted unsaturated chain moieties of about 3 to about 10 carbon atoms.

0032As used herein, the term "aryl" refers to alkyl, alkenyl, alkylaryl, amino, hydroxyl, alkoxy, halo, and / or nitrogen, oxygen. , And, but not limited to, monocyclic and polycyclic aromatic compounds which may contain heteroatoms.

0033The reduction of slow pre-ignition events can be described as the "LSPI ratio". The term "LSPI ratio" is the number of slow pre-ignition events in a boosted internal combustion engine lubricated with the lubricating oil composition of the present disclosure, lubricated with the reference lubricating oil R-1 described herein. Refers to the ratio to the number of slow lubrication events in the same boosted internal combustion engine. Lubricating oil compositions that reduce the LSPI ratio are boosted internal combustion engines lubricated with this lubricating oil composition compared to the number of slow preignition events in the same engine lubricated with reference lubricating oil R-1. It is effective in reducing the low-speed lubrication event in.

0034The lubricants, component combinations, or individual components herein may be suitable for use in various types of internal combustion engines. Suitable engine types include, but are not limited to, large diesel vehicles, passenger vehicles, small diesel vehicles, medium speed diesel vehicles, marine engines, or motorcycle engines. Internal combustion engines include diesel fuel engine, gasoline fuel engine, natural gas fuel engine, biofuel engine, mixed diesel / biofuel engine, mixed gasoline / biofuel engine, alcohol fuel engine, mixed gasoline / alcohol fuel engine, compressed natural gas. It can be a (CNG) fuel engine, or a mixture thereof. The diesel engine can be a compression ignition engine. The diesel engine can be a compression ignition engine with spark ignition assist. The gasoline engine can be a spark ignition engine. The internal combustion engine may also be used in combination with a power source or battery source. Engines so configured are commonly known as hybrid engines. The internal combustion engine can be a two-stroke engine, a four-stroke engine, or a rotary engine. Suitable internal combustion engines include marine diesel engines (such as Inland Marine), aircraft piston engines, low load diesel engines, and motorcycle, automobile, engine vehicle, and truck engines.

0035The internal combustion engine may contain one or more components of aluminum alloys, lead, tin, copper, cast iron, magnesium, ceramics, stainless steel, composites and / or mixtures thereof. The components can be coated, for example, with diamond-like carbon coatings, lubricating coatings, phosphorus-containing coatings, molybdenum-containing coatings, graphite coatings, nanoparticles-containing coatings, and / or mixtures thereof. Aluminum alloys may include aluminum silicate, aluminum oxide, or other ceramic materials. In one embodiment, the aluminum alloy is an aluminum silicate surface. As used herein, the term "aluminum alloy" is synonymous with "aluminum composite", and regardless of its detailed structure, aluminum mixed or reacted at the microscopic or near microscopic level and separately. It is intended to describe the components or surfaces that contain the components of. This includes any conventional alloy having a metal other than aluminum, and a composite or alloy-like structure having a non-metal element or compound such as a ceramic-like material.

0036Lubricating oil compositions for internal combustion engines are sulfur, phosphorus, or sulfated ash (ASTM). D-874) It may be suitable for any engine, regardless of its content. 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 be in the range of about 0.001% to about 0.5% or about 0.01% to about 0.3% by weight. Phosphorus content is 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 about 0.06% by weight or less, about 0.055% by weight or less, or about 0.05% by weight. It can be: In one embodiment, the phosphorus content can be from about 50 ppm to about 1000 ppm or from about 325 ppm to about 850 ppm. The total sulfate ash content can be about 2% by weight or less, or about 1.5% by weight or less, or about 1.1% by weight or less, or about 1% by weight or less, or about 0.8% by weight or less, or about 0.5% by weight or less. .. In one embodiment, the ash sulfate content can be from about 0.05% to about 0.9% by weight, or about 0.1% by weight or from about 0.2% to about 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 the sulfated ash content can be about 1% by weight or less. In yet another embodiment, the sulfur content can be about 0.3% by weight or less, the phosphorus content can be about 0.05% by weight or less, and the sulfated ash content can be about 0.8% by weight or less.

0037In one embodiment, the lubricating oil composition is an engine oil, which comprises (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) It can have a sulfuric acid ash content of about 1.5% by weight or less.

0038In some embodiments, the lubricating oil composition is suitable for use in engines powered by low sulfur fuels, such as fuels containing about 1 to about 5% sulfur. Highway vehicle fuel contains about 15 ppm sulfur (or about 0.0015% sulfur). The lubricating oil composition is suitable for use with a boosted internal combustion engine, including a turbocharged or supercharged internal combustion engine.

0039In addition, the lubricants herein are ILSAC GF-3, GF-4, GF-5, GF-6, PC-11, CI-4, CJ-4, ACEA A1 / B1, A2 / B2, A3 /. One or more industrial standards such as B3, A3 / B4, A5 / B5, C1, C2, C3, C4, C5, E4 / E6 / E7 / E9, Euro5 / 6, Jaso DL-1, Low SAPS, Mid SAPS, etc. Requirements, or Dexos 1, Dexos 2, MB-Approval 229.51 / 29.31, VW502.00, 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 2300, B71 2302, B71 2312, B71 2007, B71 2008, Ford Standards of partner trademark manufacturers such as WSS-M2C153-H, WSS-M2C930-A, WSS-M2C945-A, WSS-M2C913A, WSS-M2C913-B, WSS-M2C913-C, GM6094-M, Chrysler MS-6395 , Or may be suitable to meet any past or present PCMO or HDD standard not mentioned herein. In some embodiments, for passenger car motor oil (PCMO) applications, the amount of phosphorus in the final fluid is 1000 ppm or less, or 900 ppm or less, or 800 ppm or less.

0040Other hardware may not be suitable for use with the disclosed lubricants. "Functional fluid" means hydraulic fluid for tractors; power transmission fluids (including automatic transmission fluids, stepless transmission fluids, and manual transmission fluids); hydraulic fluids (including hydraulic fluids for tractors). ); Some gear oils; Power steering fluids; Fluids used in wind turbines, compressors; Some industrial fluids; as well as various, but not limited to, fluids related to the components of the power transmission system. It is a term that covers fluids. In each of these fluids, for example automatic transmission fluids, there are various different types of fluids due to the different designs in which the different transmissions create the need for fluids with significantly different functional properties. Please note. This is contrasted by the term "lubricating fluid", which is not used to generate or transmit power.

0041For example, with respect to hydraulic fluids for tractors, these fluids are versatile products used for all lubricant applications in tractors except engine lubrication. These lubrication applications include lubrication of gearboxes, power take-out devices and clutches (s), rear axles, reduction gears, wet brakes, and hydraulic oil accessories.

0042If the functional fluid is an automatic transmission fluid, the automatic transmission fluid must have sufficient friction for the clutch plate to transmit power. However, the friction coefficient of the fluid tends to decrease due to the influence of temperature because the fluid becomes hot during operation. It is important that the tractor hydraulic fluid or automatic transmission fluid maintain its high friction coefficient at high temperatures, otherwise the braking system or automatic transmission may fail. This is not a function of engine oil.

0043Tractor fluids, such as super tractor universal oils (STUO) or universal tractor transmission fluids (UTTOs), can combine the performance of engine oils with transmission fluids, differentials, final drive planetary gears, wet brakes, and hydraulic performance. Many of the additives used to formulate UTTO or STUO fluids are similar in function but can have detrimental effects if not properly incorporated. For example, some wear resistant and extreme pressure additives used in engine oils can be extremely corrosive to the copper component in hydraulic pumps. Detergents and dispersants used for the performance of gasoline or diesel engines can be detrimental to wet braking performance. Friction modifiers specific to quiet wet braking noise may lack the thermal stability required for engine oil performance. Each of these fluids, whether functional, tractor, or lubricious, is designed to meet the requirements of a particular rigorous manufacturer.

0044The present disclosure provides a novel lubricant blend formulated for use as an automotive crankcase lubricant. The embodiments of the present disclosure are suitable for crankcase applications and have the following characteristics: air inclusions, alcohol fuel compatibility, antioxidant properties, wear resistance, biofuel compatibility, foam reduction properties, friction reduction, fuel economy. Lubricants may be provided that have improvements in properties, pre-ignition prevention, rust control, sludge and / or soot dispersibility, piston cleanliness, deposition formation, and water resistance.

0045The engine oils of the present disclosure can be formulated by adding one or more of the additives detailed below to the appropriate base oil formulation. Additives may be combined with the base oil in the form of an additive package (or concentrate), or individually with the base oil (or a mixture of both). Fully blended engine oils may exhibit improved performance characteristics based on the additives added and their respective proportions.

0046Additional details and benefits of this disclosure may be in part described in the description below and / or understood by the practice of this disclosure. Additional details and advantages of the present disclosure may be realized and achieved by means of elements and combinations specifically noted in the appended claims. It should be understood that both the general description above and the detailed description below are exemplary and descriptive and do not limit the alleged disclosure.

0047Various embodiments of the present disclosure provide lubricating oil compositions and methods that can be used to provide an acceptable number of slow pre-ignition events (LSPIs) in a boosted internal combustion engine. In particular, the boosted internal combustion engines of the present disclosure include turbocharged and supercharged internal combustion engines. Boosted internal combustion engines include spark ignition engines, direct injection engines, and / or port fuel injection engines. The spark ignition internal combustion engine can be a gasoline engine.

0048In one embodiment, the present disclosure provides lubricating oil compositions and methods that provide an acceptable number of slow pre-ignition events in a boosted internal combustion engine. The lubricating oil composition consists of a base oil having a lubricating viscosity of more than 50% by weight, one or more calcium-containing hyperbasic cleaning agents having a total basic value of more than 225 mgKOH / g (s), and one or more zincs. An additive composition comprising a dialkyldithiophosphate compound, and one or more zinc dialkylthiophosphate compounds (s) comprising, with respect to the primary alcohol of a secondary alcohol of about 20: 100 to about 100: 0 The lubricating oil composition is derived from a molar ratio and has an average total carbon content of more than 10 carbon atoms per mole of phosphorus, and the lubricating oil composition contains calcium exceeding 900% by weight ppm and less than 2400% by weight ppm in the lubricating oil composition. The total weight of the lubricating oil composition is based on the total weight of the lubricating oil composition, which comprises the amount of the perbasic calcium-containing cleaning agent provided and at least 0.01% by weight of zinc dialkyldithiophosphate. Use as a reference.

0049In another embodiment, the present disclosure provides a method for providing an acceptable number of slow pre-ignition events in a boosted internal combustion engine. The method comprises a lubricating oil comprising a base oil having a lubricating viscosity, a hyperbasic calcium-containing cleaning agent having a TBN greater than 225 mgKOH / g, and an additive composition containing one or more zinc dialkyldithiophosphate compounds. In the composition, one or more zinc dialkylthiophosphate compounds are derived from the molar ratio of the secondary alcohol to the primary alcohol of about 20: 100 to about 100: 0, and 10 per mol of phosphorus. Including the step of lubricating an internal combustion engine boosted with a lubricating oil composition having an average total carbon content of more than. The perbasic calcium-containing cleaning agent is contained in the lubricating oil composition in an amount that provides more than 900% by weight ppm and less than 2400% by weight ppm of calcium based on the total weight of the lubricating oil composition, and the lubricating oil composition is lubricated. It contains at least 0.01% by weight of one or more zinc dialkyldithiophosphate compounds based on the total weight of the oil composition. The boosted internal combustion engine is lubricated and operated with a lubricating oil composition.

0050In some embodiments, the combustion chamber or cylinder wall of a spark-ignition direct-injection engine or port fuel-injection internal combustion engine with a turbocharger or supercharger is actuated and lubricated with its lubricating oil composition. It is possible to reduce low-speed pre-ignition events in engines lubricated with a lubricating oil composition.

0051Optionally, the method of the present invention may include measuring a slow pre-ignition event of a lubricated internal combustion engine. In such a method, the internal combustion engine has a reduction of LSPI events of 50% or more, or more preferably 75% or more, and the LSPI events are the number of LSPIs during the engine cycle of 25,000. The engine runs at 2000 rpm per minute with a net mean effective pressure of 18,000 kPa.

0052The composition of the present invention includes a lubricating oil composition containing a base oil having a lubricating viscosity and a specific additive composition. The method of the present disclosure uses either a specific additive composition or a lubricating oil composition containing the additive composition. As described in more detail below, the lubricating oil composition is used to provide acceptable LSPI performance and reduce slow pre-ignition events in boosted internal combustion engines lubricated with the lubricating oil composition. Can be surprisingly effective in doing so.

0053As described in more detail below, the embodiments of the present disclosure provide significant and unexpected improvements in reducing LSPI events while maintaining relatively high calcium detergent concentrations in the lubricating oil composition. obtain. In some embodiments, the lubricating oil compositions and methods of the present invention may reduce the LSPI ratio.

0054Washing soap The lubricating oil composition comprises one or more hyperbasic cleaning agents and one or more low basic / neutral cleaning agents. Suitable cleaning agent substrates include phenate, sulfur-containing phenate, sulfonate, calixarate, salixarate, salicylate, carboxylic acid, phosphoric acid, monothiophosphate and / or dithiophosphate, alkylphenol, sulfur-bound alkylphenol compound, or methylene cross-linked phenol. Be done. Suitable cleaning agents and methods for their preparation are described in US 7,732, It is described in detail in a number of patent gazettes, including No. 390 and the references cited therein. The cleaning agent substrate is an alkali metal or alkaline earth metal, such as, but not limited to, calcium, magnesium, potassium, sodium, lithium, barium, or mixtures thereof, which can be salted. In some embodiments, the cleaning agent does not contain barium. Suitable cleaning agents may include petroleum sulfonic acids and alkali metal or alkaline earth metal salts of long chain mono or dialkylaryl sulfonic acids having aryl groups of benzyl, trill, and xsilyl. Examples of suitable additional cleaning agents include calcium phenate, calcium sulfur-containing phenate, calcium sulfonate, calcium calixarate, calcium salixarate, calcium salicylate, calcium carboxylic acid, calcium phosphate, calcium monothiophosphate and / Or dithiophosphate, calcium alkylphenol, calcium sulfur-bonded alkylphenol compound, calcium methylene cross-linked phenol, magnesium phenate, magnesium sulfur-containing phenate, magnesium sulfonate, magnesium calixarate, magnesium salixarate, magnesium salicylate, magnesium carboxylic acid, Magnesium phosphate, magnesium monothiophosphate and / or dithiophosphate, magnesium alkylphenol, magnesium sulfur-bonded alkylphenol compound, magnesium methylene cross-linked phenol, sodium phenate, sodium sulfur-containing phenate, sodium sulfonate, sodium calixarate, sodium salixarate, Examples include, but are not limited to, sodium salicylate, sodium carboxylic acid, sodium phosphate, sodium monothiophosphate and / or dithiophosphate, sodium alkylphenol, sodium sulfur-bonded alkylphenol compound, or sodium methylene cross-linked phenol.

0055The superbasic detergent additive is well known in the art and can be an alkali metal or alkaline earth metal superbasic detergent additive. Such detergent additives can be prepared by reacting a metal oxide or metal hydroxide with a substrate and carbon dioxide gas. The substrate is typically an acid, such as an aliphatic-substituted sulfonic acid, an aliphatic-substituted carboxylic acid, or an aliphatic-substituted phenol.

0056The term "hyperbasic" is associated with metal salts such as sulfonate, carboxylate, and phenate metal salts, and the amount of metal present exceeds the stoichiometric amount. Such salts can have conversion levels greater than 100% (ie, they are 100 of the theoretical amount of metal required to convert an acid to its "positive", "neutral" salt. Can contain more than%). The expression "metal ratio", often abbreviated as MR, refers to the ratio of the total chemical equivalent of a metal in a perbasic salt to the chemical equivalent of a metal in a neutral salt according to known stoichiometry and stoichiometry. Used for. In normal or neutral salts, the metal ratio is 1, and in hyperbasic salts, MR is greater than 1. They are commonly referred to as hyperbasic salts, hyperbasic salts, or superbasic salts and can be salts of organic sulfur acids, carboxylic acids, or phenols.

0057Superbasic cleaners are TBN greater than 225 mgKOH / gram, or, for example, TBN greater than about 250 mgKOH / gram, or TBN greater than about 300 mgKOH / gram, or TBN greater than about 350 mgKOH / gram, approximately 375 mgKOH / gram. Have a TBN greater than or equal to, or approximately 400 mgKOH / gram or greater.

0058Examples of suitable hyperbasic cleaning agents include hyperbasic calcium phenates, hyperbasic calcium sulfur-containing phenates, hyperbasic calcium sulfonates, hyperbasic calcium calixarate, hyperbasic calcium salixarate, and excess. Basic calcium salicylate, hyperbasic calcium carboxylic acid, hyperbasic calcium phosphate, hyperbasic calcium monothiophosphate and / or dithiophosphate, hyperbasic calcium alkylphenol, hyperbasic calcium sulfur-bonded alkylphenol compound, excess Basic calcium methylene cross-linked phenol, perbasic magnesium phenate, perbasic magnesium sulfur-containing phenate, perbasic magnesium sulfonate, perbasic magnesium calixarate, perbasic magnesium salixarate, perbasic magnesium salici Rate, perbasic magnesium carboxylic acid, perbasic magnesium phosphate, perbasic magnesium monothiophosphate and / or dithiophosphate, perbasic magnesium alkylphenol, perbasic magnesium sulfur-bonded alkylphenol compound, or perbasic magnesium methylene Cross-linked phenols include, but are not limited to.

0059The superbasic cleaner can have a ratio of 1.1: 1 or 2: 1 or 4: 1 or 5: 1 or 7: 1 or 10: 1 to the metal substrate.

0060The additive composition used in the compositions and methods of the present disclosure comprises at least one hyperbasic calcium-containing cleaning agent having a TBN of greater than 225 mgKOH / g.

0061The superbasic calcium-containing detergent can be selected from a superbasic calcium sulfonate cleaning agent, a hyperbasic calcium phenate cleaning agent, and a superbasic calcium salicylate cleaning agent. In certain embodiments, the superbasic cleaner is one or more calcium-containing cleaners, preferably the superbasic cleaner is a calcium sulfonate cleaner, a calcium phenate cleaner, or a combination thereof. .. In certain embodiments, the overbasic detergent is calcium sulfonate. In certain embodiments, the lubricating composition does not contain magnesium from magnesium-containing compounds.

0062The lubricating oil compositions of the present disclosure, including the additive composition, have a total amount of calcium from a perbasic calcium-containing cleaning agent in the range of more than 900 weight ppm and less than 2400 weight ppm based on the total weight of the lubricating oil composition. Have. As a further example, one or more hyperbasic calcium cleaners may be present in an amount that provides about 900 to about 2000 ppm calcium to the final fluid. As a further example, one or more hyperbasic calcium cleaners may contain approximately 900 to approximately 2400 ppm calcium, or approximately 900 to approximately 1800 ppm calcium, or approximately 1100-1600 ppm calcium, or approximately 1200-1500 ppm calcium. It may be present in the amount provided for the final fluid.

0063In certain embodiments, a low basic / neutral calcium-containing cleaning agent having a TBN of up to 175 mgKOH / g, or up to 150 mgKOH / g, may optionally be included. Any low-basic neutral calcium-containing detergent can be selected from calcium sulfonate cleaning agents, calcium phenate cleaning agents, and calcium salicylate cleaning agents. In some embodiments, the low basic / neutral cleaner is a calcium-containing cleaner or a mixture of calcium-containing cleaners. In some embodiments, the low basic / neutral cleaner is a calcium sulfonate cleaner or a calcium phenate cleaner.

0064In some embodiments, the low basic / neutral calcium-containing cleaning agent is not included in the lubricating oil composition. In other embodiments, the low basic / neutral calcium-containing cleaning agent comprises at least 0.2% by weight based on the total weight of the lubricating oil composition. In some embodiments, at least 0.4% by weight, or at least 0.6% by weight, or at least 0.8% by weight, or at least 1.0% by weight, or at least 1.2% by weight, or at least 2.0% by weight of the total lubricating oil composition is low. It is a basic / neutral calcium-containing detergent.

0065In certain embodiments in which a low basic / neutral calcium-containing detergent is used, the low basic / neutral calcium-containing detergent is about 50 to about 1000 wt ppm based on the total weight of the lubricating oil composition. Calcium is provided in the lubricating oil composition. In some embodiments, the low basic / neutral calcium-containing cleaning agent is 75% by weight to less than 800% by weight, or 100 to 600% by weight, or 125 to 500% by weight, based on the total weight of the lubricating oil composition. Provide ppm calcium to the lubricating oil composition.

0066The superbasic calcium-containing cleaning agent can be a superbasic calcium sulfonate cleaning agent. The superbasic calcium-containing cleaning agent can optionally exclude the superbasic calcium salicylate cleaning agent. Lubricating oils may optionally exclude magnesium-containing cleaning agents or may not contain magnesium. In any of the embodiments of the present disclosure, the amount of sodium in the lubricating oil composition can be limited to 150 ppm or less of sodium based on the total weight of the lubricating oil composition.

0067Zinc dialkyldithiophosphate (s) Lubricating oil compositions herein also include one or more zinc dialkyldithiophosphates (ZDDPs). ZDDP is about 0.01% to about 15% by weight, or about 0.01% to about 10% by weight, or about 0.05% to about 5% by weight, or about 0.1% by weight, based on the total weight of the lubricating oil composition. It is present in the lubricating oil composition in an amount of% to about 3% by weight.

0068ZDDP compounds can include ZDDP derived from primary alcohols, secondary alcohols, or combinations of primary and secondary alcohols. The lubricating oil compositions described herein contain at least one ZDDP, at least a portion of that ZDDP is derived from a secondary alcohol, and more than 20% of all alkyl groups in the ZDDP compound is a secondary alcohol. Derived from. By using one or more ZDDP compounds derived from the molar ratio of secondary alcohols from about 20: 100 to about 100: 0 to primary alcohols, the same containing ZDDP derived only from primary alcohols. When compared to the lubricating oil composition, the LSPI ratio is unexpectedly reduced and the LSPI event is unexpectedly reduced. The molar ratio of secondary alcohols used to make ZDDP in lubricating oil compositions to primary alcohols is from about 20: 100 to 100: 0, or from about 25: 100 to 100: 0, or about 35. : 100 ~ 100: 0, or about 40: 100 ~ 100: 0, or about 50: 50 ~ 100: 0, or about 25: 100 ~ 75: 25, or about 35: 100 ~ 60: 40. As a result, more than 20% to 100% of all alkyl groups in ZDDP compounds are secondary alkyl groups and 25-100% of alkyl groups in ZDDP compounds are secondary alkyl groups, or 35- 100% are secondary alkyl groups, or 40-100% are secondary alkyl groups, or 50-100% are secondary alkyl groups, or 25-75% are secondary alkyl groups. Or 35-60% are secondary alkyl groups.

0069ZDDP can have a P: Zn ratio of about 1: 0.8 to about 1: 1.7. In some embodiments, the additive composition comprises at least two different zinc dialkyldithiophosphate salts. The two alkyl groups of the zinc dialkyldithiophosphate salt may be the same or different.

0070In some embodiments, 100 mole percent of the alkyl groups of at least one zinc dialkyldithiophosphate salt can be derived from a secondary alcohol group. In some embodiments, mixtures of all primary alcohol zinc dialkyldithiophosphate salts with all secondary alcohol zinc dialkyldithiophosphate salts are provided.

0071Suitable alcohols for producing zinc dialkyldithiophosphate salts can be primary alcohols, secondary alcohols, or mixtures of primary and secondary alcohols. In one embodiment, the additive package comprises one zinc dialkyldithiophosphate salt derived from an alcohol containing a primary alkyl group and another zinc dialkyldithiophosphate salt derived from an alcohol containing a secondary alkyl group. ,including. In another embodiment, the zinc dialkyldithiophosphate salt is derived from at least two secondary alcohols. Alcohols can contain either branched, cyclic, or linear.

0072In some embodiments, the alkyl group of at least one zinc dialkyldithiophosphate salt can be derived from a mixture of primary and secondary alcohol groups. Alcohol mixtures are 20: 100 to 100: 00, or about 25: 100 to about 100: 0, or about 35: 100 to about 90:10, or about 40: 100 to about 80:20, or about 40:60. It can have a molar ratio of secondary alcohols to primary alcohols of ~ about 60:40, or about 50:50.

0073At least one zinc dialkyldithiophosphate salt can be an oil-soluble salt of dihydrocarbyl dithiophosphate and can be represented by the following formula.

0074<chemistry num="1"><img id="000002" he="39" wi="113" file="JP2018520249A_D0001.tif" img-format="tif" img-content="drawing" /></chemistry>

0075(In the formula, R₅And R₆Is the same or different alkyl group that contains 1 to 18 carbon atoms, or 2 to 12 carbon atoms, or 2 to 8 carbon atoms and contains moieties such as alkyl and cycloalkyl moieties. possible. Therefore, the part is, for example, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl, amyl, n-hexyl, i-hexyl, n-octyl, decyl, dodecyl, It can be octadecyl, 2-ethylhexyl, cyclohexyl, or methylcyclopentyl.

0076For ZDDP compounds The average number of total carbon atoms per mole of phosphorus is the four alkyl groups R provided to the ZDDP compound by the alcohol (s) used to make the ZDDP compound.₅And R₆It can be calculated by dividing the sum of the carbon atoms in it by 2. For example, for a single ZDDP compound, R₅Is C₃-R with alkyl group₆Is C₆For alkyl groups, the total number of carbon atoms is 3 + 3 + 6 + 6 = 18. Dividing this by 2 moles of phosphorus per mole of ZDDP gives an average total of 9 carbon atoms per mole of phosphorus.

0077The average total number of carbon atoms per mole of phosphorus (ATCP) for a composition containing one or more ZDDP compounds is calculated from the alcohol (s) used to make the ZDDP compound according to the following formula: obtain. ATCP = 2 * [(mol% of alc1 * number of C atoms in alc1) + (mol% of alc2 * number of C atoms in alc2) + (mol% of alc3 * number of C atoms in alc3) + ...Such] (In the formula, alc1, alc2, and alc3 each represent different alcohols used to make the ZDDP compound (s), and mol% was used to make the ZDDP compound (s). The molar percentage of each of the alcohols present in the reaction mixture.) "Etc." is the alcohol present in the reaction mixture when more than three alcohols are used to make the ZDDP compound (s). It is shown that the equation can be expanded to include each of.

0078R in ZDDP₅And R₆The average total number of carbon atoms in the above is more than 10 carbon atoms per mole of phosphorus, and in one embodiment, there are more than 10 carbon atoms in the range of up to about 20 carbon atoms, and in one embodiment, 10 carbon atoms. It is a carbon atom in the range of up to about 15 in excess, and in one embodiment, it is a carbon atom in the range of about 12 to about 15, and in one embodiment, it is about 12 carbon atoms per mole of phosphorus. ..

0079The dialkyldithiophosphate zinc salt is prepared according to a known technique by first forming dialkyldithiophosphate (DDPA), usually by the reaction of one or more alcohols, and then neutralizing the formed DDPA with a zinc compound. obtain. Any basic or neutral zinc compound can be used to make the zinc salt, but oxides, hydroxides, and carbonates are most commonly used. The zinc dialkyldithiophosphate of component (i) can be made by a process such as that commonly described in US Pat. No. 7,368,596.

0080In some embodiments, the at least one zinc dialkyldithiophosphate salt is about 100 to about 1000 ppm phosphorus, or about 200 to about 1000 ppm phosphorus, or about 300 to about 300, based on the total weight of the lubricating oil composition. A sufficient amount may be present in the lubricating oil to provide about 900 ppm phosphorus, or about 400-about 800 ppm phosphorus, or about 550-about 700 ppm phosphorus.

0081Base oil The base oil used in the lubricating oil compositions herein can be selected from any of the base oils in Group IV specified in the American Petroleum Institute (API) Base Oil Interchangeability Guidelines. The groups of five base oils are as follows.

0082<tables num="1"><img id="000003" he="63" wi="170" file="JP2018520249A_D0001.tif" img-format="tif" img-content="drawing" /></tables>

0083Groups I, II, and III are mineral oil process stocks. Group IV base oils contain pure synthetic molecular species produced by the polymerization of olefinically unsaturated hydrocarbons. Many Group V base oils are also pure synthetic products, including diesters, polyol esters, polyalkylene glycols, alkylated aromatics, polyphosphate esters, polyvinyl ethers, and / or polyphenyl ethers, but vegetable oils. It can also be a naturally occurring oil such as. Note that although Group III base oils are derived from mineral oils, the rigorous treatment these fluids undergo makes their physical properties very similar to some pure compounds such as PAO. I want to be. Therefore, oils derived from Group III base oils can be referred to as synthetic fluids in the industry.

0084The base oil used in the disclosed lubricating oil compositions can be mineral oils, animal oils, vegetable oils, synthetic oils, or mixtures thereof. Suitable oils can be derived from hydrocracked, hydrogenated, hydrofinished, unrefined, refined, and re-refined oils, as well as mixtures thereof.

0085Unrefined oils are derived from natural, mineral or synthetic sources with little or no further refining. Refined oils are similar to unrefined oils, except that they are processed in one or more refining steps that can result in one or more property improvements. Examples of suitable purification techniques include solvent extraction, secondary distillation, acid or base extraction, filtration, leaching and the like. Oils refined to edible quality may or may not be useful. Cooking oil is also called white oil. In some embodiments, the lubricating oil composition is free of edible oils or white oils.

0086Rerefined oils are also known as regenerated or reprocessed oils. These oils are obtained in the same manner as refined oils using the same or similar processes. Often, these oils are additionally treated by techniques aimed at removing consumed additives and oil decomposition products.

0087Mineral oils can include oils obtained by rock drilling or from plants and animals, as well as mixtures thereof. For example, such oils include castor oil, lard oil, olive oil, peanut oil, corn oil, soybean oil, and flaxseed oil, as well as liquid petroleum and paraffin, naphthenic, or paraffin-naphthenic mixed varieties. Mineral lubricating oils such as solvent-treated or acid-treated mineral lubricating oils can be mentioned, but are not limited thereto. Such oils may be partially or completely hydrogenated, if desired. Oils derived from coal or shale can also be useful.

0088Useful synthetic lubricants include hydrocarbon oils such as polymerized, oligomerized or internally polymerized olefins (eg polybutylene, polypropylene, propylene / isobutylene copolymers); poly (1-hexene), poly (1-octene), 1 -Trimmers or oligomers of decene, such as poly (1-decene) (such materials are often referred to as α-olefins), and mixtures thereof; alkyl-benzenes (eg, dodecylbenzene, tetradecylbenzene, di). Nonylbenzene, di- (2-ethylhexyl) -benzene); polyphenyls (eg, biphenyls, terphenyls, alkylated polyphenyls); diphenylalkanes, alkylated diphenylalkanes, alkylated diphenyl ethers, and alkylated diphenyl sulfides, and these. Derivatives, analogs, and homologues of, or mixtures thereof. Polyalphaolefins are typically hydrogenated materials.

0089Other synthetic lubricants include polyol esters, diesters, liquid esters of phosphorus-containing acids (eg, tricresyl phosphate, trioctyl phosphate, diethyl esters of decanephosphonic acid), or polymers tetrahydrofuran. Synthetic oils can be produced by the Fischer-Tropsch reaction and can typically be hydrogenated isomerized Fischer-Tropsch hydrocarbons or waxes. In one embodiment, the oil can be prepared by the Fischer-Tropsch gas-liquid procedure and other gas-liquid oils.

0090The base oil containing more than 50% by weight in the lubricating oil composition can be selected from the group I, the group II, the group III, the group IV, the group V, and the group consisting of two or more combinations described above, and 50% by weight. Base oils exceeding the above are other than the base oils resulting from the provision of additive components or viscosity index improvers in the composition. In another embodiment, the base oil in excess of 50% by weight contained in the lubricating oil composition may be selected from groups II, III, IV, V, and a group consisting of two or more combinations described above. Base oils in excess of 50% by weight are other than diluent oils resulting from the provision of additive components or viscosity index improvers in the composition. In certain embodiments, the lubricating oil composition contains less than 10% by weight of Group IV and Group V oils alone or in combination. In certain embodiments, the lubricating oil composition comprises less than 5% by weight V group oil. In other embodiments, the lubricating oil composition does not contain any VI group oil, and in other predetermined embodiments, the lubricating oil composition does not contain any V group oil. In certain embodiments, the only base oil that exceeds 50% is the Group III base oil.

0091The amount of oil with a lubricating viscosity present is from 100% by weight to the amount of performance additives, including viscosity index improvers (s) and / or pour point lowering agents (s) and / or other surface treatment additives. It can be the remainder after subtracting the sum of. For example, oils with a lubricating viscosity that may be present in the final fluid are greater than about 50% by weight, more than about 60% by weight, more than about 70% by weight, more than about 80% by weight, more than about 85% by weight, or about 90% by weight. It can be a major amount such as super.

0092The lubricating oil composition may contain 10% by weight or less of Group IV base oil, Group V base oil, or a combination thereof. In each of the aforementioned embodiments, the lubricating oil composition comprises less than 5% by weight of Group V base oil. The lubricating oil composition does not contain Group IV base oil. The lubricating oil composition does not contain a group V base oil.

0093Lubricating oil compositions may also contain any one or more components selected from the various additives described below.

0094Antioxidant The lubricating oil compositions herein may also optionally contain one or more antioxidants. Antioxidant compounds are known and include, for example, phenates, phenate sulfides, olefin sulfides, terpen phosphosulfides, sulfide esters, aromatic amines, alkylated diphenylamines (eg, nonyldiphenylamine, di-nonyldiphenylamine, octyl). Diphenylamine, di-octyldiphenylamine), phenyl-alpha-naphthylamine, alkylated phenyl-alpha-naphthylamine, impaired non-aromatic amines, phenols, impaired phenols, oil-soluble molybdenum compounds, macromolecular antioxidants, or mixtures thereof. Be done. The antioxidant compounds may be used alone or in combination.

0095The damaged phenolic antioxidant may contain a secondary butyl group and / or a tertiary butyl group as steric hindrance groups. The phenolic group can be further substituted with a crosslinking group attached to a hydrocarbyl group and / or a second aromatic group. Examples of suitable impaired phenol antioxidants include 2,6-di-tert-butylphenol, 4-methyl-2,6-di-tert-butylphenol, 4-ethyl-2,6-di-tert-butylphenol, Included are 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 impaired phenolic antioxidant can be an ester, eg, an additive product derived from IRGANOX L-135 or 2,6-di-tert-butylphenol and alkyl acrylates available from BASF. It may contain about 1 to about 18, or about 2 to about 12, or about 2 to about 8, or about 2 to about 6, or about 4 carbon atoms. Another commercially available impaired phenolic antioxidant can be an ester, Albemarle It may include ETHANOX 4716 available from Corporation.

0096Useful antioxidants may include diarylamines and high molecular weight phenols. In one embodiment, the lubricating oil composition may contain a mixture of diarylamine and high molecular weight phenol, so that each antioxidant is up to about 5 weights based on the final weight of the lubricating oil composition. May be present in sufficient quantity to provide%. In one embodiment, the antioxidant may be a mixture of about 0.3 to about 1.5% by weight of diarylamine and about 0.4 to about 2.5% by weight of high molecular weight phenol, based on the final weight of the lubricating oil composition. ..

0097Examples of suitable olefins that can be sulfurized to form sulfide olefins include propylene, butylene, isobutylene, polyisobutylene, pentene, hexene, heptene, octene, nonene, decene, undecene, dodecene, tridecene, tetradecene, pentadecene, hexadecene, etc. Includes heptadecene, octadecene, nonadecene, eikosen, or mixtures thereof. In one embodiment, hexadecene, heptadecene, octadecene, nonadecene, eicosen, or mixtures thereof and their dimers, trimmers, and tetramers are particularly useful olefins. Alternatively, the olefin can be a Diels-Alder adduct of a diene such as 1,3-butadiene and an unsaturated ester such as butyl acrylate.

0098Another classification of sulphide olefins includes sulphurized fatty acids and their esters. Fatty acids are often obtained from vegetable and animal oils and typically contain from about 4 to about 22 carbon atoms. Examples of suitable fatty acids and esters thereof include triglycerides, oleic acid, linoleic acid, palmitoleic acid, or mixtures thereof. Often, fatty acids are obtained from lard oil, tall oil, peanut oil, soybean oil, cottonseed oil, sunflower seed oil, or a mixture thereof. Fatty acids and / or esters can be mixed with olefins such as α-olefins.

0099One or more antioxidants (s) are about 0% to about 20% by weight, or about 0.1% to about 10% by weight, or about 1% to about 5% by weight of the lubricating oil composition. Can exist within range.

0100Abrasion resistant The lubricating oil compositions herein may also optionally contain one or more wear resistant agents in addition to ZDDP. Examples of suitable additional abrasion resistant agents are metal thiophosphates, metal dialkyldithiophosphates, phosphates or salts thereof, phosphate esters (s), phosphite, phosphorus-containing carboxylic acid esters, ethers, or amides, sulfides. Examples include, but are not limited to, thiocarbamate-containing compounds containing olefins, thiocarbamate esters, alkylene bonded thiocarbamate, and bis (S-alkyldithiocarbamil) disulfides, and mixtures thereof. A suitable wear resistant agent can be molybdenum dithiocarbamate. Phosphorus-containing wear resistant agents are more fully described in European Patent No. 612839. The metal in the dialkyldithiophosphate salt can be an alkali metal, an alkaline earth metal, aluminum, lead, tin, molybdenum, manganese, nickel, copper, titanium, or zinc. A useful wear resistant agent can be zinc dialkylthiophosphate.

0101Further examples of suitable abrasion resistant agents include titanium compounds, tartrates, tartrate imides, oil-soluble amine salts of phosphorus compounds, olefin sulfides, phosphite (such as dibutylphosphite), phosphonates, thiocarbamate-containing compounds (thiocarbamate). Esters, thiocarbamate amides, carbamine ethers, alkylene-bonded thiocarbamate, and bis (S-alkyldithiocarbamyl) disulfides, etc.). The tartrate or tartrate imide may contain an alkyl-ester group, which may have a total of at least 8 carbon atoms on the alkyl group. Abrasion resistant agents include citrate in one embodiment.

0102The additional wear resistant is about 0% to about 15% by weight, or about 0.01% to about 10% by weight, or about 0.05% to about 5% by weight, or about 0.1% by weight to about 0.1% by weight of the lubricating oil composition. It can be present in the range containing 3% by weight.

0103Boron-containing compounds The lubricating oil composition herein may optionally contain one or more boron-containing compounds.

0104Examples of boron-containing compounds include borate esters, borooxide amines, booxide epoxides, booxide detergents, and booxide dispersants (such as the succinimide booxide dispersant disclosed in US Pat. No. 5,883,057). Be done.

0105If present, the boron-containing compound is 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. Can be used in sufficient quantity to provide%.

0106Additional cleaning agent The lubricating oil composition herein may optionally contain one or more low basic / neutral detergents. Low basic / neutral cleaners have a maximum of 175 mgKOH / g, or a maximum of 150 mgKOH / g of TBN. The low basic / neutral cleaner may include a calcium-containing cleaner. The low-basic neutral calcium-containing detergent can be selected from a calcium sulfonate cleaning agent, a calcium phenate cleaning agent, and a calcium salicylate cleaning agent. In some embodiments, the low basic / neutral cleaner is a calcium-containing cleaner or a mixture of calcium-containing cleaners. In some embodiments, the low basic / neutral cleaner is a calcium sulfonate cleaner or a calcium phenate cleaner.

0107The low basic / neutral cleaner, if present, may make up at least 0.2% by weight of the lubricating oil composition. In some embodiments, at least 0.4% by weight, or at least 0.6% by weight, or at least 0.8% by weight, or at least 1.0% by weight, or at least 1.2% by weight, or at least 2.0% by weight of the lubricating oil composition is optional. It is a low-basic / neutral detergent that is a low-basic / neutral calcium-containing detergent.

0108In certain embodiments, one or more low basic / neutral calcium-containing detergents provide the lubricating oil composition with about 50 to about 1000 wt ppm of calcium relative to the total weight of the lubricating oil composition. In some embodiments, one or more low basic / neutral calcium-containing cleaning agents are 75% by weight ppm to less than 800% by weight, or 100 to 600% by weight, based on the total weight of the lubricating oil composition. 125-500 ppm by weight of calcium is provided for the lubricating oil composition.

0109Dispersant The lubricating oil composition may optionally further contain one or more dispersants or mixtures thereof. Dispersants are often known as ashless dispersants because they do not contain ash-forming metals prior to mixing into the lubricating oil composition and they usually do not contribute to any ash upon addition to the lubricant. The ashless dispersant is characterized by a polar group attached to a relatively high molecular weight hydrocarbon chain. Typical ashless dispersants include N-substituted long chain alkenyl succinimides. Examples of N-substituted long chain alkenyl succinimides include polyisobutylene succinimides having a number average molecular weight of polyisobutylene substituents in the range of about 350 to about 50,000, or about 5,000, or about 3,000. Succinimide dispersants and their preparation are disclosed, for example, in US Pat. No. 7,897,696 or US Pat. No. 4,234,435. Polyolefins can be prepared from polymerizable monomers containing about 2 to about 16, or about 2 to about 8, or about 2 to about 6 carbon atoms. The succinimide dispersant is typically an imide formed from a polyamine, typically a poly (ethyleneamine).

0110In one embodiment, the present disclosure comprises at least one polyisobutylene succinimide dispersant derived from polyisobutylene having a number average molecular weight in the range of about 350 to about 50,000, or about 5000, or about 3000. Further included. Polyisobutylene succinimide may be used alone or in combination with other dispersants.

0111In some embodiments, polyisobutylene, when included, has a terminal double bond content of greater than 50 mol%, greater than 60 mol%, greater than 70 mol%, greater than 80 mol%, or greater than 90 mol%. Can be done. Such PIBs are also referred to as highly reactive PIBs ("HR-PIBs"). HR-PIBs having a number average molecular weight in the range of about 800 to about 5000 are suitable for use in the embodiments of the present disclosure. Conventional PIBs typically have a terminal double bond content of less than 50 mol%, less than 40 mol%, less than 30 mol%, less than 20 mol%, or less than 10 mol%.

0112HR-PIBs having a number average molecular weight in the range of about 900 to about 3000 may be suitable. Such HR-PIBs are commercially available or in the presence of non-chlorinated catalysts such as boron trifluoride described in US Pat. No. 4,152,499 to Boerzel et al. And US Pat. No. 5,739,355 to Gateau et al. It can be synthesized by the polymerization of isobutene. When used in the thermal Ene reaction described above, HR-PIB can result in higher conversion rates in the reaction and less sediment formation due to the increased reactivity. Suitable methods are described in US Pat. No. 7,897,696.

0113In one embodiment, the disclosure further comprises at least one dispersant derived from polyisobutylene succinic anhydride ("PIBSA"). PIBSA can have an average of about 1.0 to about 2.0 succinic acid moieties per polymer.

0114The% activity of alkenyl succinic anhydride or alkyl succinic anhydride can be determined using chromatographic techniques. This method is described in columns 5 and 6 of US Pat. No. 5,334,321.

0115The percent conversion of polyolefin is calculated from% activity using the equations in columns 5 and 6 of US Pat. No. 5,334,321.

0116Unless otherwise stated, all percentages are weight percent and all molecular weights are number average molecular weights.

0117In one embodiment, the dispersant may be derived from polyalphaolefin (PAO) succinic anhydride.

0118In one embodiment, the dispersant may be derived from an olefin maleic anhydride copolymer. As an example, the dispersant can be described as poly-PIBSA.

0119In one embodiment, the dispersant can be derived from the anhydride grafted onto the ethylene-propylene copolymer.

0120A classification of suitable dispersants can be Mannich bases. Mannich bases are materials formed by the condensation of higher molecular weight alkyl-substituted phenols, polyalkylene polyamines, and aldehydes (such as formaldehyde). Mannich bases are described in detail in US Pat. No. 3,634,515.

0121A suitable class of dispersants can be high molecular weight esters or semi-esteramides.

0122Suitable dispersants can also be post-treated by conventional methods by reacting with various agents. Among these are boron, urea, thiourea, dimercaptothiaizole, carbon disulfide, aldehydes, ketones, carboxylic acids, hydrocarbon-substituted succinic anhydride, maleic anhydride, nitriles, epoxides, carbonates, cyclic carbonates, etc. There are impaired phenolic esters and phosphorus compounds. US No. 7,645,726, US No. 7,214,649, and US No. 8,048,831 are incorporated herein by reference in their entirety.

0123In addition to carbonate and boric acid post-treatments, both compounds can be post-treated with various post-treatments designed to improve or confer different properties, or can be further post-treated. Such post-treatments include those summarized in columns 27-29 of US Pat. No. 5,241,003, which are incorporated herein by reference. As such processing, Inorganic phosphoric acid or anhydride (eg, US Pat. Nos. 3,403,102 and 4,648,980), Organophosphorus compounds (eg, US Pat. No. 3,502,677), Phosphorus pentasulfide, Boron compounds as already mentioned above (eg, US Pat. Nos. 3,178,663 and 4,652,387), Carboxylic acids, polycarboxylic acids, anhydrides, and / or acid halides (eg, US Pat. Nos. 3,708,522 and 4,948,386), Epoxides, polyepoxides, or thioepoxides (eg, US Pat. Nos. 3,859,318 and 5,026,495), Aldehydes or ketones (eg, US Pat. No. 3,458,530), Carbon disulfide (eg, US Pat. No. 3,256,185), Glycidol (eg, US Pat. No. 4,617,137), Urea, thiourine, or guanidine (eg, US Pat. Nos. 3,312,619, 3,865,813, and UK Pat. No. GB1,065,595), Organic sulfonic acids (eg, US Pat. No. 3,189,544 and UK Pat. No. GB2,140,811), Alkenyl cyanide (eg, US Pat. Nos. 3,278,550 and 3,366,569), Diketene (eg, US Pat. No. 3,546,243), Diisocyanate (eg, US Pat. No. 3,573,205), Alkane Sultone (eg, US Pat. No. 3,749,695), 1,3-Dicarbonyl compounds (eg, US Pat. No. 4,579,675), Alkoxylated alcohols or phenolic sulfates (eg, US Pat. No. 3,954,639), Cyclic lactones (eg, US Pat. Nos. 4,617,138, 4,645,515, 4,668,246, 4,963,275, and 4,971,711), Linear monocarbonates or polycarbonates of cyclic or thiocarbonates, or chloroformates (eg, US Pat. Nos. 4,612,132, 4,647,390, 4,648,886, 4,670,170), Nitrogen-containing carboxylic acids (eg, US Pat. No. 4,971,598 and UK Pat. No. GB2,140,811), Hydroxy-protected chlorodicarbonyloxy compounds (eg, US Pat. No. 4,614,522), Lactam, thiolactam, thiolactone, or ditholactone (eg, US Pat. Nos. 4,614,603 and 4,666,460), Linear monocarbonates or polycarbonates of cyclic or thiocarbonates, or chloroformates (eg, US Pat. Nos. 4,612,132, 4,647,390, 4,646,886, and 4,670,170), Nitrogen-containing carboxylic acids (eg, US Pat. No. 4,971,598 and UK Pat. No. GB2,440,811), Hydroxy-protected chlorodicarbonyloxy compounds (eg, US Pat. No. 4,614,522), Lactam, thiolactam, thiolactone, or dithiolactone (eg, US Pat. Nos. 4,614,603 and 4,666,460), Cyclic carbamate, cyclic thiocarbamate, or cyclic dithiocarbamate (eg, US Pat. Nos. 4,663,062 and 4,666,459), Hydroxyaliphatic carboxylic acids (eg, US Pat. Nos. 4,482,464, 4,521,318, 4,713,189), Oxidizing agents (eg, US Pat. No. 4,379,064), Combination of phosphorus pentasulfide and polyalkylene polyamines (eg, US Pat. No. 3,185,647), Combinations of carboxylic acids or aldehydes or ketones with sulfur or sulfur chloride (eg, US Pat. Nos. 3,390,086, 3,470,098), Combination of hydrazine and carbon disulfide (eg, US Pat. No. 3,519,564), Combinations of aldehydes and phenols (eg, US Pat. Nos. 3,649,229, 5,030,249, 5,039,307), A combination of aldehyde and dithiophosphate O-diesters (eg, US Pat. No. 3,865,740), Combination of hydroxyaliphatic carboxylic acid and boric acid (eg, US Pat. No. 4,554,086), Hydroxyaliphatic carboxylic acid and combination of formaldehyde and phenol (eg, US Pat. No. 4,636,322), Combination of hydroxyaliphatic carboxylic acid and aliphatic dicarboxylic acid (eg, US Pat. No. 4,663,064), A combination of formaldehyde and phenol, followed by glycolic acid (eg, US Pat. No. 4,699,724), A combination of hydroxyaliphatic carboxylic acid or oxalic acid, followed by diisocyanate (eg, US Pat. No. 4,713,191), A combination of an inorganic acid or anhydride of phosphorus or a partial or total sulfur analog thereof and a boron compound (eg, US Pat. No. 4,857,214), A combination of an organic diacid, then an unsaturated fatty acid, and then a nitroso aromatic amine, optionally a subsequent boron compound, and then a glucholing agent (eg, US Pat. No. 4,973,412), Combination of aldehyde and triazole (eg, US Pat. No. 4,963,278), Combinations of aldehydes and triazoles, followed by boron compounds (eg, US Pat. No. 4,981,492), Treatment with a combination of cyclic lactone and boron compounds (eg, US Pat. Nos. 4,963,275 and 4,971,711) can be mentioned. The above patents are incorporated herein in their entirety.

0124A suitable dispersant TBN can be from about 10 to about 65 without oil, which is about 5 to about 30 as measured on a dispersant sample containing about 50% diluted oil. Equivalent to TBN.

0125If present, the dispersant 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 dispersant that can be used is from about 0.1% to about 15% by weight, or about 0.1% to about 10% by weight, or about 3% by weight, based on the final weight of the lubricating oil composition. It can be about 10% by weight, or about 1% to about 6% by weight, or about 7% to about 12% by weight. In some embodiments, the lubricating oil composition utilizes a mixed dispersant system. A single type or a mixture of two or more dispersants in any desired ratio can be used.

0126Friction modifier The lubricating oil compositions herein may also optionally contain one or more friction modifiers. Suitable friction modifiers may include metal-containing and metal-free friction modifiers, which include imidazolines, amides, amines, succinimides, alkoxylated amines, alkoxylated etheramines, oxide amines, amidoamines, nitriles, betaines. , Tertiary amines, imines, amine salts, aminoguanazines, alkanolamides, phosphonates, metal-containing compounds, glycerol esters, aliphatic sulfide compounds and olefins, sunflower oils and other naturally occurring vegetable or animal oils, dicarboxylic acid esters, polyols and 1 Esters or partial esters with more than a species of aliphatic or aromatic carboxylic acids can be mentioned, but are not limited thereto.

0127Suitable friction modifiers may contain linear, branched, or aromatic hydrocarbyl groups, or hydrocarbyl groups selected from mixtures thereof, whether saturated or unsaturated. Good. Hydrocarbyl groups can be composed of carbon and hydrogen, or heteroatoms such as sulfur or oxygen. Hydrocarbyl groups can range from about 12 to about 25 carbon atoms. In some embodiments, the friction modifier can be a long chain fatty acid ester. In another embodiment, the long chain fatty acid ester may be a monoester, a diester, or a (tri) glyceride. The friction modifier can be a long-chain fatty acid amide, a long-chain fatty ester, a long-chain fatty epoxide derivative, or a long-chain imidazoline.

0128Other suitable friction modifiers include organic, ash-free (metal-free), and nitrogen-free organic friction modifiers. Such friction modifiers can include esters formed by reacting carboxylic acids and anhydrides with alkanols and generally have polar end groups covalently attached to lipophilic hydrocarbon chains (eg, carboxyl or hydroxyl). Including. An example of an organic ash-free, nitrogen-free friction modifier is commonly known as glycerol monooleate (GMO), which may contain monoesters, diesters, and triesters of oleic acid. Other suitable friction modifiers are described in US Pat. No. 6,723,685, which is incorporated herein by reference.

0129Amine-based friction modifiers may include amines or polyamines. Such compounds may have linear, saturated or unsaturated hydrocarbyl groups, or a mixture thereof, and may contain from about 12 to about 25 carbon atoms. Further examples of suitable friction modifiers include alkoxylated amines and alkoxylated etheramines. Such compounds may have hydrocarbyl groups that are linear and either saturated or unsaturated, or a mixture thereof. They can contain from about 12 to about 25 carbon atoms. Examples include ethoxylated amines and ethoxylated ether amines.

0130Amines and amides, even when used by themselves, are additions to boron oxides, boron halides, metaborates, boric acid, or boron compounds such as monoalkyl borate, dialkyl borate, or trialkyl borate. Alternatively, it may be used in the form of a reaction product. Other suitable friction modifiers are described in US Pat. No. 6,300,291, which is incorporated herein by reference in its entirety.

0131The friction modifier can optionally be present in the range of about 0% to about 10% by weight, or about 0.01% to about 8% by weight, or about 0.1% to about 4% by weight.

0132Molybdenum-containing ingredients The lubricating oil compositions herein may also optionally contain one or more molybdenum-containing compounds. Oil-soluble molybdenum compounds can have the functional performance of abrasion resistant agents, antioxidants, friction modifiers, or mixtures thereof. Oil-soluble molybdenum compounds include molybdenum dithiocarbamate, molybdenum dialkyldithiophosphate, molybdenum dithiophosphinate, amine salt of molybdenum compound, molybdenum xanthate, molybdenum thioxanthate, molybdenum sulfide, molybdenum carboxylate, molybdenum alkoxide, trinuclear organic molybdenum. It may contain compounds and / or mixtures thereof. Molybdenum sulfide includes molybdenum disulfide. Molybdenum disulfide can be in the form of stable dispersion. In one embodiment, the oil-soluble molybdenum compound can be selected from the group consisting of molybdenum dithiocarbamate, molybdenum dialkyldithiophosphate, amine salts of molybdenum compounds, and mixtures thereof. In one embodiment, the oil-soluble molybdenum compound can be molybdenum dithiocarbamate.

0133Preferable examples of molybdenum compounds that can be used are from RT Vanderbilt Co., Ltd. under trade names such as Molyvan 822 , Molyvan A, Molyvan 2000 , and Molyvan 855 , and from Adeka Corporation. Available on the market under trade names such as Sakura-Lube S-165, S-200, S-300, S-310G, S-525, S-600, S-700, and S-710. Materials, as well as mixtures thereof. Suitable molybdenum components are described in US 5,650,381, US RE37,363E1, US RE38,929E1, and US RE40,595E1, which are incorporated herein by reference in their entirety.

0134Moreover, the molybdenum compound can be an acidic molybdenum compound. Included are molybdate, ammonium molybdate, sodium molybdate, potassium molybdate, and other alkali metals molybdate and other molybdate salts, such as sodium molybdate, MoOCl.₄, MoO₂Br₂, Mo₂O₃Cl₆, Molybdenum trioxide, or a similar acidic molybdenum compound. Alternatively, the composition may include, for example, US Pat. Nos. 4,263,152, 4,285,822, 4,283,295, 4,272,387, 4,265,773, 4,261,843, 4,259,195, which are incorporated herein by reference in their entirety. , And 4,259,194, and US Patent Publication No. 2002/0038525, molybdenum may be provided by the molybdenum / sulfur complex of the basic nitrogen compound.

0135Another classification of suitable organic molybdenum compounds is in formula Mo₃S_kL_nQ_z, And trinuclear molybdenum compounds such as mixtures thereof, where S represents sulfur and L is an organic having a sufficient number of carbon atoms to make the compound oil-soluble or oil-dispersible. Represents an independently selected ligand with a group, n is 1 to 4, k varies from 4 to 7, and Q is neutral such as water, amines, alcohols, phosphines, and ethers. Selected from the group of electron donating compounds, z ranges from 0 to 5 and includes non-chemical quantitative values. Within all of the organic groups of the ligand, there can be at least 21 total carbon atoms, such as at least 25, at least 30, or at least 35 carbon atoms. Additional suitable molybdenum compounds are described in US Pat. No. 6,723,685, which is incorporated herein by reference in its entirety.

0136Oil-soluble molybdenum compounds are present in sufficient amounts to provide about 0.5 ppm to about 2000 ppm, about 1 ppm to about 700 ppm, about 1 ppm to about 550 ppm, about 5 ppm to about 300 ppm, or about 20 ppm to about 250 ppm molybdenum. obtain.

0137Titanium-containing compound Another classification of additives includes oil-soluble titanium compounds. The oil-soluble titanium compound may function as an abrasion resistant agent, a friction modifier, an antioxidant, a deposition control additive, or one or more of these functions. In one embodiment, the oil-soluble titanium compound can be titanium (IV) alkoxide. Titanium alkoxides can be formed from monohydric alcohols, polyols, or mixtures thereof. The monovalent alkoxide 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 an alkoxide of 1,2-diol or polyol. In one embodiment, 1,2-diol comprises a fatty acid monoester of glycerol, such as oleic acid. In one embodiment, the oil-soluble titanium compound can be titanium carboxylate. In one embodiment, the titanium (IV) carboxylate can be titanium neodecanoate.

0138In one embodiment, the oil-soluble titanium compound is present in the lubricating oil composition in an amount that provides zero to about 1500 ppm by weight, or about 10 ppm to 500 ppm by weight, or about 25 ppm to about 150 ppm by weight of titanium. Can be done.

0139Transition metal-containing compounds In another embodiment, the oil-soluble compound may be a transition metal-containing compound or a metalloid. Examples of the transition metal include, but are not limited to, titanium, vanadium, copper, zinc, zirconium, molybdenum, tantalum, and tungsten. Suitable metalloids include, but are not limited to, boron, silicon, antimony, tellurium and the like.

0140In one embodiment, the oil-soluble compound that can be used with a Ca / M weight ratio in the range of about 0.8: 1 to about 70: 1 is a titanium-containing compound, where M is the lubricant as described above. It is the total metal in the composition. The titanium-containing compound may function as an abrasion resistant agent, a friction modifier, an antioxidant, a deposition control additive, or one or more of these functions. Among the titanium-containing compounds that can be used in the disclosed techniques or in the preparation of oil-soluble materials in the disclosed techniques are various Ti (IV) compounds such as titanium (IV) oxide, titanium. (IV) sulfide, titanium (IV) nitride, titanium (IV) alkoxides such as titanium methoxydo, titanium ethoxydo, titanium propoxide, titanium isopropoxide, titanium butoxide, titanium 2-ethylhexoxide, and titanium. Other titanium compounds or complexes, including but not limited to phenates, titanium carboxylates such as titanium (IV) 2-ethyl-1-3-hexanedioate or titanium citrate, or titanium oleate, as well as titanium ( IV) There is (triethanol aminato) isopropoxide. Other forms of titanium included in the disclosed techniques include titanium phosphates such as titanium dithiophosphates (eg dialkyldithiophosphates) and titanium sulfonates (eg alkylbenzene sulfonates), or generally titanium compounds and oils. Includes reaction products with various acid materials that form salts, such as soluble salts. Therefore, titanium compounds can be derived, among other things, from organic acids, alcohols, and glycols. The Ti compound may also be present in the form of a dimer or oligomer containing a Ti-O-Ti structure. Such titanium materials may be commercially available or readily prepared by suitable synthetic techniques apparent to those skilled in the art. They may exist at room temperature as solids or liquids, depending on the particular compound. They may also be provided in solution form in a suitable inert solvent.

0141In one embodiment, titanium can be supplied as a Ti-modified dispersant, such as a succinimide dispersant. Such materials can be prepared by forming a titanium mixed anhydride between titanium alkoxide and hydrocarbyl-substituted succinic anhydride such as alkenyl (or alkyl) succinic anhydride. The resulting titanate-succinate intermediate may be used directly or reacted with any of a number of materials, which materials are, for example, (a) polyamines with free condensable-NH functional groups. Components of succinimide / amide dispersant, (b) polyamine succinimide / amide dispersant, namely alkenyl- (or alkyl-) succinic anhydride and polyamine, (c) substituted succinic anhydride, polyol, aminoalcohol, polyamine. , Or a hydroxy-containing polyester dispersant prepared by reaction with a mixture thereof. Alternatively, the titanate-succinate intermediate may be reacted with other agents, such as alcohols, amino alcohols, ether alcohols, polyether alcohols or polyols, or fatty acids, and Ti as lubricants. Those products that are used directly to impart or are further reacted with the succinic dispersants described above. As an example, one part (in moles) of tetraisopropyl titanate is reacted with about two parts (in moles) of polyisobutene-substituted succinic anhydride at 140-150 ° C for 5-6 hours to give a titanium-modified dispersant or intermediate. The body may be provided. The resulting material (30 g) was further reacted with a succinimide dispersant from a polyisobutene-substituted succinic anhydride and polyethylene polyamine mixture (127 g + diluted oil) at 150 ° C. for 1.5 hours to produce a titanium-modified succinimide dispersant. You may.

0142Another titanium-containing compound is titanium alkoxide and C₆~ C₂₅It can be a reaction product with a carboxylic acid. The reaction product has the following formula

0143<chemistry num="2"><img id="000004" he="26" wi="48" file="JP2018520249A_D0001.tif" img-format="tif" img-content="drawing" /></chemistry>

0144(n is an integer chosen from 2, 3, and 4, and R is a hydrocarbyl group containing about 5 to about 24 carbon atoms.), Or formula.

0145<chemistry num="3"><img id="000005" he="51" wi="55" file="JP2018520249A_D0001.tif" img-format="tif" img-content="drawing" /></chemistry>

0146(In the formula, R¹, R², R³, And R⁴Each of them is the same or different and is selected from hydrocarbyl groups containing about 5 to about 25 carbon atoms. ) Can be represented. Suitable carboxylic acids include caproic acid, caprylic acid, lauric acid, myristic acid, palmitic acid, stearic acid, araquinic acid, oleic acid, erucic acid, linoleic acid, linolenic acid, cyclohexanecarboxylic acid, phenylacetic acid, benzoic acid, Examples include neodecanoic acid.

0147In one embodiment, the oil-soluble titanium compound is 0 to 3000 wt ppm titanium, or 25 wt ppm to about 1500 wt ppm titanium, or about 35 ppm to 500 wt ppm titanium, or about 50 ppm to about 300 ppm. It may be present in the lubricating oil composition in the amount provided.

0148Viscosity index improver The lubricating oil compositions herein may also optionally contain one or more viscosity index improvers. Suitable viscosity index improvers include polyolefins, olefin copolymers, ethylene / propylene copolymers, polyisobutene, styrene hydride-isoprene polymers, styrene / maleic acid ester copolymers, styrene hydride / butadiene copolymers, isoprene hydride polymers, alpha-olefins. Examples thereof include maleic anhydride copolymers, polymethacrylates, polyacrylates, polyalkylstyrenes, alkenylaryl hydride conjugated copolymers, or mixtures thereof. Viscosity index improvers may include star polymers, suitable examples of which are described in US Pat. No. 8,999,905B2.

0149The lubricating oil compositions herein may also optionally contain one or more dispersant viscosity index improvers in addition to or in place of the viscosity index improvers. Suitable viscosity index improvers are functionalized polyolefins, such as ethylene-propylene copolymers functionalized with the reaction product of acylating agents (maleic anhydride, etc.) and amines, polymethacrylates functionalized with amines. , Or an esterified maleic anhydride-styrene copolymer reacted with an amine.

0150Viscosity Index Improver and / or Dispersant The total amount of Viscosity Index Improver is about 0% to about 20% by weight, about 0.1% to about 15% by weight, about 0.1% by weight to about 12% by weight of the lubricating oil composition. %, Or about 0.5% to about 10% by weight.

0151Any other additive Other additives may be selected to perform one or more functions required for the lubricating fluid. Further, one or more of the additives mentioned may be multi-functional and may provide additional or other functions to those specified herein.

0152Lubricating oil compositions according to the present disclosure may optionally contain other performance additives. Other performance additives may be in addition to the additives specified in this disclosure and / or metal deactivators, viscosity index improvers, ashless TBN boosters, friction modifiers, abrasion resistant agents, corrosion inhibitors. Agents, rust inhibitors, dispersants, dispersants, viscosity index improvers, extreme pressure agents, antioxidants, foam inhibitors, demulsifiers, emulsifiers, flow point lowering agents, seal swelling agents, and one of their mixtures. It may contain more than a seed. Typically, a fully formulated lubricant contains one or more of these performance additives.

0153Suitable metal inactivators are derivatives of benzotriazole (typically triltriazole), dimercaptothiazazole derivatives, 1,2,4-triazole, benzimidazole, 2-alkyldithiobenzimidazole, or 2-alkyldithiobenzo. Thiazol; a copolymer of ethyl acrylate and 2-ethylhexyl acrylate, and optionally a vinyl acetate, foam suppressant; trialkyldithiophosphate, polyethylene glycol, polypropylene oxide, polymer of polypropylene oxide and (ethylene oxide-propylene oxide) Derivatives; may include flow point depressants, including maleic anhydride-styrene esters, polymethacrylates, polyacrylates, or polyacrylamides.

0154Suitable foam inhibitors include silicone compounds such as siloxane.

0155Suitable pour point depressants may include polymethylmethacrylate or a mixture thereof. The pour point depressant provides about 0% to about 1% by weight, about 0.01% to about 0.5% by weight, or about 0.02% to about 0.04% by weight based on the final weight of the lubricating oil composition. Can be present in sufficient quantity to.

0156A suitable rust inhibitor may be a single compound or a mixture of compounds having the property of suppressing corrosion of the divalent iron metal surface. Non-limiting examples of rust inhibitors useful herein include 2-ethylhexanoic acid, lauric acid, myristic acid, palmitic acid, oleic acid, linoleic acid, linolenic acid, behenic acid, and cerotic acid. Examples include oil-soluble high molecular weight organic acids and oil-soluble polycarboxylic acids containing dimer acids and trimer acids such as those produced from tall oil fatty acids, oleic acids, and linoleic acids. Other suitable corrosion inhibitors include long chain alpha, omega-dicarboxylic acid, and tetrapropenyl succinic acid, tetradecenyl succinic acid, and hexadecenyl succinic acid in the molecular weight range of about 600 to about 3000. Examples thereof include alkenylsuccinic acid in which the alkenyl group of the above contains about 10 or more carbon atoms. Another useful type of acidic corrosion inhibitor is a semi-ester of alkenyl succinic acid and polyglycol, which has about 8 to about 24 carbon atoms in the alkenyl group. The corresponding semi-amides of such alkenyl succinic acid are also useful. A useful rust suppressant is a high molecular weight organic acid. In some embodiments, the engine oil lacks a rust inhibitor.

0157If present, the rust inhibitor is about 0% by weight to about 5% by weight, about 0.01% by weight to about 3% by weight, about 0.1% by weight to about 2% by weight, based on the final weight of the present lubricating oil composition. Can be used in sufficient quantity to provide.

0158In general terms, suitable crankcase lubricants may contain additive components within the range listed in the table below.

0159<tables num="2"><img id="000006" he="115" wi="170" file="JP2018520249A_D0001.tif" img-format="tif" img-content="drawing" /></tables>

0160The percentage of each of the above components represents the weight percent of each component based on the weight of the final lubricating oil composition. The rest of the lubricating oil composition consists of one or more base oils.

0161The additives used in the formulation of the compositions described herein can be blended into the base oil individually or in various partial combinations. However, it may be preferable to use an additive concentrate (ie, an additive plus a diluent such as a hydrocarbon solvent) to blend all of the ingredients at the same time. The additives used in the formulation of the compositions described herein can be blended into the base oil individually or in various partial combinations. However, it may be preferable to use an additive concentrate (ie, an additive plus a diluent such as a hydrocarbon solvent) to blend all of the ingredients at the same time.

0162The present disclosure provides a novel lubricant blend specifically formulated for use as an automotive engine lubricant. Embodiments of the present disclosure may provide suitable lubricants for engine applications that provide improvements in one or more of the following properties: Slow pre-ignition event, antioxidant, wear resistance, rust control, fuel economy, water resistance, air contamination, seal protection, deposition reduction, ie TEOST 33 test pass, and foam reduction properties.

0163Fully formulated lubricants typically include dispersant / inhibitor packages or dispersion inhibitor (DI) packages and additive packages referred to herein that provide the properties required in the formulation. contains. Suitable DI packages are described, for example, in US Pat. Nos. 5,204,012 and 6,034,040. Additives Among the types of additives included in the package are dispersants, seal swelling agents, antioxidants, foam inhibitors, lubricants, rust inhibitors, corrosion inhibitors, emulsifiers, viscosity index improvers, etc. possible. Some of these ingredients are well known to those of skill in the art and are generally used in conventional amounts with the additives and compositions described herein.

0164The following examples are exemplary, but not limited, of the methods and compositions of the present disclosure. Other suitable modifications and indications of various conditions and parameters commonly encountered in the art are apparent to those skilled in the art and are within the spirit and scope of the present disclosure. All patents and publications cited herein are incorporated herein by reference in their entirety.

<p num="0165"> A fully blended lubricating oil composition containing conventional additives was prepared and the slow ignition events occurring in a boosted internal combustion engine lubricated with the lubricating oil composition were measured. Each of the lubricating oil compositions contains a major amount of base oil, a base conventional DI package plus a viscosity index improver (s), and the base DI package does not contain a viscosity index improver and is a lubricating oil composition. Provided about 8-12 weight percent of the thing. Base DI packages include conventional amounts of dispersants (s), abrasion resistant additives (s), defoamers (s), and antioxidants, as provided in Table 3 below. It contained (s). Specifically, the base DI package includes a succinimide dispersant, a succinimide booxide dispersant, a molybdenum-containing compound in an amount that supplies about 80 ppm of molybdenum to the lubricating oil composition, an organic friction modifier, and an antioxidant (s). , And a wear-resistant agent (s) (unless otherwise specified). 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 the diluting oil for the viscosity index improver (s). The main amount of base oil (about 78 to about 87% by weight) was in Group III. The modified components are identified in the tables and discussions of the examples below. All of the listed values are described as weight percent of the components in the lubricating oil composition (ie, the active ingredient plus the diluted oil, if any), unless otherwise specified.</p><p num="0166"><tables num="3"><img id="000007" he="84" wi="170" file="JP2018520249A_D0001.tif" img-format="tif" img-content="drawing" /></tables></p><p num="0167"> Low-speed pre-ignition (LSPI) events were measured with GM's 2.0-liter 4-cylinder Ecotec turbocharged gasoline direct injection (TGDi) engine. One complete LSPI combustion engine test consisted of four test cycles. Within a single test cycle, two stages of operation or segments were repeated to generate LSPI events. At stage A, when LSPI is most likely to occur, the engine is operated at a net mean effective pressure (BMEP) of about 2000 rpm and about 18,000 kPa. In stage B, if LSPI is unlikely to occur, the engine will run at about 1500 rpm and about 17,000 kPa BMEP. Collect data for each stage over 25,000 engine cycles. The structure of the test cycle is as follows. Stage A-Stage A-Stage B-Stage B-Stage A-Stage A. Each stage is separated by an idle period. Since LSPI is statistically significant during Stage A, the LSPI event data considered in this example included only LSPI generated during Stage A operation. Therefore, for one complete LSPI combustion engine test, the data were typically generated over a total of 16 stages and used for comparison and to assess the performance of the oils of the invention.</p><p num="0168"> The LSPI event was determined when 2% of the flammable material in the combustion chamber burned (MFB02) by monitoring the peak cylinder pressure (PP). The peak cylinder pressure threshold is calculated for each cylinder and each stage and is typically 65,000-85,000 kPa. The MFB02 threshold is calculated for each cylinder and each stage and typically ranges from about 3.0 to about 7.5 after top dead center (ATDC) crank angle (CAD). LSPI was recorded when both PP and MFB02 thresholds were exceeded in a single engine cycle. LSPI events can be directed in many ways. If different combustion engine tests can be performed with different numbers of engine cycles, the relative LSPI events of the oils of the invention for comparison are referred to as "relative LSPI events" for comparison and to eliminate the ambiguity involved in reporting the number per engine cycle. Reported as "LSPI ratio". In this way, improvements to some standard responses are clearly demonstrated.</p><p num="0169"> All reference oils are commercially available engine oils that meet all ILSAC GF-5 performance requirements.</p><p num="0170"> In the following examples, the LSPI ratio was reported as the ratio of the LSPI event of the test oil to the LSPI event of the reference oil "R-1". R-1 was a lubricating oil composition blended with a base DI package and an amount of a perbasic calcium cleaner that provided about 2400 ppm by weight Ca to the lubricating oil composition. R-1 also contained a sulfur-free molybdenum / amine complex in an amount sufficient to provide about 80 ppm by weight of molybdenum to the lubricating oil composition.</p><p num="0171"> Significant improvement in LSPI is observed when LSPI events are reduced by more than 50% compared to R-1 (LSPI ratio less than 0.5). If LSPI events are reduced by more than 70% (LSPI ratio less than 0.3), further improvement in LSPI is observed, and if LSPI events are reduced by more than 75% (LSPI ratio less than 0.25), more than LSPI. If further improvement is observed and the LSPI event is reduced by more than 80% for R-1 (LSPI ratio less than 0.20), further improvement for LSPI is observed and the LSPI event for R-1. If is reduced by more than 90% (LSPI ratio less than 0.10), further improvement in LSPI is observed. Therefore, the LSPI ratio of the R-1 reference oil is considered to be 1.00.</p><p num="0172"> Combinations of superbasic calcium cleaners with a variety of different zinc dialkyldithiophosphates (s) (ZDDP) were tested using the base formulation. Specifically, the effect on LSPI was determined by changing the type of alcohol (primary / secondary).</p><p num="0173"> The commercially available oil, R-1, is included as a reference oil to demonstrate current highest levels. Reference oil R-1 contains approximately 80.7% by weight of Group III base oil, 12.1% by weight of HiTEC® 11150PCMO additive package available from Afton Chemical Corporation, and 7.2% by weight of 35SSI ethylene / propylene copolymer viscosity. It was formulated from an index improver. The HiTEC® 11150 Passenger Car Motor Oil Additive Package is an API SN, ILSAC-GF-5, and ACEA A5 / B5 certified DI package. R-1 also showed the following properties and partial elemental analysis.</p><p num="0174"><tables num="4"><img id="000008" he="84" wi="170" file="JP2018520249A_D0001.tif" img-format="tif" img-content="drawing" /></tables></p><p num="0175"> The following examples evaluated the effect on the LSPI ratio caused by the inclusion of ZDDP compounds from different ratios of primary and secondary alcohols. In all of the following compositions, the sulfur-free molybdenum / amine complex was used in an amount that provided about 80 ppm by weight of molybdenum in the lubricating oil composition. Comparative Example C-1 contained the same formulation as R-1, but contained a smaller amount of perbasic calcium cleaner. The hyperbasic calcium cleaner was included in Formulation C-1 in an amount that provided approximately 1600 wt ppm Ca to the lubricating oil composition. In addition, formulation C-1 contained ZDDP derived only from primary alcohols. Since each of Comparative Formulation C-1 and Example Compositions I-1 and I-2 were tested using the same engine, a direct performance comparison could be made.</p><p num="0176"> R-1 is a commercially available oil and is included to demonstrate current highest standards. R-1 meets all the performance requirements of ILSAC GF-5. Comparative Example C-1 was designed to show the effect of ZDDP derived only from primary alcohols on the LSPI ratio. Formulation I-1 contained a ZDDP compound derived only from secondary alcohols. Formulation I-2 is a secondary alcohol of 50:50 derived from both primary and secondary alcohols and indicated in terms of phosphorus content by weight supplied to the lubricating oil composition. It contained a ZDDP compound with a ratio to alcohol. Table 5 shows the specific concentration of each component of the lubricating oil composition. The results are also included in Table 5, showing the contribution of Zn and P from the ZDDP compound.</p><p num="0177"><tables num="5"><img id="000009" he="89" wi="170" file="JP2018520249A_D0001.tif" img-format="tif" img-content="drawing" /></tables></p><p num="0178"> In Table 5, formulation C-1 shows that the use of a significantly reduced amount of calcium in the lubricating oil composition reduces the LSPI ratio compared to reference oil R-1. Formulation C-1 used ZDDP derived only from primary alcohols. Formulations I-1 and I-2 increase the ratio of secondary alcohols used to make ZDDP compounds to primary alcohols, as in Comparative Example C-1, only primary alcohols. Using ZDDP derived from, it has been shown that the LSPI ratio is significantly reduced compared to when all other components are maintained at the same level. Comparisons of formulations C-1 and I-2 also show that as the ratio of secondary alcohols in ZDDP to primary alcohols increases, the LSPI ratio decreases. Table 5 shows that lubricating oil compositions with ZDDP compounds derived from at least a portion of secondary alcohols are more effective at reducing the LSPI ratio than ZDDP compounds derived solely from primary alcohols. ..</p><p num="0179"> Numerous US patents and other documents are referenced in many places throughout the specification. All such cited documents are fully expressly incorporated into this disclosure as if fully described herein.</p><p num="0180"> Other embodiments of the present disclosure will become apparent to those skilled in the art from the discussion herein and the implementation of the embodiments disclosed herein. As used herein and throughout the claims, "one (a)" and / or "one (an)" can refer to one or more. Unless otherwise indicated, all numbers used herein and in the claims to represent properties such as raw material weights, molecular weights, percentages, reaction conditions, etc., whether or not the term "about" is present. Regardless, in all cases it should be understood as being modified by the term "about". Thus, unless otherwise indicated, the numerical parameters described herein and in the claims are approximations that may vary depending on the desired properties required to be obtained by the present disclosure. At a minimum, we do not attempt to limit the application of the equivalent doctrine to the claims, but each numerical parameter is at least in light of the number of effective digits reported and is usually rounded off. It should be interpreted by applying the technology. Although the numerical ranges and parameters that describe the broad scope of the present disclosure are approximations, the numerical values described in the particular embodiment are reported as accurately as possible. However, any number essentially contains certain errors that inevitably result from the standard deviations found in their respective test measurements. It is intended that the present specification and examples are merely exemplary and the true scope and intent of the present disclosure is to be considered as set forth by the following claims.</p><p num="0181"> The aforementioned embodiments are in fact susceptible to significant fluctuations. Therefore, embodiments are not intended to be limited to the particular illustrations described above herein. Rather, the embodiments described above are within the spirit and scope of the appended claims, including their legally available equivalents.</p><p num="0182"> To the extent that the patentee does not intend to publicly dedicate any disclosed embodiments, and any disclosed modifications or modifications may not be within the scope of the claims in the literature. Under equivalent doctrine, it is considered part of this specification.</p><p num="0183"> Each component, compound, substituent, or parameter disclosed herein may be used alone or as one of each and all other components, compounds, substituents, or parameters disclosed herein. It should be construed as disclosed for use in combination with one or more.</p><p num="0184"> Also, each quantity / value or range of quantities for each component, compound, substituent, or parameter disclosed herein is any other component (s), compound disclosed herein. It should also be construed as being disclosed in combination with each quantity / value or range of quantities (s), substituents (s), or parameters (s), and is also described herein. Any combination of two or more of the disclosed components (s), compounds (s), substituents (s), or quantities / values or ranges of quantities for a parameter is therefore also described herein. It should be understood that they are disclosed in combination with each other for the purposes of the book.</p><p num="0185"> It is further understood that each range disclosed herein should be construed as a disclosure of each particular value within the disclosed range having the same number of significant digits. Therefore, the range 1-4 should be construed as a clear disclosure of the values 1, 2, 3, and 4.</p><p num="0186"> Each lower limit of each range disclosed herein is disclosed in combination with each upper limit of each range disclosed herein and each specific value within each range for the same component, compound, substituent, or parameter. It is further understood that it should be interpreted as being. Therefore, in the present disclosure, each lower limit of each range is combined with each upper limit of each range, or with each specific value within each range, or each upper limit of each range is combined with each specific value within each range. It should be construed as a full range of disclosures induced by combining with.</p><p num="0187"> In addition, specific quantities / values of components, compounds, substituents, or parameters disclosed herein or in Examples should be construed as disclosures of either lower or upper limits of the range. , Any other upper or lower limit of the range for the same component, compound, substituent, or parameter disclosed elsewhere in the application, or in combination with a particular quantity / value, the component, compound, substitution. A range for a group or parameter can be formed.</p>