Mixed fleet capable lubricant composition

Abstract

To provide a lubricating additive and a lubricant composition including such additive suitable for and / or configured for mixed fleet use.SOLUTION: A lubricant composition includes: a detergent system that provides both calcium and magnesium from one or more of sulfonates, phenates, salicylates, or mixtures thereof, and has a weight ratio of calcium to magnesium of about 1.5:1 to about 2:1; and an antiwear and friction system that includes two or more metal dialkyldithiophosphates derived from a specific ratio of primary and secondary alcohols, wherein an amount of magnesium from the detergent system is at least 500 ppm based on the lubricant composition, and amounts of phosphorus and zinc from the antiwear and friction system are less than 1,200 ppm and less than 1,000 ppm, respectively, based on the lubricant composition.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present disclosure relates to additive systems configured for mixed fleet use and lubricating compositions containing the additive systems, particularly lubricating compositions capable of meeting the performance standards of both compression ignition heavy duty applications and spark ignition passenger car applications. [Background technology]

[0002] Automotive manufacturers continue to seek improved efficiency and fuel economy, which continues to increase the demands on engines, lubricants, and their components. Today's spark-ignition passenger car engines are often smaller, lighter, and more efficient with technologies designed to improve fuel economy, performance, and power. Meanwhile, engines for compression-ignition heavy-duty applications are often designed for heavier loads, operation at or near peak power, extreme conditions, and / or more cyclical operation, but such engines must meet stringent standards for improved efficiency and fuel economy. These requirements also mean that the performance of engine oils must evolve to meet the higher demands of such modern engines and their corresponding performance standards associated with their unique uses and applications. Such stringent demands on engine oils often lead lubricant manufacturers to tailor lubricants, such as fluids configured for compression-ignition heavy-duty engines or fluids configured for passenger cars, and their additives to meet the specific performance requirements for each unique application. Typically, a lubricant designed for one application will not meet all of the performance specifications of a different application, since each application requires specific performance criteria.

[0003] For example, the American Petroleum Institute (API) sets standards for passenger car motor oils designed to meet the needs and performance characteristics of various passenger vehicle manufacturers. Recent updates to API standards include performance testing for an undesirable phenomenon typically characterized as low-speed pre-ignition (LSPI), which is considered to be a form of combustion that results in ignition of the air-fuel mixture in the combustion chamber before the desired ignition. Often, turbocharged or supercharged engines are prone to LSPI, which is a pre-ignition event that may include high pressure spikes, early combustion, and / or knock. When premature ignition occurs in the combustion chamber before the spark plug fires, it can cause abnormal combustion and high cylinder pressures. LSPI events can cause a knocking sound or other abnormal characteristics from an uncontrolled pressure rise in the cylinder. LSPI events are undesirable, and recent API specifications set LSPI performance standards for passenger car motor oils.

[0004] On the other hand, lubricants designed for compression ignition heavy duty engine applications, such as heavy duty diesel engines, tend to offer some outside use cases, with an emphasis on suitability for truck engines, fleet operators, mining facilities, and construction equipment engines. Fluids for such applications therefore often focus on performance characteristics that are different from typical passenger vehicles. For example, lubricants for heavy duty use are often configured to maintain friction and viscosity performance with soot and / or sludge control that may be specific to more heavy duty applications, as is common in diesel engines.

[0005] However, because motor oils for spark ignition passenger cars have unique and distinct performance requirements compared to compression ignition heavy duty applications, fluids designed for one application do not necessarily meet the performance standards for the other application. For example, lubricants designed for spark ignition passenger car standards do not necessarily meet the friction requirements for compression ignition heavy duty applications, and fluids for compression ignition heavy duty applications do not necessarily meet the LSPI performance standards for spark ignition passenger car applications. Summary of the Invention

[0006] In one approach or embodiment, a lubricating composition suitable for compression ignition heavy duty applications and spark ignition engines. In one aspect, the lubricating composition includes a detergent system providing both calcium and magnesium from one or more of a sulfonate, phenate, salicylate, or mixtures thereof, and an antiwear and friction system including one or more metal dialkyldithiophosphates derived from primary and secondary alcohols, wherein the weight ratio of primary to secondary alcohols in the antiwear and friction system is at least about 3:1, the amount of magnesium from the detergent system is at least 500 ppm magnesium based on the lubricating composition, the amount of phosphorus from the antiwear and friction system is less than 1200 ppm phosphorus based on the lubricating composition (in other approaches or embodiments, less than 1000 ppm phosphorus or less than 800 ppm phosphorus), and the amount of zinc from the antiwear and friction system is less than 1000 ppm zinc based on the lubricating composition.

[0007] In other embodiments or approaches, the compositions may include optional embodiments or features in any composition. Such optional features or embodiments include the calcium provided by the detergent system is provided by one or more of calcium phenate, calcium sulfonate, or mixtures thereof in an amount providing from about 900 to about 1500 ppm of calcium; and / or the weight ratio of calcium to magnesium provided by the detergent system is from about 1.5:1 to about 2:1; and / or the detergent system comprises from about 50 to about 70 weight percent calcium phenate, from about 30 to about 40 weight percent magnesium sulfonate, and from 0 to about 10 weight percent calcium sulfonate; and / or the detergent system comprises from about 60 to about 70 weight percent calcium phenate, from about 32 to about 38 weight percent magnesium sulfonate, and from about 1 to about 4 weight percent calcium sulfonate; and / or the calcium sulfonate has a total alkali number of less than 50; and / or the antiwear and friction system comprises two zinc dialkyldithiophosphates; and / or the antiwear and friction system comprises a first zinc dialkyldithiophosphate derived from a primary alcohol. and / or the antiwear and friction system comprises one or more zinc dialkyldithiophosphate additives derived from a majority amount of a primary alcohol; and / or the antiwear and friction system comprises up to about 60 weight percent of a first zinc dialkyldithiophosphate derived from a primary alcohol and about 40 to about 50 weight percent of a second zinc dialkyldithiophosphate derived from a mixture of primary and secondary alcohols; and / or the second zinc dialkyldithiophosphate derived from a mixture of primary and secondary alcohols is derived from about 50 to about 70 weight percent of a primary alcohol and about 30 to about 50 weight percent of a secondary alcohol; and / or the detergent system comprises a calcium sulfonate having a neat total base number of 20 to 80; and / or the detergent system comprises a calcium phenate having a neat total base number of 300 to 450;and a magnesium sulfonate having a neat total base number of from about 500 to about 700; and / or the total base number of the lubricating composition is less than about 15 (or in other approaches, less than about 12, or even less than about 10); and / or the lubricating composition further comprises a viscosity modifier additive selected from polyolefins, olefin copolymers, ethylene / propylene copolymers, polyisobutene, hydrogenated styrene-isoprene polymers, styrene / maleic acid ester copolymers, hydrogenated styrene / butadiene copolymers, hydrogenated isoprene polymers, alpha-olefin maleic anhydride copolymers, polymethacrylates, polyacrylates, polyalkylstyrenes, hydrogenated alkenyl aryl conjugated diene copolymers, or mixtures thereof; and / or the lubricating composition comprises about 9 weight percent or less of a viscosity modifier additive; and / or the lubricating composition comprises a viscosity modifier additive selected from the group consisting of ... and / or the lubricating composition has one or more of: an absolute percent change from initial slip time of about 10 percent or less, according to Allison Transmission Friction Test TES-439, November 2010; and an absolute percent change from initial coefficient of friction (median) of 10 percent or less, according to Allison Transmission Friction Test TES-439, November 2010.

[0008] In another embodiment, a method of lubricating an engine with a lubricating composition that meets API SP, API CK-4, and API FA-4 certifications. In some aspects, the method includes lubricating an engine with the lubricating composition, the lubricating composition comprising a detergent system providing both calcium and magnesium from one or more of a sulfonate, a phenate, a salicylate, or mixtures thereof, and an antiwear and friction system comprising one or more zinc dialkyldithiophosphates derived from primary and secondary alcohols, wherein the weight ratio of primary to secondary alcohols in the antiwear and friction system is at least about 3:1, the amount of magnesium from the detergent system is greater than 500 ppm magnesium based on the lubricating composition, the amount of phosphorus from the antiwear and friction system is less than 1200 ppm phosphorus based on the lubricating composition (in other embodiments less than 1000 ppm phosphorus or less than 800 ppm phosphorus), the amount of zinc from the antiwear system is less than 1000 ppm zinc based on the lubricating composition, and the lubricating composition is a lubricating composition that meets ASTM A2314 standard using two iterations. The lubricating composition exhibits an average number of events of five or less according to the Sequence IX Low Speed ​​Pre-ignition Test according to D8291-21a, and has an absolute percent change from initial slip time of about 10 percent or less according to Allison Transmission Friction Test TES-439, November 2010, and an absolute percent change from initial median coefficient of friction of 10 percent or less according to Allison Transmission Friction Test TES-439, November 2010.

[0009] In other embodiments or approaches, the method may include optional embodiments, steps, or features in any of the compositions. Such optional features, steps, or embodiments may include, but are not limited to, the calcium provided by the detergent system being provided by one or more of calcium phenate, calcium sulfonate, or mixtures thereof in an amount providing from about 900 to about 1500 ppm of calcium; and / or the weight ratio of calcium to magnesium provided by the detergent system is from about 1.5:1 to about 2:1; and / or the detergent system comprises from about 50 to about 70 weight percent calcium phenate, from about 30 to about 40 weight percent magnesium sulfonate, and from about 0 to about 10 weight percent calcium sulfonate; and / or the detergent system comprises from about 60 to about 70 weight percent calcium phenate, from about 32 to about 38 weight percent magnesium sulfonate, and from about 1 to about 4 weight percent calcium sulfonate; and / or the calcium sulfonate has a total alkali number of less than 50; and / or the antiwear and friction system comprises a first zinc dialkyldithiophosphate derived from a primary alcohol and a mixture of a primary alcohol and a secondary alcohol. and / or the antiwear and friction system includes one or more zinc dialkyldithiophosphate additives derived from a majority amount of a primary alcohol, and / or the antiwear and friction system includes up to about 60 weight percent of the first zinc dialkyldithiophosphate derived from a primary alcohol and about 40 to about 50 weight percent of the second zinc dialkyldithiophosphate derived from a mixture of primary and secondary alcohols, and / or the antiwear and friction system includes one or more zinc dialkyldithiophosphate additives derived from a majority amount of a primary alcohol and a mixture of primary and secondary alcohols. the second zinc dialkyldithiophosphate derived from a mixture with a secondary alcohol is derived from about 50 to about 70 weight percent primary alcohol and about 30 to about 50 weight percent secondary alcohol; and / or the detergent system includes a calcium sulfonate having a neat total base number of 20 to 80; and / or the detergent system includes a calcium phenate having a neat total base number of 300 to 450, and a magnesium sulfonate having a neat total base number of about 500 to about 700.

[0010] In yet other embodiments, the present disclosure provides for the use of any of the embodiments of the lubricating compositions of this overview for API SP, API CK-4, and API FA-4 certification, particularly achieving an average number of events greater than 5 according to a Sequence IX Low Speed ​​Pre-Ignition Test according to ASTM D8291-21a using 2 replicates, and achieving an absolute percent change from initial slip time of about 10 percent or less according to Allison Transmission Friction Test TES-439, November 2010, and an absolute percent change from initial median coefficient of friction of 10 percent or less according to Allison Transmission Friction Test TES-439, November 2010.

[0011] Other embodiments of the present disclosure will be apparent to those skilled in the art from consideration of the specification and practice of the invention disclosed herein. The following definitions are provided to clarify the meaning of certain terms used herein.

[0012] The terms "lubricant oil," "lubricant composition," "lubricant composition," "lubricant," and "lubricating fluid" refer to a finished lubricant product comprising a majority of a base oil and a minor amount of an additive composition.

[0013] As used herein, the terms "additive package," "additive concentrate," or "additive composition" refer to that portion of a lubricating oil composition other than a majority of the base oil.

[0014] As used herein, the term "hydrocarbyl substituent" or "hydrocarbyl group" is used in its ordinary sense and is known to those skilled in the art. Specifically, it refers to a group having a carbon atom directly attached to the remainder of the molecule and having a predominantly hydrocarbon character. Each hydrocarbyl group is independently selected from hydrocarbon substituents and substituted hydrocarbon substituents containing one or more of halo, hydroxyl, alkoxy, mercapto, nitro, nitroso, amino, pyridyl, furyl, imidazolyl, oxygen, and nitrogen, with not more than two non-hydrocarbon substituents present for every 10 carbon atoms in the hydrocarbyl group.

[0015] As used herein, the term "weight percent" or "wt. %" means the percentage of the listed component expressed by weight of the entire composition, unless otherwise specified. All percentages herein are weight percent unless otherwise specified.

[0016] The terms "soluble", "oil-soluble" or "dispersible" used herein may, but do not necessarily, indicate that a compound or additive is soluble, dissolvable, miscible or suspendable in oil in all proportions. However, the terms mean that they are, for example, soluble, suspendable, soluble or stably dispersible in oil to a sufficient degree to exert their intended effect in the environment in which the oil is used. Furthermore, if desired, the incorporation of other additives may also allow the incorporation of higher levels of the specific additive.

[0017] As used herein, the term "alkyl" refers to straight, branched, cyclic, and / or substituted saturated chain moieties of about 1 to about 200 carbon atoms. As used herein, the term "alkenyl" refers to straight, branched, cyclic, and / or substituted saturated chain moieties of about 3 to about 30 carbon atoms. As used herein, the term "aryl" refers to monocyclic and polycyclic aromatic compounds that may contain alkyl, alkenyl, alkylaryl, amino, hydroxyl, alkoxy, halo substituents, and / or heteroatoms such as, but not limited to, nitrogen and oxygen.

[0018] As used herein, molecular weight is measured by gel permeation chromatography (GPC) using commercially available polystyrene standards (with Mn of about 180 to about 18,000 as calibration standards). The number average molecular weight (Mn) of any embodiment herein may be determined by a gel permeation chromatography (GPC) instrument obtained from Waters or a similar instrument and data processed with Waters Empower Software or a similar software. The GPC instrument may be equipped with a Waters separation module and a Waters refractive index detector (or similar optional instrument). GPC operating conditions may include a guard column, four Agilent PLgel columns (length 300×7.5 mm, particle size 5μ, and pore size range 100-10000 Å), column temperature about 40° C. Non-stabilized HPLC grade tetrahydrofuran (THF) may be used as the solvent at a flow rate of 1.0 mL / min. GPC instruments can be calibrated with commercially available polystyrene (PS) standards with narrow molecular weight distributions ranging from 500 to 380,000 g / mol. The calibration curve can be extrapolated for samples with masses less than 500 g / mol. Samples and PS standards can be dissolved in THF and prepared at concentrations of 0.1 to 0.5 weight percent and can be used without filtration. GPC measurements are also described in U.S. Pat. No. 5,266,223, which is incorporated herein by reference. The GPC method also provides molecular weight distribution information. See, for example, W.W. Yau, J.J. Kirkland and D.D. Ly, "Modern Size Exclusion Liquid Chromatography", John Wiley and Sons, New York, 1979, which is incorporated herein by reference.

[0019] Throughout this disclosure, the terms "comprises," "includes," "contains," and the like are considered to be open ended and should be understood to include any element, step, or ingredient not expressly recited. The phrase "consisting essentially of" is meant to include any explicitly recited element, step, or ingredient, as well as any additional elements, steps, or ingredients that do not materially affect the basic and novel aspects of the invention. This disclosure also contemplates that any composition described using the terms "comprises," "includes," or "contains" should be construed as including a disclosure of the same composition "consisting essentially of" or "consisting of" that specifically recited ingredient. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0020] In one aspect, the present disclosure describes lubricant additives and lubricants including such additives suitable and / or configured for mixed fleet use, such as unique additives and lubricants that meet the performance criteria for a typical spark ignition passenger car lubricant as well as the performance criteria for a lubricant suitable for a typical compression ignition heavy duty engine application. Thus, the fluids herein are mixed fleet, configured for and / or usable in either or both applications as the circumstances require.

[0021] In another approach, the lubricating compositions described herein are suitable for diesel and gasoline engine applications. The lubricating compositions include at least a base oil of lubricating viscosity and a unique detergent system combined with a characteristic antiwear and friction system that achieves both the LSPI performance criteria designed for, for example, spark ignition passenger cars and the friction performance for compression ignition heavy duty engine applications. Previously, fluids designed to meet LSPI requirements did not necessarily meet the friction requirements of heavy duty engines, and fluids designed for heavy duty friction requirements did not necessarily meet the LSPI requirements for passenger cars. The fluids herein meet both properties.

[0022] In one approach, the lubricating compositions herein include a base oil or blend of base oils; (i) a detergent system having a plurality of additives providing calcium and magnesium from one or more of sulfonates, phenates, salicylates, or mixtures thereof, and which may include or consist essentially of calcium phenate and magnesium sulfonate and optionally calcium sulfonate; and (ii) an antiwear and friction system comprising or consisting essentially of one or more metal dialkyldithiophosphates, preferably a mixture of metal dialkyldithiophosphates, preferably a mixture of zinc dialkylthiophosphates, derived from a blend of primary and secondary alcohols, and in multiple approaches, an antiwear and friction system comprising a specific blend of metal dialkyldithiophosphates within the total mixture derived from primary to secondary alcohols, wherein the weight ratio of primary alcohol to secondary alcohol used to form the metal dialkyldithiophosphate in the antiwear and friction system is at least 3:1.

[0023] In other approaches, the lubricating compositions further include specific amounts of magnesium, phosphorus, and metal (preferably zinc) in the final fluid to achieve performance suitable for mixed fleet applications. For example, in some approaches, the lubricating compositions have an amount of magnesium from the detergent system that is greater than 500 ppm magnesium based on the lubricating composition, an amount of phosphorus from the antiwear and friction system that is less than 1200 ppm phosphorus (preferably less than 1000 ppm phosphorus, even more preferably less than 800 ppm phosphorus) based on the lubricating composition, and an amount of metal (such as zinc) from the antiwear and friction system that is less than about 1000 ppm metal (such as zinc) based on the lubricating composition. In yet other embodiments, the lubricating compositions herein can also include calcium provided by the detergent system, but can include up to about 1500 ppm calcium, and in yet other optional embodiments, the fluids herein have a weight ratio of calcium to magnesium provided by the detergent system ranging from about 1.5:1 to about 4:1. Lubricating compositions having such characteristics surprisingly meet the LSPI requirements for passenger cars and, at the same time, the friction performance requirements for heavy duty engine applications, thus recognizing that the fluids herein are so-called mixed fleet compatible fluids that can be used in either application depending on the desired use and circumstances.

[0024] Detergent-based The lubricant compositions herein include a unique detergent system that provides a selected amount of magnesium, and in some embodiments also a selected amount of calcium, delivered from detergent additives such as phenates and sulfonates, particularly calcium phenates and magnesium sulfonates, and optionally calcium sulfonates (preferably low based on neutral calcium phenates, if included). Suitable detergents and methods for their preparation are described in more detail in numerous patent publications, including U.S. Pat. No. 7,732,390 and the references cited therein, which are incorporated herein by reference. The lubricant compositions herein may include from about 1 to about 5 weight percent, and in other approaches, from about 1.5 to about 3 weight percent of the detergent system.

[0025] As noted above, in some approaches, the detergent system provides a selected amount of magnesium, and in some approaches, it also provides a selected amount of calcium. For example, the detergent system provides an amount of magnesium that is greater than about 500 ppm magnesium, and in other approaches, about 500 ppm to about 1000 ppm magnesium, about 600 ppm to about 800 ppm magnesium, or about 700 to about 800 ppm magnesium, based on the total lubricating composition. At the same time, the fluid may also have a limited amount of calcium provided by the detergent system. In embodiments, the detergent system optionally provides about 1500 ppm or less of calcium, about 1400 ppm or less of calcium, about 1300 ppm or less of calcium, or about 900 to about 1500 ppm of calcium, or about 1000 ppm to about 1300 ppm of calcium. In this approach, calcium and magnesium are provided by phenates and / or sulfonates, preferably calcium is provided by a combination of a phenate and optionally a sulfonate, while magnesium is provided by a sulfonate.

[0026] In some approaches, the correct balance between calcium and magnesium from the detergent system is one factor that helps maintain a mixed fleet compatible fluid because if the balance is not set properly, the fluid will not meet the performance benefits for both spark ignition passenger vehicles as well as compression ignition heavy duty applications and will not qualify for mixed fleet use. In some embodiments, the detergent system has a weight ratio of calcium to magnesium provided by the detergent system of about 1.5:1 to about 4:1, about 1.6:1 to about 3:1, about 1.6:1 to about 2:1, or about 1.7:1 to about 2:1. The majority of the calcium can be provided by calcium phenate, and the remainder can be provided by optional calcium sulfonate. The magnesium can be provided by magnesium sulfonate. For example, the detergent system can include about 50 to about 70 weight percent calcium phenate, about 30 to about 40 weight percent magnesium sulfonate, and about 0 to about 10 weight percent calcium sulfonate.

[0027] The detergent system may also include other optional detergents as required by circumstances, so long as the weight ratio of magnesium to calcium described above is met. Generally, the detergent base may be salted with an alkali metal or alkaline earth metal, such as, but not limited to, calcium and magnesium as described above, but other optional detergents may also be salted with potassium, sodium, lithium, barium, zinc, or mixtures thereof, so long as the detergent system meets the calcium and magnesium requirements described herein.

[0028] In one approach, suitable detergents in the system can include alkali metal or alkaline earth metal salts of petroleum sulfonic acids, such as calcium or magnesium salts, and long chain mono- or di-alkylaryl sulfonic acids, where the aryl groups can include benzyl, tolyl, and xylyl, and / or various phenates or derivatives of phenates. Examples of suitable detergents include the following detergents: calcium phenate, calcium sulfur-containing phenates, calcium sulfonates, calcium calixarates, calcium salixalates, calcium salicylates, calcium carboxylates, calcium phosphates, calcium mono- and / or di-thiophosphates, calcium alkylphenols, calcium sulfur-bound alkylphenol compounds, calcium methylene bridged phenols, magnesium phenate, magnesium sulfur-containing phenates, magnesium sulfonates, magnesium calixarates ... magnesium phosphates, calcium phosphates, calcium mono- and / or di-thiophosphates, calcium alkylphenols, calcium sulfur-bound alkylphenol compounds, calcium methylene bridged phenols, magnesium phenate, magnesium sulfur-containing phenates, magnesium sulfonates, magnesium calixarates, magnesium phosphates, calcium phosphates, calcium phosphates, calcium mono- and / or di-thiophosphates, calcium alkylphenols, calcium sulfur-bound alkylphenol compounds, calixarates), magnesium salixarates, magnesium salicylates, magnesium carboxylates, magnesium phosphates, magnesium mono- and / or di-thiophosphates, magnesium alkylphenols, magnesium sulfur-linked alkylphenol compounds, magnesium methylene bridged phenols, sodium phenates, sodium sulfonates, sodium calixarates, sodium salixarates, sodium salicylates, sodium carboxylates, sodium phosphates, sodium mono- and / or di-thiophosphates, sodium alkylphenols, sodium sulfur-linked alkylphenol compounds, or sodium methylene bridged phenols.

[0029] The detergent can also be neutral / low based or overbased. Overbased detergent additives are known in the art and can be alkali metal or alkaline earth metal overbased detergent additives. Such detergent additives can be prepared by reacting a metal oxide or metal hydroxide with a substrate and carbon dioxide gas. The substrate is typically an acid, such as an aliphatic substituted sulfonic acid, an aliphatic substituted carboxylic acid, or an aliphatic substituted phenol.

[0030] The term "overbased" refers to metal salts, such as metal salts of sulfonates, carboxylates, salicylates, and / or phenates, in which the amount of metal present exceeds the stoichiometric amount. Such salts may have a conversion level of more than 100% (i.e., they may contain more than 100% of the theoretical amount of metal required to convert the acid to its "normal" or "neutral" salt). The expression "metal ratio", often abbreviated as MR, is used to indicate the ratio of the total chemical equivalents of the metal in an overbased salt to the chemical equivalents of the metal in a neutral salt, according to known chemical reactivity and stoichiometry. In normal or neutral salts, the MR is 1, and in overbased salts, the MR is greater than 1. They are generally referred to as overbased, hyperbasic, or superbasic salts and may be salts of organic sulfur acids, carboxylic acids, or phenols.

[0031] As used herein, the term "TBN (Total Base Number)" is used to represent the total base number in mg KOH / g as measured by the method of ASTM D2896. The overbased detergent of the lubricating oil composition may have a total base number (TBN) of about 200 mg KOH / gram or more, or about 250 mg KOH / gram or more, or about 350 mg KOH / gram or more, or about 375 mg KOH / gram or more, or about 400 mg KOH / gram or more. The overbased detergent may have a metal to substrate ratio of from 1.1:1, or from 2:1, or from 4:1, or from 5:1, or from 7:1, or from 10:1.

[0032] Examples of suitable overbased detergents include, but are not limited to, overbased calcium phenate, overbased calcium sulfur-containing phenate, overbased calcium sulfonate, overbased calcium calixarate, overbased calcium salixarate, overbased calcium salicylate, overbased calcium carboxylic acid, overbased calcium phosphate, overbased calcium mono- and / or di-thiophosphate, overbased calcium alkylphenol, overbased calcium sulfur-bound alkylphenol compound, overbased calcium methylene bridged phenol, overbased magnesium phenate, overbased magnesium sulfonate, overbased magnesium calixarate, overbased magnesium salicylate, overbased magnesium salicylate, overbased magnesium salicylate, overbased magnesium carboxylate, overbased magnesium salixarate, overbased magnesium mono- and / or di-thiophosphate, overbased magnesium alkylphenol, overbased magnesium sulfur-bound alkylphenol compound, or overbased magnesium methylene bridged phenol.

[0033] When a low-based or neutral detergent is incorporated into the detergent system, it generally has a TBN of up to 175 mg KOH / g, up to 150 mg KOH / g, up to 100 mg KOH / g, or up to 50 mg KOH / g. The low-based / neutral detergent may include a calcium or magnesium-containing detergent. Examples of suitable low-based / neutral detergents include, but are not limited to, calcium sulfonate, calcium phenate, calcium salicylate, magnesium sulfonate, magnesium phenate, and / or magnesium salicylate.

[0034] In some embodiments, when optional calcium sulfonate is incorporated into the detergent system herein, it can be a neutral or low based detergent, in some approaches, having a total base number of about 0 to about 100, and in other approaches, having a total base number of about 0 to about 50. When calcium phenate is incorporated into the detergent system, it can be an overbased detergent, having a total base number of 150 to 400, and in other approaches, about 200 to about 350. When magnesium sulfonate is incorporated into the detergent system, it can be an overbased detergent, having a total base number of 300 to 500, and in other approaches, about 350 to about 450. In some approaches, the detergent systems and lubricants herein also do not contain overbased calcium sulfonate, or do not contain calcium sulfonate additives having a TBN of 200 or more, preferably 300 or more. As used herein, "free" generally means that the particular ingredient is present in an amount of less than 0.5% by weight, less than 0.1% by weight, less than 0.05% by weight, or not at all. The TBN values ​​above reflect the TBN value of the final detergent diluted in the base oil.

[0035] In other embodiments, the TBN of the detergent may reflect the neat or undiluted version of the detergent ingredient. For example, calcium sulfonate as a neat (or undiluted) additive may have a TBN of 0 to about 80, in other approaches about 20 to about 80. Calcium phenate as a neat additive may have a TBN of about 300 to about 450, in other approaches about 380 to about 420. Magnesium sulfonate as a neat additive may have a TBN of about 500 to about 700, in other approaches about 600 to about 700. In yet other embodiments, the detergent systems and lubricants herein may be free of overbased calcium sulfonates having a neat TBN of about 600 or greater.

[0036] Wear and friction systems The lubricating compositions herein also include an anti-wear and friction system in combination with the detergent system described above. The anti-wear and friction system provides, among other features, a mixture of metal and phosphorus-containing compounds effective to achieve friction performance. In embodiments, the lubricating compositions herein may include from about 0.7 to about 2 weight percent, and in other approaches from about 0.9 to about 1.5 weight percent of the anti-wear and friction system.

[0037] In some approaches, the antiwear and friction system includes one or more metal dihydrocarbyl dithiophosphate compounds, and in some approaches, a mixture of two or more metal dihydrocarbyl dithiophosphate compounds, such as, but not limited to, a mixture of zinc dihydrocarbyl dithiophosphate compound(s) (ZDDP). Suitable metal dithiophosphates such as ZDDP may include 5 to about 12 weight percent metal (in other approaches, about 6 to about 10 weight percent metal, where the metal is preferably zinc), and about 8 to about 20 weight percent sulfur (in other approaches, about 11 to about 19 weight percent sulfur). Metal dithiophosphates such as ZDDP may also include about 5 to about 10 weight percent phosphorus. Suitable metal dihydrocarbyl dithiophosphates can be any metal dihydrocarbyl dithiophosphate salt, where the metal can be an alkali metal, alkaline earth metal, aluminum, lead, tin, molybdenum, manganese, nickel, copper, titanium, zirconium, zinc, or combinations thereof, however, the metal is preferably zinc.

[0038] When the phosphorus-containing compound of the antiwear and friction system is ZDDP, the alkyl group on the ZDDP can be derived from a primary alcohol, a secondary alcohol, and / or a mixture thereof. For example, suitable primary alcohols for forming the alkyl group of the ZDDP include, but are not limited to, ethylhexyl alcohol, 2-ethylhexyl alcohol, butanol, isobutyl alcohol, amyl alcohol, and / or C6 or higher primary alcohols. Suitable secondary alcohols for forming the alkyl group of the ZDDP include, but are not limited to, methyl isobutyl carbinol, isopropyl alcohol, or a mixture thereof. In some cases, the alkyl group of the ZDDP can be derived from a mixture of primary and secondary alcohols, such as 2-ethylhexanol (primary), isobutanol (primary), and isopropanol (secondary). For example, in one embodiment, one of the ZDDP additives in the antiwear and friction system contains about 20% alkyl groups derived from 2-ethylhexanol, about 40% alkyl groups derived from isobutanol, and about 40% alkyl groups derived from isopropanol. In another embodiment, the second ZDDP in the antiwear and friction system contains all alkyl groups derived from a primary alcohol, such as 2-ethylhexanol. In one approach, the antiwear and friction system herein contains a mixture of metal dialkyldithiophosphates (preferably zinc dialkyldithiophosphates) derived from primary and secondary alcohols. In an embodiment, the weight ratio of primary alcohol to secondary alcohol from the two ZDDP additives combined in the antiwear and friction system is at least 3:1, as discussed further below.

[0039] Examples of suitable ZDDPs include metal O,O-di(C1- 14-alkyl)dithiophosphate;(mixed O,O-bis(sec-butyl and isooctyl))dithiophosphate;Zinc-O,O-bis(branched and linear C3-8-alkyl)dithiophosphate;Zinc O,O-bis(2-ethylhexyl)dithiophosphate;Zinc O,O-bis(mixed isobutyl and pentyl)dithiophosphate;Zinc mixed O,O-bis(1,3-dimethylbutyl and isopropyl)dithiophosphate;Zinc O,O-diisooctyldithiophosphate;Zinc O,O-dibutyldithiophosphate;Zinc mixed O,O-bis(2-ethylhexyl and isobutyl and isopropyl)dithiophosphate;Zinc O,O-bis(dodecylphenyl)dithiophosphate;Zinc O,O-di zinc O-(6-methylheptyl)-O-(1-methylpropyl)dithiophosphate; zinc O-(2-ethylhexyl)-O-(isobutyl)dithiophosphate; zinc O,O-diisopropyldithiophosphate; zinc (mixed hexyl and isopropyl)dithiophosphate; zinc (mixed O-(2-ethylhexyl) and O-isopropyl)dithiophosphate; zinc O,O-dioctyldithiophosphate; zinc O,O-dipentyldithiophosphate; zinc O-(2-methylbutyl)-O-(2-methylpropyl)dithiophosphate; and zinc O-(3-methylbutyl)-O-(2-methylpropyl)dithiophosphate.

[0040] In yet another approach, each of the phosphorus-containing compounds in the antiwear system herein can each have the structure of Formula I:

[0041] [ka] In formula I, R independently contains 1 to 18 carbon atoms, or 2 to 12 carbon atoms, or about 3 to 8 carbon atoms. The antiwear and friction system may contain two compounds of the structure of formula I. In each compound, R may be ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl, amyl, n-hexyl, i-hexyl, n-octyl, decyl, dodecyl, octadecyl, 2-ethylhexyl, phenyl, butylphenyl, cyclohexyl, methylcyclopentyl, propenyl, butenyl, as needed to meet the selectivity ratio of primary alcohol to secondary alcohol described above in the antiwear system. In some embodiments, the number of carbon atoms in each R group in formula I above is generally about 3 or more, about 4 or more, about 6 or more, or about 8 or more. Each R group may have an average of 3 to 8 carbons. The total number of carbon atoms in the R groups may be 5 to about 72, or 12 to about 32. In formula I, A is a metal such as aluminum, lead, tin, molybdenum, manganese, nickel, copper, titanium, zirconium, zinc, or a combination thereof. Preferably, A is zinc.

[0042] In yet another approach, the zinc dialkyldithiophosphate of the antiwear and friction system has a sulfur-zinc coordination arrangement of the phosphorus compound in the antiwear system shown under the chemical structure of formula II, which can be used interchangeably with formula I shown above. It is also understood that the structures shown in formulas I and II can exist as monomers, dimers, trimers, or oligomers (e.g., tetramers).

[0043] [ka]

[0044] In some embodiments, each phosphorus-containing compound of the antiwear and friction system has the structure of Formula I, where A is zinc, and the total of the compounds in the antiwear and friction system provides about 600 to about 900 ppm (in other approaches, about 700 to about 800 ppm) of phosphorus to the lubricant composition. In some cases, the antiwear and friction system includes a zinc dialkyldithiophosphate derived from a mixture of primary and secondary alcohols. In other cases, the antiwear and friction system includes at least two zinc dialkyldithiophosphates, a first zinc dialkyldithiophosphate derived only from primary alcohols and a second zinc dialkyldithiophosphate derived from a mixture of primary and secondary alcohols. Preferably, the antiwear and friction system comprises one or more zinc dialkyldithiophosphates, and the majority of the alkyl groups are derived from primary alcohols, for example, the weight ratio of primary alcohols to secondary alcohols forming the ZDDP in the antiwear and friction system (i.e., all compounds in the antiwear mixture) is at least 3:1 (i.e., about 75 to about 85% of all alkyl groups in the ZDDP contained in the antiwear and friction system are derived from primary alcohols, and about 15 to about 25% of the alkyl groups are derived from secondary alcohols). In another approach, the ratio of primary alcohols to secondary alcohols forming the ZDDP in the antiwear and friction system is at least about 4.1, or about 3:1 to about 5.5:1.

[0045] In another embodiment, the antiwear and friction system can include up to about 60 weight percent of a first zinc dialkyldithiophosphate derived exclusively from primary alcohols and about 40 to about 50 weight percent of a second zinc dialkyldithiophosphate derived from a mixture of primary and secondary alcohols. The second zinc dialkyldithiophosphate can be derived from a mixture of primary and secondary alcohols including about 50 to about 70 weight percent primary alcohol and about 30 to about 50 weight percent secondary alcohol.

[0046] Typically, lubricating compositions designed for compression ignition heavy duty applications have required up to 1200 ppm phosphorus, and in some cases from about 1000 to about 1200 ppm phosphorus. In contrast, the lubricating compositions herein have 1200 ppm or less phosphorus, 1000 ppm or less phosphorus, or even 800 ppm or less phosphorus. In other approaches, the lubricating compositions herein include at least about 100 ppm phosphorus, at least about 200 ppm phosphorus, at least about 300 ppm phosphorus, at least about 400 ppm phosphorus, at least about 500 ppm phosphorus, at least about 600 ppm phosphorus, or even at least about 700 ppm phosphorus. However, even at such low levels of phosphorus, the fluids herein surprisingly meet the performance requirements described herein for both passenger car applications and compression ignition heavy duty engine applications.

[0047] Dihydrocarbyl dithiophosphate metal salts can be prepared according to known techniques, typically by reacting one or more alcohols or phenols with P2S5 to first form dihydrocarbyl dithiophosphoric acid (DDPA), and then neutralizing the formed DDPA with a metal compound such as zinc oxide. For example, DDPA can be made by reacting a mixture of primary and secondary alcohols with P2S5. In this case, the DDPA contains alkyl groups derived from both primary and secondary alcohols. Alternatively, multiple DDPAs can be prepared, with the alkyl groups on one DDPA derived entirely from secondary alcohols and the alkyl groups on another DDPA derived entirely from primary alcohols. The DDPAs are then blended together to form a mixture of DDPAs with alkyl groups derived from both primary and secondary alcohols.

[0048] Base Oil The base oil used in the lubricating oil compositions herein may be an oil of lubricating viscosity and may be selected from any of the base oils in Groups I to V as defined in the American Petroleum Institute (API) Base Oil Interchangeability Guidelines. The five base oil groups are as follows:

[0049] [Table 1]

[0050] Groups I, II, and III are mineral oil process feedstocks. Group IV base oils contain true synthetic molecular species produced by polymerization of olefinically unsaturated hydrocarbons. Many Group V base oils are also true synthetic products and may include diesters, polyol esters, polyalkylene glycols, alkylated aromatics, polyphosphate esters, polyvinyl ethers, and / or polyphenyl ethers, etc., but may also be natural oils, such as vegetable oils. It should be noted that Group III base oils are derived from mineral oils, but the rigorous processing these fluids undergo makes their physical properties very similar to some true synthetic oils, such as PAOs. Thus, oils derived from Group III base oils may be referred to as synthetic fluids in the industry. Group II+ may include high viscosity index Group II.

[0051] The base oil or base oil blend used in the disclosed lubricating oil composition may be a mineral oil, an animal oil, a vegetable oil, a synthetic oil, a synthetic oil blend, or a mixture thereof. Suitable oils may be derived from hydrocracked, hydrogenated, hydrofinished, unrefined, refined, and rerefined oils, and mixtures thereof.

[0052] Unrefined oils are derived from natural, mineral, or synthetic sources with little or no further purification treatment. Refined oils are similar to unrefined oils, except that they have been treated with one or more purification steps that may result in the improvement of one or more properties. Examples of suitable purification techniques are solvent extraction, secondary distillation, acid or base extraction, filtration, percolation, etc. Oils refined to edible quality may or may not be useful. Edible oils may also be referred to as white oils. In some embodiments, the lubricating oil composition does not include edible oils or white oils.

[0053] Rerefined oils are also known as reclaimed or reprocessed oils. These oils are obtained similarly to refined oils using the same or similar processes. Often these oils are further processed by techniques aimed at removing spent additives and oil breakdown products.

[0054] Mineral oils may include oils obtained by drilling or from plants and animals, or any mixture thereof. For example, such oils may include, but are not limited to, castor oil, lard oil, olive oil, peanut oil, corn oil, soybean oil, and linseed oil, as well as mineral lubricating oils, such as liquid petroleum oils, and solvent- or acid-treated mineral lubricating oils of the paraffinic, naphthenic, or mixed paraffinic-naphthenic types. Such oils may be partially or fully hydrogenated, if desired. Oils derived from coal or shale may also be useful.

[0055] Useful synthetic lubricating oils can include hydrocarbon oils such as polymerized, oligomerized, or interpolymerized olefins (e.g., polybutylene, polypropylene, propylene isobutylene copolymers); poly(1-hexene), poly(1-octene), trimers or oligomers of 1-decene, such as poly(1-decene) (such materials are often referred to as alpha-olefins), and mixtures thereof; alkyl-benzenes (e.g., dodecylbenzene, tetradecylbenzene, dinonylbenzene, di-(2-ethylhexyl)-benzene); polyphenyls (e.g., biphenyl, terphenyl, alkylated polyphenyls); diphenylalkanes, alkylated diphenylalkanes, alkylated diphenyl ethers, and alkylated diphenyl sulfides, and derivatives, analogs, and homologs thereof, or mixtures thereof. The polyalphaolefins are typically hydrogenated materials.

[0056] Other synthetic lubricating oils include polyol esters, diesters, liquid esters of phosphorus-containing acids (e.g., tricresyl phosphate, trioctyl phosphate, and diethyl ester of decane phosphonic acid), or polymeric tetrahydrofurans. Synthetic oils can be produced by the Fischer-Tropsch reaction and typically can be hydroisomerized Fischer-Tropsch hydrocarbons or waxes. In one embodiment, the oils can be prepared by the Fischer-Tropsch gas-liquid synthesis procedure, as well as other gas-liquid oils.

[0057] A majority of the base oil included in the lubricating composition may be selected from the group consisting of Group I, Group II, Group III, Group IV, Group V, and combinations of two or more of the foregoing, wherein the majority of the base oil is other than the base oil resulting from the provision of an additive component or viscosity index improver in the composition. In another embodiment, a majority of the base oil included in the lubricating composition may be selected from the group consisting of Group I, Group II, Group III, Group IV, Group V, and combinations of two or more of the foregoing, wherein the majority of the base oil is other than the base oil resulting from the provision of an additive component or viscosity index improver in the composition.

[0058] The amount of oil of lubricating viscosity present may be the remainder remaining after subtracting the sum of the amounts of performance additives, including viscosity index improver(s) and / or pour point depressant(s) and / or other top treat additives, from 100% by weight. For example, the oil of lubricating viscosity may be present in the final fluid in a "major amount," such as greater than about 50% by weight, greater than about 60% by weight, greater than about 70% by weight, greater than about 80% by weight, greater than about 85% by weight, or greater than about 90% by weight.

[0059] Optional Additives The lubricating compositions described herein may also contain other additives in addition to the detergent and antiwear system components described above, including, but not limited to, antioxidant(s), viscosity modifier(s), other phosphorus-containing components, other detergent(s), corrosion inhibitor(s), rust inhibitor(s), antifoam agent(s), demulsifier(s), pour point depressant(s), seal swell agent(s), additional dispersant(s), friction modifier(s), and / or additional sulfur-containing component(s), so long as the other additives do not affect the above-mentioned compositional characteristics and relationships suitable for mixed fleet fluids.

[0060] Antioxidants Antioxidants reduce the tendency of base stocks to deteriorate during use. Such deterioration may be manifested by oxidation products such as sludge and varnish that build up on metal surfaces. Such antioxidants include hindered phenols, aromatic amine antioxidants, and sulfur-containing antioxidants.

[0061] Examples of phenolic antioxidants include 2,6-di-tert-butylphenol, liquid mixtures of tertiary butylated phenols, 2,6-di-tert-butyl-4-methylphenol, 4,4'-methylenebis(2,6-di-tert-butylphenol), 2,2'-methylenebis(4-methyl-6-tert-butylphenol), and mixed methylene bridged polyalkylphenols, and 4,4'-thiobis(2-methyl-6-tert-butylphenol), N,N'-di-sec-butyl-phenylenediamine, 4-isopropylaminodiphenylamine, phenyl-alpha-naphthylamine, phenyl-alpha-naphthylamine, and ring alkylated diphenylamines. Examples include sterically hindered tertiary butylated phenols, bisphenols and cinnamic acid derivatives, and combinations thereof.

[0062] Aromatic amine antioxidants include those having the following formula:

[0063] [ka] (wherein R' and R'' each independently represent a substituted or unsubstituted aryl group having 6 to 30 carbon atoms). Examples of the substituent of the aryl group include an aliphatic hydrocarbon group such as an alkyl group having 1 to 30 carbon atoms, a hydroxy group, a halogen radical, a carboxylic acid or ester group, or a nitro group.

[0064] The aryl groups are preferably substituted or unsubstituted phenyl or naphthyl, in particular where one or both of the aryl groups are substituted with at least one alkyl having from 4 to 30 carbon atoms, preferably from 4 to 18 carbon atoms, most preferably from 4 to 9 carbon atoms. It is preferred that one or both of the aryl groups are substituted, for example mono-alkylated diphenylamines, di-alkylated diphenylamines, or mixtures of mono- and di-alkylated diphenylamines.

[0065] Examples of diarylamines that may be used include, but are not limited to, diphenylamine; the various alkylated diphenylamines, 3-hydroxydiphenylamine, N-phenyl-1,2-phenylenediamine, N-phenyl-1,4-phenylenediamine, monobutyldiphenyl-amine, dibutyldiphenylamine, monooctyldiphenylamine, dioctyldiphenylamine, monononyldiphenylamine, dinonyldiphenylamine, monotetradecyldiphenylamine, ditetradecyldiphenylamine, phenyl-alpha-naphthylamine, monooctylphenyl-alpha-naphthylamine, phenyl-beta-naphthylamine, monoheptyldiphenylamine, diheptyl-diphenylamine, p-oriented styrenated diphenylamines, mixed butyloctyldi-phenylamines, and mixed octylstyryldiphenylamines.

[0066] Sulfur-containing antioxidants include, but are not limited to, sulfurized hindered phenols, sulfurized olefins, metal thiocarbamates, and ashless dialkyl dithiocarbamates. Sulfurized olefins are characterized by the type of olefin used in their preparation and the final sulfur content of the antioxidant. High molecular weight olefins, i.e., having an average molecular weight of 168 to 351 g / mole, are preferred. Examples of olefins that can be used include alpha-olefins, isomerized alpha-olefins, branched olefins, cyclic olefins, and combinations thereof.

[0067] Alpha-olefins include, but are not limited to, any C4-C25 alpha-olefin. The alpha-olefins may be isomerized prior to or during the sulfurization reaction. Structural and / or conformational isomers of alpha-olefins containing internal double bonds and / or branching may also be used. For example, isobutylene is the branched olefin counterpart of the alpha-olefin 1-butene.

[0068] Sulfur sources that may be used in the sulfurization reaction of olefins include elemental sulfur, sulfur monochloride, sulfur dichloride, sodium sulfide, sodium polysulfide, and mixtures thereof added together or at different stages of the sulfurization process.

[0069] Unsaturated oils may also be sulfurized and used as antioxidants due to their unsaturation. Examples of oils or fats that may be used include corn oil, canola oil, cottonseed oil, grapeseed oil, olive oil, palm oil, peanut oil, coconut oil, rapeseed oil, safflower seed oil, sesame seed oil, soybean oil, sunflower seed oil, tallow, and combinations thereof.

[0070] Ashless dialkyldithiocarbamates that may be used as antioxidant additives include compounds that are soluble or dispersible in the additive package. It is also preferred that the ashless dialkyldithiocarbamates have low volatility, preferably having a molecular weight greater than 250 Daltons, and most preferably having a molecular weight greater than 400 Daltons. Examples of dialkyldithiocarbamates that may be used are disclosed in the following patents: U.S. Pat. Nos. 5,693,598, 4,876,375, 4,927,552, 4,957,643, 4,885,365, 5,789,357, 5,686,397, 5,902,776, 2,786,866, 2,710,872, 2,384,577, 2,897,152, 3,407,222, 3,867,359, and 4,758,362.

[0071] The total amount of antioxidant in the lubricating compositions herein may be present in an amount to deliver up to about 200 ppm nitrogen, or up to about 100 ppm nitrogen, or up to about 150 ppm nitrogen, or up to about 100 to about 150 ppm nitrogen.

[0072] Friction modifiers In some embodiments, the lubricating composition herein may contain friction modifiers.Suitable additional friction modifiers may include metal-containing and metal-free friction modifiers, and suitable friction modifiers may include, but are not limited to, imidazolines, amides, amines, succinimides, alkoxylated amines, alkoxylated etheramines, amine oxides, amidoamines, nitriles, betaines, quaternary amines, imines, amine salts, aminoguanidines, alkanolamides, phosphonates, metal-containing compounds, glycerol esters, sulfurized fatty compounds and olefins, sunflower oil, other naturally occurring vegetable or animal oils, dicarboxylic acid esters, esters or partial esters of polyols, and one or more aliphatic or aromatic carboxylic acids.

[0073] Suitable friction modifiers may contain hydrocarbyl groups selected from linear, branched, or aromatic hydrocarbyl groups, or mixtures thereof, and such hydrocarbyl groups may be saturated or unsaturated. The hydrocarbyl groups may be composed of carbon and hydrogen or heteroatoms, such as sulfur or oxygen. The hydrocarbyl groups may range from 12 to 25 carbon atoms. In some embodiments, the friction modifier may be a long chain fatty acid ester. In other embodiments, the long chain fatty acid ester may be a monoester, or a diester, or a (tri)glyceride. The friction modifier may be a long chain fatty amide, a long chain fatty ester, a long chain fatty epoxide derivative, or a long chain imidazoline.

[0074] Other suitable friction modifiers include organic, ashless (metal-free), nitrogen-free organic friction modifiers. Such friction modifiers may include esters formed by reacting carboxylic acids and anhydrides with alkanols, and generally include a polar end group (e.g., carboxyl or hydroxyl) covalently bonded to an oleophilic hydrocarbon chain. An example of an organic ashless, nitrogen-free friction modifier is commonly known as glycerol monooleate (GMO), which may include mono-, di-, and tri-esters of oleic acid. Other suitable friction modifiers are described in U.S. Pat. No. 6,723,685.

[0075] Amine-based friction modifiers can include amines or polyamines. Such compounds can have hydrocarbyl groups that are either linear, saturated or unsaturated or a mixture thereof, and can contain from 12 to 25 carbon atoms. Further examples of suitable friction modifiers include alkoxylated amines and alkoxylated ether amines. Such compounds can have hydrocarbyl groups that are either linear, 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.

[0076] The amines and amides may be used by themselves or in the form of adducts or reaction products with boron compounds such as boron oxides, boron halides, metaborates, boric acid or mono-, di-, or tri-alkyl borates. Other suitable friction modifiers are described in U.S. Pat. No. 6,300,291.

[0077] When friction modifiers contain nitrogen, such friction modifiers may be present in the lubricating compositions herein in an amount to deliver up to about 200 ppm nitrogen, or up to about 150 ppm nitrogen, or from about 100 to about 150 ppm nitrogen.

[0078] Corrosion Inhibitors Rust or corrosion inhibitors may also be included in the lubricating compositions described herein. Such materials include mono- and polycarboxylic acids. Examples of suitable monocarboxylic acids are octanoic acid, decanoic acid, and dodecanoic acid. Suitable polycarboxylic acids include dimer and trimer acids produced from acids such as tall oil fatty acid, oleic acid, and linoleic acid.

[0079] Another useful class of rust inhibitors can be alkenyl succinic acid and alkenyl succinic anhydride corrosion inhibitors, such as tetrapropenyl succinic acid, tetrapropenyl succinic anhydride, tetradecenyl succinic acid, tetradecenyl succinic anhydride, hexadecenyl succinic acid, hexadecenyl succinic anhydride, and the like. Half esters of alkenyl succinic acids having 8 to 24 carbon atoms in the alkenyl group with alcohols such as polyglycols are also useful. Other suitable rust or corrosion inhibitors include ether amines, acid phosphates, amines, polyethoxylated compounds such as ethoxylated amines, ethoxylated phenols, and ethoxylated alcohols, imidazolines, aminosuccinic acids, or derivatives thereof, and the like. Mixtures of such rust or corrosion inhibitors can be used. The total amount of corrosion inhibitor, when present in the lubricating compositions described herein, can be up to 2.0 wt. %, or in the range of 0.01 to 1.0 wt. %, based on the total weight of the lubricating composition.

[0080] Viscosity modifier The lubricating compositions herein may optionally contain one or more viscosity modifiers, and if included within the fluid, the viscosity modifier may preferably be an olefin copolymer viscosity modifier as discussed further below, and / or the composition may contain from about 4 to about 10, or from about 6 to about 9 weight percent.

[0081] Suitable viscosity modifiers may include polyolefins, olefin copolymers, ethylene / propylene copolymers, polyisobutene, hydrogenated styrene-isoprene polymers, styrene / maleic acid ester copolymers, hydrogenated styrene / butadiene copolymers, hydrogenated isoprene polymers, alpha-olefin maleic anhydride copolymers, polymethacrylates, polyacrylates, polyalkylstyrenes, hydrogenated alkenylaryl conjugated diene copolymers, or mixtures thereof. The viscosity modifier may include star polymers, suitable examples of which are described in U.S. Patent Application Publication No. 2012 / 0101017(A1).

[0082] The lubricating compositions described herein may also optionally contain one or more dispersant viscosity modifiers in addition to or instead of a viscosity modifier. Suitable dispersant viscosity modifiers may include functionalized polyolefins, such as ethylene-propylene copolymers functionalized with the reaction product of an acylating agent (such as maleic anhydride) with an amine, amine-functionalized polymethacrylates, or esterified maleic anhydride-styrene copolymers reacted with amines.

[0083] Demulsifier Demulsifiers include trialkyl phosphates and various polymers and copolymers of ethylene glycol, ethylene oxide, propylene oxide, or mixtures thereof, such as polyethylene oxide, polypropylene oxide, and (ethylene oxide-propylene oxide) polymers. If present, the amount of demulsifier in the lubricating compositions herein can be up to about 0.05 wt.%, or up to about 0.02 wt.%, or less than about 0.015 wt.%, based on the total weight of the lubricating and cooling fluid.

[0084] Defoamer Antifoaming agents used to reduce or prevent the formation of stable foam include silicones, polyacrylates, or organic polymers. Antifoaming agents that may be useful in the disclosed inventive compositions include polysiloxanes, copolymers of ethyl acrylate and 2-ethylhexyl acrylate, and optionally vinyl acetate. If present, the amount of antifoaming agent in the lubricating composition herein may be up to about 0.1 wt.%, or up to about 0.08 wt.%, or less than about 0.07 wt.%, based on the total weight of the lubricating and cooling fluid.

[0085] Pour Point Depressants The lubricating and cooling fluids may optionally contain one or more pour point depressants. Suitable pour point depressants may include esters of maleic anhydride-styrene, polymethacrylates, polymethyl methacrylates, polyacrylates or polyacrylamides, or mixtures thereof. If present, the pour point depressants may be present in an amount of about 0.001% to about 0.04% by weight, based on the total weight of the lubricating and cooling fluid.

[0086] Molybdenum-Containing Compounds The lubricating oil compositions herein may also optionally contain one or more molybdenum-containing compounds. The oil-soluble molybdenum compounds may have the functional properties of an antiwear agent, an antioxidant, a friction modifier, or mixtures thereof.

[0087] Exemplary molybdenum-containing components may include molybdenum dithiocarbamate, molybdenum dialkyl dithiophosphate, molybdenum dithiophosphinate, amine salts of molybdenum compounds, molybdenum xanthates, molybdenum thioxanthates, molybdenum sulfides, molybdenum carboxylates, molybdenum alkoxides, trinuclear organomolybdenum compounds, and / or mixtures thereof. Alternatively, oil-soluble molybdenum compounds may include molybdenum dithiocarbamate, molybdenum dialkyl dithiophosphate, molybdenum dithiophosphinate, amine salts of molybdenum compounds, molybdenum xanthates, molybdenum thioxanthone, molybdenum sulfides, molybdenum carboxylates, molybdenum alkoxides, trinuclear organomolybdenum compounds, and / or mixtures thereof. Molybdenum sulfides include molybdenum disulfide. Molybdenum disulfide may be in the form of a stable dispersion. In one embodiment, the oil soluble molybdenum compound may be selected from the group consisting of molybdenum dithiocarbamate, molybdenum dialkyldithiophosphate, amine salts of molybdenum compounds, and mixtures thereof. In one embodiment, the oil soluble molybdenum compound may be molybdenum dithiocarbamate.

[0088] Suitable examples of molybdenum compounds that may be used include commercially available materials sold under trade names such as Molyvan® 822, Molyvan® A, Molyvan® 2000, and Molyvan® 855 from R.T. Vanderbilt Co., Ltd., and Sakura-Lube™ S-165, S-200, S-300, S-310G, S-525, S-600, S-700, and S-710 available from Adeka Corporation, and mixtures thereof. Suitable molybdenum components are described in U.S. Pat. Nos. 5,650,381, Reissue Pat. Nos. 37,363 (E1), 38,929 (E1), and 40,595 (E1), which are incorporated herein by reference in their entireties.

[0089] Additionally, the molybdenum compound can be an acidic molybdenum compound, including molybdic acid, ammonium molybdate, sodium molybdate, potassium molybdate, and other alkali metal molybdates and other molybdenum salts, such as sodium hydrogen molybdate, MoOCl4, MoO2Br2, Mo2O3Cl6, molybdenum trioxide, or similar acidic molybdenum compounds. Alternatively, the composition can provide the molybdenum via a molybdenum / sulfur complex of a basic nitrogen compound as described, for example, in U.S. Pat. Nos. 4,263,152, 4,285,822, 4,283,295, 4,272,387, 4,265,773, 4,261,843, 4,259,195 and 4,259,194, and WO 94 / 06897, the foregoing patents being incorporated herein by reference in their entireties.

[0090] Another class of suitable organo-molybdenum compounds is the trinuclear molybdenum compounds, e.g., those of the formula MoS k L n Q z and mixtures thereof, where S represents sulfur, L represents an independently selected ligand having an organic group having a sufficient number of carbon atoms to render the compound soluble or dispersible in oil, n is 1 to 4, k varies from 4 to 7, Q is selected from the group of neutral electron donor compounds, such as water, amines, alcohols, phosphines, and ethers, and z ranges from 0 to 5, including non-stoichiometric values. At least 21 total carbon atoms may be present among all of the ligand organic groups, e.g., at least 25, at least 30, or at least 35 carbon atoms. Additional suitable molybdenum compounds are described in U.S. Pat. No. 6,723,685, the entirety of which is incorporated herein by reference.

[0091] If included, the oil-soluble molybdenum compound may be present in an amount sufficient to provide from about 10 ppm to about 1000 ppm, from about 20 ppm to about 700 ppm, from about 20 ppm to about 550 ppm, from about 20 ppm to about 300 ppm, or from about 20 ppm to about 150 ppm of molybdenum.

[0092] In general terms, the mixed fleet lubricant compositions described herein may contain additive components in the ranges listed in Table 2 below.

[0093] [Table 2]

[0094] The percentages of each component above represent the weight percent of each component based on the weight of the total final lubricating oil composition. The remainder of the lubricating oil composition consists of one or more base oils. The additives used in formulating the compositions described herein can be blended into the base oil individually or in various partial combinations. However, it may be preferred to use an additive concentrate (i.e., additives plus a diluent such as a hydrocarbon solvent) and mix all of the components at the same time.

[0095] Fully formulated lubricants conventionally contain an additive package, often referred to as a dispersant / inhibitor package or DI package, which typically imparts specific performance and / or characteristics required in the formulation. Suitable DI packages are described, for example, in U.S. Pat. Nos. 5,204,012 and 6,034,040. The types of additives included in the additive package may include dispersants, seal swell agents, antioxidants, antifoam agents, lubricants, rust inhibitors, corrosion inhibitors, demulsifiers, viscosity index improvers, and the like. Some of these components are well known to those skilled in the art and are generally used in conventional amounts with the additives and compositions described herein.

[0096] The lubricants, combinations of components, or individual components described herein may be suitable for use as lubricants in various types of internal combustion engines. Suitable engine types may include, but are not limited to, heavy duty diesel, passenger car, light duty diesel, medium speed diesel, or marine engines. The internal combustion engine may be a diesel fueled engine, a gasoline fueled engine, a natural gas fueled engine, a biofuel engine, a mixed diesel / biofuel fueled engine, a mixed gasoline / biofuel fueled engine, an alcohol fueled engine, a mixed gasoline / alcohol fueled engine, a compressed natural gas (CNG) fueled engine, or a mixture thereof. The diesel engine may be a compression ignition engine. The gasoline engine may be a spark ignition engine. The internal combustion engine may also be used in combination with an electric power source or a battery power source. Engines so configured are usually known as hybrid engines. The internal combustion engine may be a two-stroke, four-stroke, or rotary engine. Suitable internal combustion engines include marine diesel engines (such as inland marine), aviation piston engines, light duty diesel engines, as well as motorcycle, automobile, combustion car, and truck engines.

[0097] The lubricating oil composition for an internal combustion engine may be suitable for any engine lubricant, regardless of sulfur, phosphorus, or sulfated ash (ASTM D-874) content. The sulfur content of the engine oil lubricants herein may be about 1 weight percent or less, or about 0.8 weight percent or less, or about 0.5 weight percent or less, or about 0.3 weight percent or less, or about 0.2 weight percent or less. In one embodiment, the sulfur content may range from about 0.001 weight percent to about 0.5 weight percent, or about 0.01 weight percent to about 0.3 weight percent. The total sulfated ash content of the engine oil lubricants herein may be about 2 weight percent or less, or about 1.5 weight percent or less, or about 1.1 weight percent or less, or about 1 weight percent or less, or about 0.8 weight percent or less, or about 0.5 weight percent or less. In one embodiment, the sulfated ash content may be about 0.1 weight percent to about 0.9 weight percent, or about 0.1 weight percent, or about 0.2 weight percent to about 0.8 weight percent.

[0098] Additionally, the lubricants of the present description may meet one or more industry specification requirements, such as ILSAC GF-3, GF-4, GF-5, GF-6, CK-4, FA-4, CJ-4, CI-4 Plus, CI-4, ACEA A1 / B1, A2 / B2, A3 / B3, A3 / B4, A5 / B5, A7 / B7, C1, C2, C3, C4, C5, C6, E4 / E6 / E7 / E9, Euro 5 / 6, JASO DL-1, low SAPS, medium SAPS, or original equipment manufacturer specifications, such as Dexos™ 1, Dexos™ 2, MB-Approval 229.51 / 229.31, VW 502.00, 503.00 / 503.01, 504.00, 505.00, 506.00 / 506.01, 507.00, 508.00, 509.00, BMW Longlife-04, Porsche C30, Peugeot Citroen Automobiles B71 2290, B71 2296, B71 2297, B71 2300, B71 2302, B71 2312, B71 2007, B71 2008, Ford WSS-M2C153-H, WSS-M2C930-A, WSS-M2C945-A, WSS-M2C913A, WSS-M2C913-B, WSS-M2C913-C, GM 6094-M, Chrysler MS-6395, or past or future passenger car motor oil or heavy duty diesel oil specifications not listed herein. In some embodiments for passenger car motor oil applications, the amount of phosphorus in the final fluid is surprisingly only about 800 ppm or less, or 600 ppm or less. In some embodiments for heavy duty diesel applications, the amount of phosphorus in the final fluid is also surprisingly about 800 ppm or less.

[0099] In certain applications, the lubricants of the present disclosure may also be suitable for automatic transmission fluids, continuously variable transmission fluids, manual transmission fluids, gear oils, other fluids associated with powertrain components, off-road fluids, power steering fluids, fluids used in wind turbines, compressors, working fluids, slideway fluids, and other industrial fluids. In certain applications, these lubrication applications may include the lubrication of gearboxes, power take-offs and clutch(es), rear axles, reduction gears, wet brakes, and hydraulic accessories. EXAMPLES

[0100] The following examples illustrate exemplary embodiments of the present disclosure. In these examples, as well as elsewhere in this application, all ratios, parts, and percentages are by weight unless otherwise indicated. These examples are presented for illustrative purposes only, and are not intended to limit the scope of the invention disclosed herein.

[0101] Comparative Example 1 Comparative lubricating compositions C-1, C-2, and C-3 were subjected to Allison friction test TES-439 (available from Allison Transmission, released November 2010) and modified ASTM D8291-21a, Sequence IX Low Speed ​​Pre-Ignition (LSPI) test. The LSPI test was slightly modified so that only two replicates were reported. Table 3 below shows the detergent system and antiwear and friction system included in the comparative lubricating compositions formulated using Group II base oil as 15W-40 fluids, with the same amounts of other additives including dispersants, antioxidants, organomolybdenum additives, antifoam agents, ashless antiwear additives, olefin copolymer viscosity modifiers, and base oil blends. The results of the Allison friction and LSPI properties are shown in Tables 4 and 5. The pass / fail criteria are described in the TES test guidelines and as per the friction plate setup received from Allison Transmission and / or provided in the ASTM test guidelines mentioned above.

[0102] [Table 3]

[0103] In the detergent system of Table 3, calcium phenate had a TBN of 250 and 9.3 weight percent calcium (neat TBN of 413), calcium sulfonate 1 had a TBN of 300 and 11.9 weight percent calcium (neat TBN of 605), magnesium sulfonate had a TBN of 400 and 9.6 weight percent magnesium (neat TBN of 680), and calcium sulfonate 2 had a TBN of 28 and 2.6 weight percent calcium (neat TBN of 69). In the antiwear and friction system, ZDDP A was a zinc dialkyldithiophosphate containing mixed alkyl groups where about 40% of the alkyl groups were C3 and derived from a secondary alcohol (isopropanol), about 40% of the alkyl groups were C4 and derived from a primary alcohol (isobutanol), and about 20% of the alkyl groups were C8 and derived from a primary alcohol (2-ethylhexanol). ZDDP A contained about 8.4% by weight phosphorus, 17.8% by weight sulfur, and about 9.2% by weight zinc. ZDDP B used in this example was a zinc dialkyldithiophosphate, 100% of the alkyl groups were C8, and derived from a primary alcohol (2-ethylhexanol). ZDDP B contained about 6.1% by weight phosphorus, about 12.7% by weight sulfur, and about 6.75% by weight zinc.

[0104] [Table 4] * NOTE: Pass / Fail criteria are based on minimum and maximum slip time and coefficient of friction values ​​provided by Allison Transmission when supplying a particular friction plate.

[0105] [Table 5]

[0106] As shown in Tables 4 and 5, none of the comparative lubricants C-1, C-2, or C-3 were able to pass both the Sequence IX LSPI requirements for passenger car motor oils and the Allison friction requirements for heavy duty engine applications. Fluids C-1 and C-3 passed the Allison friction test, but these fluids failed the LSPI test. Fluid C-2 contained magnesium from the detergent and had good LSPI properties, but failed with respect to Allison friction properties. Thus, none of the comparative lubricant compositions C1, C2, or C3 are mixed fleet compatible with both compression ignition heavy duty applications and spark ignition passenger car applications.

[0107] Example 1 The lubricating compositions of the present invention consistent with the present disclosure were evaluated for LSPI and Allison friction. Table 6 below shows the detergents and antiwear and friction systems included in the inventive fluids, which were also formulated as 15W-40 fluids using the same amounts of other additives used in the comparative fluid of Comparative Example 1, including dispersants, antioxidants, organomolybdenum additives, antifoaming agents, ashless antiwear additives, olefin copolymer viscosity modifiers, and base oil blends. Inventive composition I-1 used Group III base oil, and inventive composition I-2 used Group II base oil to obtain the final fluid. Meanwhile, other additives and loadings are the same as those of Comparative Example 1. The results of the LSPI and Allison friction tests are shown in Tables 7 and 8 below.

[0108] [Table 6]

[0109] In the detergent system of Table 6, the additives were the same as in the detergent system of Comparative Example 1. In the antiwear and friction system, ZDDP A was also the same as that used in Comparative Examples 1-3, and ZDDP B was the same as that used in Comparative Example 3. Performance testing is shown in Tables 7 and 8 below.

[0110] [Table 7] * NOTE: Pass / Fail criteria are based on minimum and maximum slip time and coefficient of friction values ​​provided by Allison Transmission when supplying a particular friction plate.

[0111] [Table 8]

[0112] As shown in Tables 7 and 8 above, the inventive lubricating compositions I-1 and I-2 passed both the LSPI property test for spark ignition passenger car motor oils and also the Allison friction test for compression ignition heavy duty engine applications. These compositions contain the unique detergent system and antiwear and friction system described herein. Thus, both lubricating compositions I-1 and I-2 were suitable for mixed fleet applications or uses.

[0113] In embodiments herein, the lubricating compositions exhibit an average number of events of 5 or less according to a Sequence IX Low Speed ​​Pre-Ignition Test according to ASTM D8291-21a using 2 replicates, the lubricating compositions have an absolute percent change from initial slip time according to Allison Transmission Friction Test TES-439, November 2010 of about 10 percent or less (preferably, 5 percent or less, or even 2 percent or less), and an absolute percent change from initial coefficient of friction (median) according to Allison Transmission Friction Test TES-439, November 2010 of 10 percent or less (preferably, 5 percent or less, or even 2 percent or less).

[0114] Unless otherwise stated in the above examples, the amounts of calcium, magnesium, phosphorus, and zinc are calculated based on the treat rates and amounts of each element provided by the individual additives.

[0115] It should be noted that, as used herein and in the appended claims, the singular forms "a," "an," and "the" include plural referents unless expressly and unambiguously limited to one referent. Thus, for example, a reference to "an antioxidant" includes two or more different antioxidants. As used herein, the term "include" and grammatical variations thereof are intended to be open-ended, and the enumeration of items in a list does not exclude other similar items that may be substituted for or added to the listed items.

[0116] For purposes of this specification and the appended claims, unless otherwise indicated, all numbers expressing quantities, percentages or proportions, and other numerical values ​​used in the specification and claims should be understood to be modified in all instances by the term "about". Accordingly, unless otherwise indicated, the numerical parameters set forth in the following specification and appended claims are approximations that may vary depending on the desired properties sought to be obtained by the present disclosure. At the very least, and not as an attempt to limit the application of the doctrine of equivalents to the scope of the claims, each numerical parameter should at least be construed in light of the number of reported significant digits and by applying ordinary rounding techniques.

[0117] It is understood that each component, compound, substituent, or parameter disclosed herein should be construed as disclosed for use alone, or in combination with one or more of any and all other components, compounds, substituents, or parameters disclosed herein.

[0118] It is further understood that each range disclosed herein should be construed as a disclosure of each specific value within the disclosed range having the same significant digits. Thus, for example, a range of 1 to 4 should be construed as an explicit disclosure of the values ​​1, 2, 3, and 4, and any range of such values.

[0119] It is further understood that each lower limit of each range disclosed herein should be interpreted as being disclosed in combination with each upper limit of each range and each specific value within each range disclosed herein for the same component, compound, substituent, or parameter. Thus, the present disclosure should be interpreted as a disclosure of all ranges derived by combining each lower limit of each range with each upper limit of each range or each specific value within each range, or by combining each upper limit of each range with each specific value within each range. That is, it is further understood that any range between the endpoint values ​​within the broad range is also discussed herein. Thus, a range of 1 to 4 also means a range of 1 to 3, 1 to 2, 2 to 4, 2 to 3, etc.

[0120] Furthermore, a specific amount / value of a component, compound, substituent, or parameter disclosed in the description or examples should be construed as a disclosure of either a lower or upper limit of a range and, therefore, can be combined with any other lower or upper limit of a range or specific amount / value for the same component, compound, substituent, or parameter disclosed elsewhere in this application to form a range for that component, compound, substituent, or parameter.

[0121] While particular embodiments have been described, presently unforeseen or unforeseeable alternatives, modifications, variations, improvements, and substantial equivalents may occur to applicant or others skilled in the art. It is therefore intended that the appended claims, as filed and as they may be amended, cover all such alternatives, modifications, variations, improvements, and substantial equivalents.

[0122] The following examples illustrate, but do not limit, the method and composition of the present disclosure. Other suitable modifications and adaptations of various conditions and parameters normally encountered in the art and obvious to those skilled in the art are within the spirit and scope of the present disclosure. All patents and publications cited herein are fully incorporated herein by reference in their entirety. Examples 1-6 illustrate different lubricating compositions containing viscosity index improvers containing ethylene and propylene units reacted with macromonomer alcohols and methods for making them.

Claims

1. 1. A lubricating composition suitable for diesel and gasoline engines, said lubricating composition comprising: a detergent system providing both calcium and magnesium from one or more of a sulfonate, a phenate, a salicylate, or mixtures thereof, wherein the weight ratio of calcium to magnesium provided by said detergent system is from 1.5:1 to 2:1; an antiwear and friction system comprising one or more metal dialkyldithiophosphates derived from a primary alcohol and a secondary alcohol, wherein the weight ratio of the primary alcohol to the secondary alcohol in the antiwear and friction system is at least 3:1 to 5.5:1; the amount of magnesium from the detergent system is at least 500 ppm magnesium based on the lubricating composition; the amount of phosphorus from the antiwear and friction system is less than 1200 ppm phosphorus based on the lubricating composition, and the amount of zinc from the antiwear and friction system is less than 1000 ppm zinc based on the lubricating composition; the lubricating composition exhibits an average number of events of 5 or less according to a Sequence IX Slow Speed ​​Pre-Ignition Test according to ASTM D8291-21a using 2 replicates; 1. A lubricating composition having an absolute percent change from initial slip time according to Allison Transmission Friction Test TES-439 (November 2010) of 10 percent or less, and an absolute percent change from initial median coefficient of friction according to Allison Transmission Friction Test TES-439 (November 2010) of 10 percent or less.

2. 1. A method of lubricating an engine with a lubricating composition meeting API SP, API CK-4, and API FA-4 certifications, said method comprising: lubricating the engine with a lubricating composition, the lubricating composition comprising a detergent system providing both calcium and magnesium from one or more of a sulfonate, a phenate, a salicylate, or a mixture thereof, wherein the weight ratio of calcium to magnesium provided by the detergent system is from 1.5:1 to 2:1; and an antiwear and friction system comprising two or more zinc dialkyldithiophosphates derived from a primary alcohol and a secondary alcohol, wherein a first metal dialkyldithiophosphate is derived from a primary alcohol and a second metal dialkyldithiophosphate is derived from a primary alcohol. an antiwear and friction system derived from a mixture of an alcohol and a secondary alcohol, wherein the weight ratio of primary alcohol to secondary alcohol from the two or more metal dialkyldithiophosphates combined in the antiwear and friction system is at least 3:1 to 5.5:1, wherein the amount of magnesium from the detergent system is greater than at least 500 ppm magnesium based on the lubricating composition, the amount of phosphorus from the antiwear and friction system is less than 1200 ppm phosphorus based on the lubricating composition, and the amount of zinc from the antiwear system is less than 1000 ppm zinc based on the lubricating composition; The lubricating composition exhibits an average number of events of 5 or less according to a Sequence IX Low Speed ​​Pre-ignition Test according to ASTM D8291-21a using 2 replicates, and the lubricating composition has an absolute percent change from initial slip time according to Allison Transmission Friction Test TES-439 (November 2010) of 10 percent or less, and an absolute percent change from initial median coefficient of friction according to Allison Transmission Friction Test TES-439 (November 2010) of 10 percent or less.

3. 3. The method of claim 2, wherein the calcium provided by the detergent system is provided by one or more of calcium phenate, calcium sulfonate, or mixtures thereof in an amount providing 900 to 1500 ppm of calcium; or wherein the detergent system comprises 50 to 70 weight percent calcium phenate, 30 to 40 weight percent magnesium sulfonate, and 0 to 10 weight percent calcium sulfonate; or wherein the detergent system comprises calcium sulfonate having a neat total base number of 20 to 80; or wherein the detergent system comprises calcium phenate having a neat total base number of 300 to 450 and magnesium sulfonate having a neat total base number of 500 to 700.

4. 4. The method of claim 3, wherein the detergent system comprises 60 to 70 weight percent of the calcium phenate, 32 to 38 weight percent of the magnesium sulfonate, and 1 to 4 weight percent of the calcium sulfonate.

5. 5. The method of claim 4, wherein the calcium sulfonate has a total alkalinity of less than 50.

6. 3. The method of claim 2, wherein the antiwear and friction system comprises a first zinc dialkyldithiophosphate derived from a primary alcohol and a second zinc dialkyldithiophosphate derived from a mixture of primary and secondary alcohols, or the antiwear and friction system comprises one or more zinc dialkyldithiophosphate additives derived from a majority amount of a primary alcohol.

7. 7. The method of claim 6, wherein the antiwear and friction system comprises up to 60 weight percent of a first zinc dialkyldithiophosphate derived from a primary alcohol and 40 to 50 weight percent of a second zinc dialkyldithiophosphate derived from a mixture of primary and secondary alcohols, or wherein the second zinc dialkyldithiophosphate derived from a mixture of primary and secondary alcohols is derived from 50 to 70 weight percent of a primary alcohol and 30 to 50 weight percent of a secondary alcohol.