Lubricant composition for reducing high-temperature deposit

Abstract

To provide a lubricant composition and a method for lubricating an engine, which are effective in reducing high-temperature deposits, particularly those present in low-ash compositions.SOLUTION: A lubricant composition comprises at least one base oil of lubricating viscosity, a detergent system, and an antiwear system comprising a metal dialkyldithiophosphate that provides phosphorus to the lubricant composition. A total base number (TBN) of the lubricant composition is about 0.5 to about 20 and the amount of the phosphorus from the antiwear system relative to the TBN of the lubricant composition is 150 or less.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present disclosure relates to an additive system configured for high temperature deposit reduction and lubricating compositions containing the additive system, particularly lubricating compositions capable of achieving high temperature deposit reduction in low ash formulations. [Background technology]

[0002] Automobile manufacturers continue to demand improved efficiency and fuel economy, thereby increasing the demands on engines, lubricants, and their components. Today's passenger vehicle engines are often becoming smaller, lighter, and more efficient, with technologies designed to improve fuel economy, performance, and power output. These requirements also mean that the performance of engine oils must evolve to meet the higher demands of such modern engines and the corresponding performance standards associated with their unique uses and applications. Due to these stringent demands on engine oils, lubricant manufacturers often tailor lubricants and their additives to meet the specific performance requirements for each unique application.

[0003] For example, the Thermo-Oxidation Engine Oil Simulation Test (TEOST-33C) was developed as a lubricant test for evaluating turbocharger coking characteristics. In this test, the test lubricant is passed through a test specimen, or depositor rod, and the mass of deposits formed on the depositor rod is measured as it is heated to approximately 200°C to approximately 500°C. This test, designed in part to predict the high-temperature deposit formation tendency of engine oils subjected to the additional oxidative stresses of a turbocharger, has generally been a component of API and ILSAC standards for many years.

[0004] Lubricant specifications often include compositional constraints on allowable levels of sulfated ash, phosphorus, and sulfur (so-called SAPS limits), and maintaining such constraints while still meeting the increasing demands of modern lubricant standards can be difficult. For example, due to environmental considerations, vehicles often are fitted with exhaust aftertreatment devices to reduce particulate matter and various other emissions. However, the sulfated ash, sulfur, and / or phosphorus levels in lubricating oil compositions conventionally used in internal combustion engines can adversely affect such aftertreatment devices, and lubricants are generally formulated to minimize the sulfated ash, phosphorus, and sulfur therein.

[0005] Sulfated ash is a measure of the total weight percent of ash in a lubricating oil composition. The sulfated ash measurement of a lubricating oil composition is related to the total metal content therein and can be conveniently measured according to ASTM D-874 and / or other common evaluation methods known in the art and described herein. However, in many situations, varying one component in a lubricating oil composition to improve a particular performance characteristic tends to adversely affect one or more other performance characteristics. For example, the primary source of ash in a lubricating oil composition is generally metal detergent additives and / or antiwear additives. However, reducing the amount of detergent or antiwear additive components to reduce sulfated ash content tends to adversely affect other performance characteristics. In particular, it has been found that reducing detergent and / or antiwear additives tends to increase deposits, for example, in the TEOST-33C high temperature performance test. Summary of the Invention

[0006] In one approach or embodiment, a lubricating composition for reducing high-temperature deposits is provided. In one aspect, the lubricating composition includes one or more base oils of lubricating viscosity, a detergent system providing a metal to the lubricating composition, the metal being at least one of sodium, calcium, magnesium, or a combination thereof, and an antiwear system including one or more metal dialkyldithiophosphates derived from one of a primary alcohol, a secondary alcohol, or a combination thereof, and providing a phosphorus amount to the lubricating composition, the lubricating composition having a Total Base Number (TBN) of about 0.5 to about 20, and the amount of phosphorus from the antiwear system relative to the TBN of the lubricating composition is about 150 or less.

[0007] In another approach, the lubricating composition of the preceding paragraph may include optional features or embodiments, which may include one or more of the following, in any combination:and / or the lubricating composition contains about 800 ppm or less of phosphorus from the antiwear system and / or the lubricating composition contains about 1800 ppm or less of metals from the detergent system and / or the amount of phosphorus from the antiwear system relative to the amount of metals from the detergent system is about 0.5 or less and / or the amount of phosphorus from the antiwear system relative to the lubricant TBN is less than or equal to ASTM and / or the detergent system comprises from about 55 to about 75 weight percent of a detergent additive providing calcium and from about 25 to about 45 weight percent of a detergent additive providing magnesium, and / or the detergent system provides from about 10 to about 1500 ppm of calcium and from about 10 to about 500 ppm of magnesium, and / or the antiwear system comprises two metal dialkyldithiophosphates, and / or the antiwear system comprises two zinc dialkyldithiophosphates, wherein the first zinc dialkyldithiophosphate is derived from a primary alcohol and the second zinc dialkyldithiophosphate is derived from a secondary alcohol, and / or the antiwear system comprises a majority of the second zinc dialkyldithiophosphate derived from a secondary alcohol, and / or the wear agent system comprises about 20 to about 30 weight percent of a first zinc dialkyldithiophosphate derived from a primary alcohol and about 70 to about 80 weight percent of a second zinc dialkyldithiophosphate derived from a secondary alcohol; and / or the detergent system comprises a calcium sulfonate, calcium phenate, or combination thereof having a total base number of 200 to 500; and / or the detergent system comprises a magnesium sulfonate, magnesium phenate, or combination thereof having a total base number of 200 to about 500; and / or the lubricating composition has a total base number of less than about 10; and / or further comprises an amount of zinc provided by an antiwear agent system, wherein the amount of zinc from the antiwear agent system to the amount of total metals from the detergent system is about 0.6 or less; and / or the antiwear agent system provides about 50 to about 850 ppm of zinc to the lubricating composition; and / or the lubricating composition is a passenger car motor oil.

[0008] In another approach or embodiment, provided herein is a low-ash lubricating composition for reducing high-temperature deposits. In an aspect, the low-ash lubricating composition includes one or more base oils of lubricating viscosity, a detergent system that provides an amount of metal to the lubricant composition, where the metal is at least one of sodium, calcium, magnesium, or a combination thereof, and an antiwear system that includes one or more metal dialkyldithiophosphates derived from one of a primary alcohol, a secondary alcohol, or a combination thereof and provides an amount of phosphorus to the lubricant composition, where the amount of phosphorus from the antiwear system to the amount of metal from the detergent system is less than or equal to about 0.5.

[0009] The low ash lubricating compositions of the preceding paragraph may also include one or more optional features or embodiments, which may include one or more of the following, in any combination:The lubricating composition comprises about 800 ppm or less of phosphorus from the antiwear system and about 1800 ppm or less of metals from the detergent system, and / or the amount of phosphorus from the antiwear system relative to the TBN is about 120 or less, and / or the amount of phosphorus from the antiwear system relative to the lubricant TBN is less than or equal to ASTM and / or the detergent system comprises from about 55 to about 75 weight percent of a detergent additive providing calcium and from about 25 to about 45 weight percent of a detergent additive providing magnesium, and / or the detergent system provides from about 10 to about 1500 ppm of calcium and from about 10 to about 500 ppm of magnesium, and / or the antiwear system comprises two metal dialkyldithiophosphates, and / or the antiwear system comprises two zinc dialkyldithiophosphates, wherein the first zinc dialkyldithiophosphate is derived from a primary alcohol and the second zinc dialkyldithiophosphate is derived from a secondary alcohol, and / or the antiwear system comprises a majority of the second zinc dialkyldithiophosphate derived from a secondary alcohol, and / or the wear agent system comprises about 20 to about 30 weight percent of a first zinc dialkyldithiophosphate derived from a primary alcohol and about 70 to about 80 weight percent of a second zinc dialkyldithiophosphate derived from a secondary alcohol; and / or the detergent system comprises a calcium sulfonate, calcium phenate, or combination thereof having a total base number of 200 to 500; and / or the detergent system comprises a magnesium sulfonate, magnesium phenate, or combination thereof having a total base number of 200 to about 500; and / or the lubricating composition has a total base number of less than about 10; and / or further comprises an amount of zinc provided by an antiwear agent system, wherein the amount of zinc from the antiwear agent system to the amount of total metals from the detergent system is about 0.6 or less; and / or the antiwear agent system provides about 50 to about 850 ppm of zinc to the lubricating composition; and / or the lubricating composition is a passenger car motor oil.

[0010] In yet another approach or embodiment, there is provided a method for lubricating an engine with a lubricating composition that meets API SP / ILSAC GF-6 specifications. In one aspect, the method includes lubricating an engine with the lubricating composition, the lubricating composition comprising one or more base oils of lubricating viscosity, a detergent system that provides an amount of metal to the lubricant composition, the metal being at least one of sodium, calcium, magnesium, or a combination thereof, and an antiwear system that includes one or more metal dialkyldithiophosphates derived from one of a primary alcohol, a secondary alcohol, or a combination thereof and that provides an amount of phosphorus to the lubricating composition, the lubricating composition having a total base number (TBN) of about 0.5 to about 20, the amount of phosphorus from the antiwear system relative to the TBN of the lubricating composition being about 150 or less, and the lubricating composition having a calculated sulfated ash content of about 0.8 weight percent or less and less than about 30 mg of deposits when subjected to the ASTM D6335 High Temperature Deposit Formation Test.

[0011] In other approaches or embodiments, the method of the preceding paragraph may include optional features, embodiments, or method steps in any combination. The optional features, embodiments, or steps may include one or more of the following: The lubricating composition contains about 800 ppm or less of phosphorus from the antiwear system, and / or the lubricating composition contains about 1800 ppm or less of total metals from the detergent system, the detergent system provides about 10 to about 1500 ppm of calcium and about 10 to about 500 ppm of magnesium, and / or the lubricating composition has a total base number of less than about 10, and / or the antiwear system provides about 50 to about 850 ppm of zinc to the lubricating composition, and the amount of zinc from the antiwear system to the amount of total metals from the detergent system is about 0.6 or less, and / or the amount of phosphorus from the antiwear system to the TBN is about 120 or less, and / or the amount of phosphorus from the antiwear system to the lubricant TBN is about 0.5 or less when the lubricating composition is subjected to the high temperature deposit formation test of ASTM D6335.and / or the detergent system comprises from about 55 to about 75 weight percent of a detergent additive providing calcium and from about 25 to about 45 weight percent of a detergent additive providing magnesium, and / or the detergent system provides from about 10 to about 1500 ppm of calcium and from about 10 to about 500 ppm of magnesium, and / or the antiwear system comprises two metal dialkyldithiophosphates, and / or the antiwear system comprises two zinc dialkyldithiophosphates, wherein the first zinc dialkyldithiophosphate is derived from a primary alcohol and the second zinc dialkyldithiophosphate is derived from a secondary alcohol, and / or the antiwear system comprises a majority of the second zinc dialkyldithiophosphate derived from a secondary alcohol, and / or the antiwear system comprises a majority of the second zinc dialkyldithiophosphate derived from a primary alcohol. and about 20 to about 30 weight percent of a first zinc dialkyldithiophosphate derived from a secondary alcohol, and about 70 to about 80 weight percent of a second zinc dialkyldithiophosphate derived from a secondary alcohol; and / or the detergent system comprises a calcium sulfonate, a calcium phenate, or a combination thereof having a total base number of 200 to 500; and / or the detergent system comprises a magnesium sulfonate, a magnesium phenate, or a combination thereof having a total base number of 200 to about 500; and / or the lubricating composition has a total base number of less than about 10; and / or further comprises an amount of zinc provided by an antiwear system, wherein the amount of zinc from the antiwear system to the amount of total metals from the detergent system is about 0.6 or less; and / or the antiwear system provides about 50 to about 850 ppm of zinc to the lubricating composition; and / or the lubricating composition is a passenger car motor oil.

[0012] In another approach or embodiment, there is provided the use of any embodiment of the lubricating composition in this summary to achieve less than 30 mg of deposits when subjected to the ASTM D6335 High Temperature Deposit Formation Test.

[0013] In other embodiments herein, any of the use, method, or composition embodiments herein may have a calculated sulfated ash (SASH), calculated by the method described below, of less than about 0.8 weight percent, less than about 0.75 weight percent, less than about 0.7 weight percent, less than about 0.6 weight percent, less than about 0.5 weight percent, less than about 0.4 weight percent, less than about 0.3 weight percent, or even less than about 0.2 weight percent.

[0014] 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.

[0015] The terms "oil composition," "lubrication composition," "lubricating oil composition," "lubricating oil," "lubricant composition," "lubricating composition," "fully formulated lubricant composition," "lubricant," "crankcase oil," "crankcase lubricant," "engine oil," "engine lubricant," "motor oil," and "motor lubricant" are considered to be synonymous and fully interchangeable terms that refer to a finished lubricant product that includes a major amount of a base oil plus a minor amount of an additive composition.

[0016] As used herein, the terms "additive package," "additive concentrate," "additive composition," "engine oil additive package," "engine oil additive concentrate," "crankcase additive package," "crankcase additive concentrate," "motor oil additive package," and "motor oil concentrate" are considered synonymous and fully interchangeable terms that refer to that portion of a lubricating oil composition that excludes a major amount of a base oil stock blend. The additive package may or may not include a viscosity index improver or a pour point depressant.

[0017] The term "overbased" refers to metal salts, such as those of sulfonates, carboxylates, salicylates, and / or phenates, in which the amount of metal present exceeds the stoichiometric amount. Such salts may have conversion levels greater than 100% (i.e., they may contain more than 100% of the theoretical amount of metal required to convert the acid to its "standard" or "neutral" salt). The expression "metal ratio," often abbreviated as MR, is used to indicate the ratio of the total chemical equivalents of metal in an overbased salt to the chemical equivalents of metal in a neutral salt, according to known chemical reactivity and stoichiometry. In standard or neutral salts, the metal ratio (MR) is 1, whereas in overbased salts, the MR is greater than 1. These are commonly referred to as overbased, highly based, or superbased salts and may be salts of organic sulfur acids, carboxylic acids, salicylates, sulfonates, and / or phenols.

[0018] The term "alkaline earth metals" refers to calcium, barium, magnesium, and strontium, and the term "alkali metals" refers to lithium, sodium, potassium, rubidium, and cesium.

[0019] As used herein, the term "hydrocarbyl" or "hydrocarbyl substituent" or "hydrocarbyl group" is used in its ordinary sense, as is well 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 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.

[0020] As used herein, the term "hydrocarbylene substituent" or "hydrocarbylene group" is used in its ordinary sense, as is well known to those skilled in the art. Specifically, it refers to a group that is directly attached to the remainder of the molecule by carbon atoms at two locations and has a predominantly hydrocarbon character. Each hydrocarbylene group is independently selected from divalent hydrocarbon substituents, including halo, alkyl, aryl, alkylaryl, arylalkyl, hydroxyl, alkoxy, mercapto, nitro, nitroso, amino, pyridyl, furyl, imidazolyl, oxygen, and nitrogen, and no more than two non-hydrocarbon substituents are present for every 10 carbon atoms in the hydrocarbylene group.

[0021] As used herein, the term "weight percent" means the percentage that the recited component represents relative to the weight of the entire composition, unless expressly stated otherwise.

[0022] As used herein, the term "ppmw" refers to parts per million by weight, unless otherwise specified.

[0023] The terms "soluble," "oil-soluble," or "dispersible" as used herein may, but do not necessarily, indicate that a compound or additive is soluble, dissolvable, miscible, or capable of being suspended in oil in any proportion. However, the terms do mean that they are, for example, soluble, suspendable, dissolvable, 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 for the incorporation of higher levels of the specific additive.

[0024] As used herein, the term "TBN" is used to indicate the total base number in mg KOH / g as measured by the method of ASTM D2896.

[0025] The term "alkyl," as used herein, refers to straight, branched, cyclic, and / or substituted saturated chain moieties of about 1 to about 100 carbon atoms. The term "alkenyl," as used herein, refers to straight, branched, cyclic, and / or substituted unsaturated chain moieties of about 3 to about 10 carbon atoms. The term "aryl," as used herein, refers to mono- and polycyclic aromatic compounds that may contain alkyl, alkenyl, alkylaryl, amino, hydroxyl, alkoxy, halo substituents, and / or heteroatoms, including, but not limited to, nitrogen, oxygen, and sulfur.

[0026] As used herein, "post-reacted" or "post-treated" refers to a component that is further reacted or treated, for example, with boron, phosphorus, and / or maleic anhydride, and may refer to a dispersant in which primary and / or secondary amines are further reacted with such compounds to convert at least a portion of such amines to tertiary amines. Such subsequent reactions or treatments are further described in U.S. Pat. No. 5,241,003, which is incorporated herein by reference. Conversely, a "non-post-reacted" or "non-post-treated" component has not been subjected to such further treatment, reaction, and / or processing, and in the context of a dispersant, contains a certain amount of primary and / or secondary amines.

[0027] The molecular weight of any embodiment herein can be determined using a gel permeation chromatography (GPC) instrument from Waters or similar instrumentation, and data processed with Waters Empower Software or similar software. The GPC instrument can be equipped with a Waters Separation Module and a Waters Refractive Index Detector (or similar optional instrumentation). GPC operating conditions can include a guard column, four Agilent PLgel columns (300 x 7.5 mm long, 5 μm particle size, and pore size range 100-10,000 Å), and a column temperature of approximately 40°C. Unstabilized HPLC-grade tetrahydrofuran (THF) can be used as the solvent at a flow rate of 1.0 mL / min. The GPC instrument 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 at concentrations of 0.1 to 0.5% by weight and 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. Bly, "Modern Size Exclusion Liquid Chromatography," John Wiley and Sons, New York, 1979, which is incorporated herein by reference.

[0028] As used herein, "sulfated ash" or "SASH" refers to the amount of sulfated ash calculated based on the amount of metal in the lubricant. For example, sulfated ash (SASH) is calculated based on the total metallic elements contributing to SASH in a lubricant composition adjusted by a factor for each metallic type. Metals contributing to SASH (with adjustment factors) include barium (1.7), boron (3.22), calcium (3.4), copper (1.252), lead (1.464), lithium (7.92), magnesium (4.95), manganese (1.291), molybdenum (1.5), potassium (2.33), sodium (3.09), and zinc (1.5). Specifically, the ppmw content of each of the metallic elements present in the lubricating oil composition that are considered to contribute to sulfated ash is multiplied by the corresponding factor above, and then each metallic element / factor adjustment product is summed and the sum is divided by 10,000 to calculate the weight percent of SASH in the lubricating composition. Further details of such calculations are provided in the Examples below.

[0029] Additional details and advantages of the present disclosure are set forth in part in the description which follows, and / or may be learned by practice of the present disclosure. The details and advantages of the present disclosure may be realized and attained by means of the elements and combinations particularly pointed out in the appended claims. It is to be understood that both the foregoing general description and the following detailed description are exemplary and explanatory only and are not restrictive of the present disclosure as claimed. [Brief explanation of the drawings]

[0030] [Figure 1] 1 is a plot of phosphorus relative to total detergent metals versus high temperature deposit levels. [Figure 2] 1 is a plot of phosphorus content versus detergent TBN versus high temperature deposit content. [Figure 3] 1 is a plot of calculated SASH against the amount of high-temperature deposits. DETAILED DESCRIPTION OF THE INVENTION

[0031] In one aspect, the present disclosure describes a blend of detergent and antiwear lubricant additives and lubricants containing such additive blends, conforming to and / or conforming to at least API SP / ILSAC GF-6 specifications. In one approach, the lubricating compositions are effective in reducing high-temperature deposits, particularly in low-ash compositions. As shown in the examples below, reducing additives known to lower ash levels can be detrimental to high-temperature deposits. However, improved high-temperature deposit performance can be achieved in lubricant compositions with low ash levels if a specific relationship between detergent and antiwear characteristics is maintained. For example, the lubricating composition herein includes a base oil of lubricating viscosity, a detergent system that provides the lubricating composition with an amount of metal, preferably at least sodium, calcium, magnesium, or a combination thereof, and an antiwear system that includes one or more metal dialkyldithiophosphates derived from one of a primary alcohol, a secondary alcohol, or a combination thereof, and that provides the lubricating composition with an amount of phosphorus, wherein the lubricating composition has a total base number (TBN) of from about 0.5 to about 20.

[0032] Uniquely, embodiments of the lubricating compositions herein also include a unique relationship between the amount of phosphorus from the antiwear system relative to the TBN of the overall lubricating composition effective to achieve low high-temperature deposits, and, in embodiments, low high-temperature deposits in compositions that also have low levels of ash, calculated as sulfated ash. In embodiments, the lubricating compositions have a ratio of the amount of phosphorus from the antiwear system to the TBN of the lubricating composition of about 150 or less, which surprisingly achieves low high-temperature deposits, particularly low high-temperature deposits in lubricating compositions that also have low levels of ash. In yet another approach, the lubricating compositions herein may also have an amount of phosphorus from the antiwear system relative to the amount of metal from the detergent system of about 0.5 or less, and in another approach, about 0.38 or less, in compositions effective to achieve low high-temperature deposits in low-ash formulations. For example, such relationships of phosphorus, TBN, and / or detergent metals are effective so that the lubricating compositions herein, when subjected to the High Temperature Deposit Formation Test of ASTM D6335 (i.e., TEOST-33C), contain less than about 30 mg of deposits, while having a calculated sulfated ash content (calculated as described herein) of about 0.8 weight percent or less. Each of the lubricant components is described in more detail below.

[0033] Detergents The lubricant compositions herein include a detergent system that provides a metal source, preferably sodium, calcium, magnesium, or a combination thereof, from a detergent additive such as a phenate, sulfonate, or salicylate, as further described below. Suitable detergents and methods for their preparation are described in more detail in numerous patent publications, such as U.S. Pat. No. 7,732,390 and the references cited therein, which are incorporated herein by reference. The lubricant compositions herein may include up to about 3.0 weight percent, or from about 0.01 to about 2.0 weight percent, or in other approaches, from about 0.1 to about 1.5 weight percent, of a detergent system, so long as the composition includes the recited relationship between the antiwear agent phosphorus and either the lubricant TBN or the detergent metal, as further discussed herein.

[0034] As noted above, in some approaches, the detergent system provides a selected amount of metal, preferably a combination of calcium and magnesium, to the lubricating composition. For example, the detergent systems herein provide amounts of up to about 1800 ppm, up to about 1700 ppmw, up to about 1600 ppmw, up to about 1500 ppmw, up to about 1400 ppmw, up to about 1300 ppmw of metal, up to about 1200 ppmw of metal, or up to about 1100 ppmw of metal. In other cases, the detergent system provides at least about 100 ppmw of metal, at least about 200 ppmw of metal, at least about 300 ppmw of metal, or at least about 400 ppmw of metal.

[0035] Preferably, the detergent system provides calcium and magnesium. In some approaches, the detergent system includes about 55 to about 75 weight percent (in other approaches, about 60 to about 70 weight percent) of detergent additive providing calcium and about 25 to about 45 weight percent (in other approaches, about 30 to about 40 weight percent) of detergent additive providing magnesium. The detergent system may also provide about 10 to about 1500 ppm of calcium and about 10 to about 500 ppm of magnesium to the lubricant composition in other embodiments. In some approaches, both calcium and magnesium are provided by a sulfonate or phenate detergent additive (preferably a sulfonate detergent additive) having a TBN of 0 to about 500, or in other approaches, an overbased detergent additive having a TBN of about 180 to about 500, about 200 to about 450, or about 300 to about 425.

[0036] Generally, the detergent base may be salted with alkali or alkaline earth metals, such as, but not limited to, calcium and magnesium as described above, but the detergent may also be salted with potassium, sodium, lithium, barium, zinc, or mixtures thereof, so long as the detergent system meets the total metal, and, in any approach, calcium and magnesium requirements described herein. In one approach, suitable detergents in the system may include alkali or alkaline earth metal salts, such as calcium or magnesium, of petroleum sulfonic acids and long-chain mono- or di-alkylaryl sulfonic acids in which the aryl groups are benzyl, tolyl, and xylyl, and / or various phenates or phenate derivatives. Examples of suitable detergents include, but are not limited to, lowbased / neutral and / or overbased variations of the following detergents: calcium phenate, calcium sulfur-containing phenate, calcium sulfonate, calcium calixarate, calcium salixarate, calcium salicylate, calcium carboxylic acid, calcium phosphate, calcium mono- and / or di-thiophosphate, calcium alkyl phenol, calcium sulfur-bound alkyl phenol compound, calcium methylene bridged phenol, magnesium phenate, magnesium sulfur-containing phenate, magnesium sulfonate, magnesium calixarate, magnesium salixarate, magnesium salicylate, magnesium carboxylic acid, magnesium phosphate, magnesium mono- and / or di-thiophosphate, magnesium alkyl phenol, magnesium sulfur-bound alkyl phenol compound, magnesium methylene bridged phenol, sodium phenate, sodium sulfur-containing phenate, sodium sulfonate, sodium calixarate, sodium salixarate, sodium salicylate, sodium carboxylic acid, sodium phosphate, sodium mono- and / or di-thiophosphate, sodium alkyl phenol, sodium sulfur-bound alkyl phenol compound, or sodium methylene bridged phenol.

[0037] The detergent may be neutral to overbased, preferably an overbased detergent. Overbased detergent additives are known in the art and may be alkali metal or alkaline earth metal overbased detergent additives. Such detergent additives may be prepared by reacting a metal oxide or metal hydroxide with a base material and carbon dioxide gas. The base material is typically an acid, such as an aliphatic-substituted sulfonic acid, aliphatic-substituted carboxylic acid, or aliphatic-substituted phenol.

[0038] As will be understood, the term "overbased" refers to metal salts in which the amount of metal present exceeds the stoichiometric amount, such as, but not limited to, metal salts of sulfonates, carboxylates, salicylates, and / or phenates. Such salts may have a conversion level of greater than 100% (i.e., they may contain more than 100% of the theoretical amount of metal required to convert the acid to its "standard" or "neutral" salt). The expression "metal ratio," often abbreviated as MR, may be used to indicate the ratio of the total chemical equivalents of metal in an overbased salt to the chemical equivalents of metal in a neutral salt, according to known chemical reactivity and stoichiometry. In standard or neutral salts, the MR is 1, while in overbased salts, the MR is greater than 1. These are commonly referred to as overbased, highly based, or superbased salts and may be salts of organic sulfur acids, carboxylic acids, or phenols.

[0039] As used herein, the term "TBN" is used to represent a total base number in units of "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 1.1:1 or more, or 2:1 or more, or 4:1 or more, or 5:1 or more, or 7:1 or more, or 10:1 or more.

[0040] Examples of suitable overbased detergents include, but are not limited to, overbased calcium phenates, overbased calcium sulfur-containing phenates, overbased calcium sulfonates, overbased calcium calixarates, overbased calcium salixarates, overbased calcium salicylates, overbased calcium carboxylic acids, overbased calcium phosphates, overbased calcium mono- and / or di-thiophosphates, overbased calcium alkylphenols, overbased calcium sulfur-bound alkylphenol compounds, overbased calcium methylene-bridged phenols, overbased magnesium phenates, overbased magnesium sulfonates, overbased magnesium calixarates, overbased magnesium salixarates, overbased magnesium salicylates, overbased magnesium carboxylic acids, overbased magnesium phosphates, overbased magnesium mono- and / or di-thiophosphates, overbased magnesium alkylphenols, overbased magnesium sulfur-bound alkylphenol compounds, or overbased magnesium methylene-bridged phenols.

[0041] The detergent can also be a low-based or neutral detergent. For example, low-based or neutral detergents, when used in the systems herein, generally have 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 can 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.

[0042] In an embodiment, the detergent system includes a combination of calcium sulfonate and magnesium sulfonate, but is not necessarily limited to such a detergent combination. In one approach, the calcium sulfonate in the detergent system herein is preferably an overbased detergent, having a total base number of from about 200 to about 500, and in another approach, from about 300 to about 450. In another approach, the magnesium sulfonate in the detergent system herein is also preferably an overbased detergent, having a total base number of from about 200 to about 500, and in another approach, from about 300 to about 425.

[0043] Anti-wear agent The lubricating compositions herein also include an antiwear system in combination with the detergent system described above. The antiwear system provides a mixture of wear-resistant metals and phosphorus effective to achieve, among other characteristics, friction performance and, surprisingly, high-temperature deposit performance when balanced against the characteristics of the detergent system. The lubricating compositions herein can contain up to about 3.0 weight percent of the antiwear system, or from about 0.01 to about 2.0 weight percent, or alternatively, from about 0.1 to about 1.5 weight percent, of the antiwear system, so long as the composition includes the recited relationship of antiwear phosphorus to either the lubricant TBN or detergent metal, as discussed further herein.

[0044] In one approach, the antiwear system includes a mixture of two or more metal dihydrocarbyl dithiophosphate compounds, such as, but not limited to, two or more zinc dihydrocarbyl dithiophosphate compounds (ZDDPs). Suitable metal dithiophosphates, such as ZDDPs, may each contain 5 to about 10 weight percent metal (in other approaches, about 6 to about 9 weight percent metal, preferably zinc) and about 8 to about 18 weight percent sulfur (in other approaches, about 12 to about 18 weight percent sulfur, or about 8 to about 15 weight percent sulfur). Metal dithiophosphates, such as ZDDPs, may also contain about 5 to about 10 weight percent phosphorus. Suitable metal dihydrocarbyl dithiophosphates can be any of the metal dihydrocarbyl dithiophosphates, where the metal can be an alkali metal, alkaline earth metal, aluminum, lead, tin, molybdenum, manganese, nickel, copper, titanium, zirconium, zinc, or a combination thereof. However, the metal is preferably zinc.

[0045] When the phosphorus-containing compound of the antiwear system is ZDDP, the alkyl groups on the ZDDP may be derived from primary alcohols, secondary alcohols, and / or mixtures thereof. For example, primary alcohols suitable for forming the alkyl groups on the ZDDP include, but are not limited to, ethylhexyl alcohol, butanol, and / or C6 and higher primary alcohols. Secondary alcohols suitable for forming the alkyl groups on the ZDDP include, but are not limited to, methyl isobutyl carbinol, isopropyl alcohol, or mixtures thereof. In some cases, the alkyl groups on the ZDDP may be derived from mixtures of primary and secondary alcohols, such as 2-ethylhexanol (primary), isobutanol (primary), and isopropanol (secondary). For example, in one embodiment, one ZDDP additive in the antiwear system contains approximately the alkyl groups derived from a C6-C8 primary alcohol, particularly ethylhexyl alcohol. In another embodiment, a second ZDDP in the antiwear system contains all alkyl groups derived from a secondary alcohol, such as methyl isobutyl carbinol. In one approach, the antiwear system herein comprises a mixture of metal dialkyldithiophosphates (preferably zinc dialkyldithiophosphates) derived from primary and secondary alcohols. In embodiments, the weight ratio of primary alcohol to secondary alcohol from the two ZDDP additives combined in the antiwear system is at least about 0.25:1.0 to about 0.5:1.0, and in another approach, from about 0.3:1 to about 0.4:1, as discussed further below.

[0046] Examples of suitable ZDDPs include metal O,O-di(C 1~14 -Alkyl)dithiophosphate; (Mixed O,O-bis(sec-butyl and isooctyl))zinc dithiophosphate; O,O-Bis(branched and linear C 3~8-alkyl)dithiophosphate;Zinc O,O-bis(2-ethylhexyl)dithiophosphate;Zinc O,O-bis(mixed isobutyl and pentyl)dithiophosphate;Zinc 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-diisodecyldithiophosphate;O-(6-methylheptyl)-O-(1-methyl 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.

[0047] In yet another approach, each of the phosphorus-containing compounds in the antiwear systems herein can each have the structure of Formula I:

[0048] [ka] wherein R in Formula I independently contains 1 to 18 carbon atoms, or 2 to 12 carbon atoms, or about 3 to 8 carbon atoms. The antiwear 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, or butenyl, as needed to meet the selected ratio of primary and secondary alcohols described above in the antiwear system. In some embodiments, the number of carbon atoms in each R group in Formula I above will generally be 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.

[0049] In yet another approach, the zinc dialkyldithiophosphate of the antiwear system has a sulfur-zinc coordination arrangement of the phosphorus compound in the antiwear system shown under the chemical structure of Formula II, which may be interchangeable with Formula I shown above. It is also understood that the structures shown in Formulas I and II may exist as monomers, dimers, trimers, or oligomers (e.g., tetramers).

[0050] [ka]

[0051] In some embodiments, each phosphorus-containing compound of the antiwear system has the structure of Formula I, where A is zinc, and the combined total amount of compounds in the antiwear system provides the lubricant composition with about 70 to about 800 ppm phosphorus (or, in other approaches, about 250 to about 800 ppm) and about 50 to about 850 ppm zinc. As noted above, the antiwear system includes a mixture of zinc dialkyldithiophosphates. Preferably, the antiwear system includes at least two zinc dialkyldithiophosphates, with the first zinc dialkyldithiophosphate derived solely from a primary alcohol and the second zinc dialkyldithiophosphate derived solely from a secondary alcohol. Preferably, the antiwear system comprises a majority of the second zinc dialkyldithiophosphate derived exclusively from secondary alcohols; for example, the weight ratio of primary alcohols to secondary alcohols forming the ZDDP in the antiwear mixture (i.e., all compounds in the antiwear mixture) is at least 0.25:1.0 (i.e., about 70 to about 80% of all alkyl groups in the antiwear mixture are derived from secondary alcohols, and about 20 to about 30% of all alkyl groups in the antiwear mixture are derived from primary alcohols). In another approach, the ratio of primary alcohols to secondary alcohols forming the ZDDP in the antiwear mixture is at least about 0.25:1.0 to about 0.5:1.0, and in another approach, about 0.3:1 to about 0.4:1.

[0052] In some approaches, the lubricating compositions herein have an antiwear system that provides an amount of phosphorus, in embodiments, about 800 ppm or less of phosphorus to the lubricating composition. In other approaches, the antiwear system provides about 700 ppm or less of phosphorus, about 500 ppm or less of phosphorus, 400 ppm or less of phosphorus, or about 300 ppm or less of phosphorus. In yet other approaches, the antiwear system provides at least about 50 ppm of phosphorus, at least about 75 ppm of phosphorus, or at least about 100 ppm of phosphorus.

[0053] In another approach, the lubricating compositions herein have an antiwear agent system that provides an amount of wear-resistant metal (preferably zinc), in embodiments providing the lubricating composition with about 850 ppm or less of zinc. In another approach, the antiwear agent system provides about 800 ppm or less of zinc, about 700 ppm or less of zinc, 500 ppm or less of zinc, or about 400 ppm or less of zinc. In yet another approach, the antiwear agent system provides at least about 50 ppm of zinc, at least about 75 ppm of zinc, or at least about 100 ppm of zinc. In embodiments, the lubricating compositions herein comprise an amount of zinc provided by the antiwear agent system relative to the amount of total metals from the detergent system of about 0.6 or less.

[0054] Dihydrocarbyl dithiophosphate metal salts can be prepared according to known techniques, typically by first forming a dihydrocarbyl dithiophosphate (DDPA) by reacting one or more alcohols or phenols with P2S5, and then neutralizing the resulting 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.

[0055] lubricating oil composition The above-described detergent and antiwear systems, in combination with one or more further optional additives, may be combined with a major amount of a base oil or base oil blend of lubricating viscosity (as described below) to produce a lubricating oil composition, in an approach comprising at least about 50 weight percent of the base oil blend, at least about 60 weight percent, at least about 70 weight percent, or at least about 80 weight percent to at most about 95 weight percent, at most about 90 weight percent, at most about 85 weight percent of the base oil blend, such blends being discussed further below.

[0056] As noted above, the lubricating oil compositions comprise a unique relationship between phosphorus provided from the antiwear system relative to either (i) the TBN of the overall lubricating composition, (ii) the amount of total detergent metals (preferably calcium and / or magnesium), and / or (iii) a ratio of both effective to reduce and / or maintain low levels of high temperature deposits, particularly low levels of high temperature deposits associated with lubricating compositions having low levels of ash, calculated as sulfated ash, for example, lubricating compositions having a calculated sulfated ash content of about 0.8 weight percent or less.

[0057] For example, the overall lubricating compositions herein preferably have a total base number (TBN) of about 0.5 to about 20 (alternatively, about 0.5 to about 10), and, in relation to the detergent and antiwear systems described above, have a specific relationship between the amount of phosphorus from the antiwear system to the TBN of the lubricating composition of about 150 or less, or in other embodiments, the amount of phosphorus from the antiwear system to the lubricant TBN of about 120 or less (preferably about 10 or more, about 20 or more, about 50 or more, or about 80 or more, or even about 80 or more). In still other embodiments, the amount of phosphorus from the antiwear system relative to the amount of metal from the detergent system may be about 0.5 or less, or even about 0.38 or less (preferably about 0.02 or more, about 0.05 or more, about 0.1 or more, or about 0.2 or more, or even about 0.25 or more). In this regard, the lubricating compositions herein have less than about 30 mg of deposits when subjected to the High Temperature Deposit Formation Test of ASTM D6335 (TEOST-33C), and, for low ash compositions, contain about 0.8 weight percent or less calculated sulfated ash (or about 0.1 to about 0.8 weight percent calculated sulfated ash).

[0058] Base Oil Blends: 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 specified in the American Petroleum Institute (API) Base Oil Interchangeability Guidelines. The five base oil groups are as follows:

[0059] [Table 1]

[0060] Group I, Group II, and Group III are mineral oil process feedstocks. Group IV base oils contain true synthetic molecular species produced by the 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, but may also be natural oils such as vegetable oils. Group III base oils are derived from mineral oils, but it should be noted that the rigorous processing these fluids undergo makes their physical properties very similar to some true synthetic oils, such as PAOs. Therefore, oils derived from Group III base oils may be referred to in industry as synthetic fluids. Group II+ may include high viscosity index Group II.

[0061] The base oil blends used in the disclosed lubricating oil compositions can be mineral, animal, vegetable, synthetic, synthetic oil blends, or mixtures thereof. Suitable oils can be derived from hydrocracked, hydrogenated, hydrofinished, unrefined, refined, and rerefined oils, and mixtures thereof.

[0062] Unrefined oils are derived from natural, mineral, or synthetic sources with little or no further purification processing. Refined oils are similar to unrefined oils except that they have been treated with one or more purification steps, which may result in the improvement of one or more properties. Examples of suitable purification techniques include 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 called white oils. In some embodiments, the lubricating oil composition does not include edible oils or white oils.

[0063] Re-refined oils are also known as reclaimed or reprocessed oils. These oils are obtained using the same or similar processes as refined oils. Often, these oils are further processed by techniques directed to the removal of spent additives and oil breakdown products.

[0064] 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.

[0065] Useful synthetic lubricating oils may 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 α-olefins), and mixtures thereof; alkyl-benzenes (e.g., dodecylbenzene, tetradecylbenzene, dinonylbenzene, di-(2-ethylhexyl)-benzene); polyphenyls (e.g., biphenyl, terphenyl, alkylated polyphenyls); diphenylalkanes, alkylated diphenylalkanes, alkylated diphenyl ethers, and alkylated diphenyl sulfides, as well as their derivatives, analogs, and homologs, or mixtures thereof. Polyalphaolefins are typically hydrogenated materials.

[0066] 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 are typically hydroisomerized Fischer-Tropsch hydrocarbons or waxes. In one embodiment, the oils can be prepared by the Fischer-Tropsch gas-to-liquid synthesis procedure, as well as other gas-to-liquid oils.

[0067] A major amount of 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, but the major amount of base oil is other than the base oil resulting from the provision of additive components or viscosity index improvers in the composition. In another embodiment, a major amount of base oil included in the lubricating composition may be selected from the group consisting of Group II, Group III, Group IV, Group V, and combinations of two or more of the foregoing, but the major amount of base oil is other than the base oil resulting from the provision of additive components or viscosity index improvers in the composition.

[0068] 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 depressants 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.

[0069] Optional Additives: The lubricating oil compositions herein may also contain a number of optional additives, described in the following paragraphs, in combination with the dispersant, antioxidant, and antiwear systems discussed above, as needed to meet performance specifications, so long as the described relationships regarding nitrogen and nitrogen sources are maintained.

[0070] Optional Dispersants: The lubricating oil composition may optionally contain one or more additional dispersants or mixtures thereof. Dispersants are often referred to as ashless dispersants because they do not contain ash-forming metals prior to incorporation into the lubricating oil composition and do not typically contribute ash when added to the lubricant. Ashless dispersants are characterized by polar groups 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 in which the number average molecular weight of the polyisobutylene substituent ranges from about 350 to about 50,000, or from about 5,000, or from about 3,000, as measured by GPC. Succinimide dispersants and their preparation are disclosed, for example, in U.S. Pat. No. 7,897,696 or U.S. Pat. No. 4,234,435. The alkenyl substituent may be prepared from polymerizable monomers containing from about 2 to about 16, or from about 2 to about 8, or from about 2 to about 6 carbon atoms. Succinimide dispersants are typically imides formed from polyamines, typically poly(ethyleneamines).

[0071] Preferred amines are selected from polyamines and hydroxyamines. Examples of polyamines that can be used include, but are not limited to, diethylenetriamine (DETA), triethylenetetramine (TETA), tetraethylenepentamine (TEPA), and higher homologs such as pentaethylaminehexamine (PEHA).

[0072] Suitable heavy polyamines are mixtures of polyalkylene-polyamines containing oligomers with six or more nitrogen atoms, two or more primary amines per molecule, and more extensive branching than conventional polyamine mixtures, although they contain small amounts of lower polyamine oligomers such as TEPA and PEHA (pentaethylenehexamine). Heavy polyamines preferably include polyamine oligomers containing seven or more nitrogen atoms per molecule and two or more primary amines per molecule. Heavy polyamines contain greater than 28% by weight (e.g., greater than 32% by weight) of total nitrogen and an equivalent weight of 120 to 160 grams of primary amine groups per equivalent.

[0073] In some approaches, suitable polyamines are commonly known as PAMs and contain a mixture of ethyleneamines, with TEPA and pentaethylenehexamine (PEHA) being the major portion of the polyamine, usually less than about 80%.

[0074] Typically, PAM has 8.7-8.9 milliequivalents of primary amine per gram (115-112 milliequivalents per equivalent of primary amine) and a total nitrogen content of about 33-34% by weight. Heavier cuts of PAM oligomers that are substantially free of TEPA and contain only small amounts of PEHA, but contain primarily oligomers with more than six nitrogen atoms and more extensive branching, may produce dispersants with improved dispersancy.

[0075] In some embodiments, the present disclosure further comprises at least one polyisobutylene succinimide dispersant derived from polyisobutylene having a number average molecular weight, as determined by GPC, ranging from about 350 to about 50,000, or from about 5,000, or from about 3,000. The polyisobutylene succinimide may be used alone or in combination with other dispersants.

[0076] In some embodiments, when polyisobutylene is included, the polyisobutylene may have 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%. Such PIB is also referred to as highly reactive PIB ("HR-PIB"). HR-PIB having a number average molecular weight in the range of about 800 to about 5000 as determined by GPC is suitable for use in embodiments of the present disclosure. Conventional PIB typically has a terminal double bond content of less than 50 mol%, less than 40 mol%, less than 30 mol%, less than 20 mol%, or less than 10 mol%.

[0077] HR-PIB having a number-average molecular weight ranging from about 900 to about 3000, as determined by GPC, may be suitable. Such HR-PIB is commercially available or can be synthesized by polymerization of isobutene in the presence of a non-chlorinated catalyst, such as boron trifluoride, as described in U.S. Patent No. 4,152,499 to Boerzel et al. and U.S. Patent No. 5,739,355 to Gateau et al. When HR-PIB is used in the thermal ene reaction, it can result in higher conversion and less precipitate formation during the reaction due to increased reactivity. A suitable method is described in U.S. Patent No. 7,897,696.

[0078] In one embodiment, the present disclosure further comprises at least one dispersant derived from polyisobutylene succinic anhydride ("PIBSA"), which may have an average of about 1.0 to about 2.0 succinic moieties per polymer.

[0079] The percent active ingredient of the alkenyl or alkyl succinic anhydride can be determined using chromatographic techniques, which are described in columns 5 and 6 of U.S. Patent No. 5,334,321.

[0080] Polyolefin conversion is calculated from the % active ingredient using the formula in columns 5 and 6 of US Pat. No. 5,334,321.

[0081] Unless otherwise specified, all percentages are weight percent and all molecular weights are number average molecular weights as determined by gel permeation chromatography (GPC) using commercially available polystyrene standards (having number average molecular weights of 180 to about 18,000) as calibration standards.

[0082] In one embodiment, the dispersant may be derived from a polyalphaolefin (PAO) succinic anhydride. In one embodiment, the dispersant may be derived from an olefin maleic anhydride copolymer. As an example, the dispersant may be described as poly-PIBSA. In one embodiment, the dispersant may be derived from an anhydride grafted to an ethylene-propylene copolymer.

[0083] A suitable type of nitrogen-containing dispersant can be derived from an olefin copolymer (OCP), more specifically, an ethylene-propylene dispersant, which can be grafted with maleic anhydride. A more complete list of nitrogen-containing compounds that can be reacted with the functionalized OCP is described in U.S. Patent Nos. 7,485,603, 7,786,057, 7,253,231, 6,107,257, and 5,075,383, and / or is commercially available.

[0084] One class of suitable dispersants can also 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 more detail in U.S. Pat. No. 3,634,515.

[0085] A suitable class of dispersants may also be high molecular weight esters or half-ester amides. Suitable dispersants may also be post-treated by conventional methods with any of a variety of agents. Among these are boron, urea, thiourea, dimercaptothiadiazole, carbon disulfide, aldehydes, ketones, carboxylic acids, hydrocarbon-substituted succinic anhydrides, maleic anhydride, nitriles, epoxides, carbonates, cyclic carbonates, hindered phenol esters, and phosphorus compounds. U.S. Patent Nos. 7,645,726, 7,214,649, and 8,048,831 are incorporated herein by reference in their entireties.

[0086] In addition to the carbonate and boric acid post-treatments, any of the compounds may be post-treated or further post-treated with a variety of post-treatments designed to improve or impart different properties. Such post-treatments include those summarized in columns 27-29 of U.S. Pat. No. 5,241,003, which is incorporated herein by reference. Such treatments include treatment with inorganic phosphoric acids or anhydrides (e.g., U.S. Pat. Nos. 3,403,102 and 4,648,980); organic phosphorus compounds (e.g., U.S. Pat. No. 3,502,677); phosphorus pentasulfide; boron compounds as already mentioned above (e.g., U.S. Pat. Nos. 3,178,663 and 4,652,387); carboxylic acids, polycarboxylic acids, anhydrides, and / or acid halides (e.g., U.S. Pat. Nos. 3,708,522 and 4,909,910). 48,386); epoxide polyepoxides or thioepoxides (e.g., U.S. Pat. Nos. 3,859,318 and 5,026,495); aldehydes or ketones (e.g., U.S. Pat. No. 3,458,530); carbon disulfide (e.g., U.S. Pat. No. 3,256,185); glycidol (e.g., U.S. Pat. No. 4,617,137); urea, thiourea, or guanidine (e.g., U.S. Pat. No. 3,312,61 Nos. 9, 3,865,813, and British Patent No. 1,065,595; organic sulfonic acids (e.g., U.S. Pat. No. 3,189,544 and British Patent No. 2,140,811); alkenyl cyanides (e.g., U.S. Pat. Nos. 3,278,550 and 3,366,569); diketene (e.g., U.S. Pat. No. 3,546,243); diisocyanates (e.g., U.S. Pat. No. 3,573,205); alkanesulf ...546,243); ton (e.g., U.S. Pat. No. 3,749,695); 1,3-dicarbonyl compounds (e.g., U.S. Pat. No. 4,579,675); sulfates of alkoxylated alcohols or phenols (e.g., U.S. Pat. No. 3,954,639); cyclic lactones (e.g., U.S. Pat. Nos. 4,617,138, 4,645,515, 4,668,246, 4,963,275, and 4,971,711);Cyclic carbonates or thiocarbonates, linear monocarbonates or polycarbonates, or chloroformates (e.g., U.S. Pat. Nos. 4,612,132, 4,647,390, 4,648,886, 4,670,170); nitrogen-containing carboxylic acids (e.g., U.S. Pat. No. 4,971,598 and British Patent No. 2,140,811); hydroxy-protected chlorodicarbonyloxy compounds (e.g., U.S. Pat. No. 4,614,522); lactams, thiolactams, thiolactones, or dithiolactones (e.g., U.S. Pat. Nos. 4,614,522, ... Nos. 4,614,603 and 4,666,460; cyclic carbonates or thiocarbonates, linear monocarbonates or polycarbonates, or chloroformates (e.g., U.S. Pat. Nos. 4,612,132, 4,647,390, 4,646,860, and 4,670,170); nitrogen-containing carboxylic acids (e.g., U.S. Pat. No. 4,971,598 and British Patent No. 2,440,811); hydroxy-protected chlorodicarbonyloxy compounds (e.g., U.S. Pat. No. 4,614,522); lactams, thiocarbonates, and the like. olactams, thiolactones, or dithiolactones (e.g., U.S. Pat. Nos. 4,614,603 and 4,666,460); cyclic carbamates, cyclic thiocarbamates, or cyclic dithiocarbamates (e.g., U.S. Pat. Nos. 4,663,062 and 4,666,459); hydroxyaliphatic carboxylic acids (e.g., U.S. Pat. Nos. 4,482,464, 4,521,318, and 4,713,189); oxidizing agents (e.g., U.S. Pat. No. 4,379,064); combinations of phosphorus pentasulfide and polyalkylene polyamines (e.g., U.S. Pat. Nos. 4,379,064, 4,379,064); , U.S. Pat. No. 3,185,647); combinations of carboxylic acids or aldehydes or ketones and sulfur or sulfur chloride (e.g., U.S. Pat. Nos. 3,390,086, 3,470,098); combinations of hydrazine and carbon disulfide (e.g., U.S. Pat. No. 3,519,564); combinations of aldehydes and phenols (e.g., U.S. Pat. Nos. 3,649,229, 5,030,249, 5,039,307); combinations of aldehydes and O-diesters of dithiophosphoric acids (e.g., U.S. Pat. No. 3,865,740);Combinations of hydroxyaliphatic carboxylic acids and boric acid (e.g., U.S. Pat. No. 4,554,086); combinations of hydroxyaliphatic carboxylic acids followed by formaldehyde and phenol (e.g., U.S. Pat. No. 4,636,322); combinations of hydroxyaliphatic carboxylic acids followed by aliphatic dicarboxylic acids (e.g., U.S. Pat. No. 4,663,064); combinations of formaldehyde and phenol followed by glycolic acid (e.g., U.S. Pat. No. 4,699,724); combinations of hydroxyaliphatic carboxylic acids or oxalic acid followed by a diisocyanate (e.g., U.S. Pat. No. 4,713,191); inorganic acids or anhydrides of phosphorus or a combination of its partial or total sulfur analogue and a boron compound (e.g., U.S. Pat. No. 4,857,214); a combination of an organic diacid, followed by an unsaturated fatty acid, followed by a nitrosoaromatic amine, optionally followed by a boron compound, and then a glycosylation agent (e.g., U.S. Pat. No. 4,973,412); a combination of an aldehyde and a triazole (e.g., U.S. Pat. No. 4,963,278); a combination of an aldehyde and a triazole, followed by a boron compound (e.g., U.S. Pat. No. 4,981,492); a combination of a cyclic lactone and a boron compound (e.g., U.S. Pat. Nos. 4,963,275 and 4,971,711). The above-mentioned patents are incorporated herein in their entirety.

[0087] The TBN of suitable dispersants can be from about 10 to about 65 mg KOH / g on an oil-free basis, which equates to about 5 to about 30 TBN when measured on a dispersant sample containing about 50% diluent oil. TBN is measured by the method of ASTM D2896.

[0088] In yet another embodiment, the optional dispersant additive may be a hydrocarbyl-substituted succinamide or succinimide dispersant. In some approaches, the hydrocarbyl-substituted succinamide or succinimide dispersant may be derived from a hydrocarbyl-substituted acylating agent reacted with a polyalkylene polyamine, wherein the hydrocarbyl substituent of the succinamide or succinimide dispersant is a linear or branched hydrocarbyl group having a number average molecular weight of about 250 to about 5,000 as determined by GPC using polystyrene as a calibration standard.

[0089] In some approaches, the polyalkylene polyamine used to form the dispersant has the following formula:

[0090] [ka] wherein each R and R' is independently a divalent C1-C6 alkylene linker, and each R1 and R2 is independently hydrogen, a C1-C6 alkyl group, or together with the nitrogen atom to which they are attached form a 5- or 6-membered ring optionally fused to one or more aromatic or non-aromatic rings, and n is an integer from 0 to 8. In another approach, the polyalkylene polyamine is selected from the group consisting of a mixture of polyethylene polyamines having an average of 5 to 7 nitrogen atoms, triethylenetetramine, tetraethylenepentamine, and combinations thereof.

[0091] The optional dispersant, when present, may be used in an amount sufficient to provide up to about 20 wt. % dispersant ...

[0092] Additional Antioxidants: The lubricating oil compositions herein may also optionally contain one or more additional antioxidants. Antioxidant compounds are known and include, for example, phenates, phenate sulfides, sulfurized olefins, phosphosulfurized terpenes, sulfurized esters, aromatic amines, alkylated diphenylamines (e.g., nonyldiphenylamine, di-nonyldiphenylamine, octyldiphenylamine, di-octyldiphenylamine), phenyl-alpha-naphthylamines, alkylated phenyl-alpha-naphthylamines, hindered non-aromatic amines, phenols, hindered phenols, oil-soluble molybdenum compounds, polymeric antioxidants, or mixtures thereof. The antioxidant compounds may be used alone or in combination.

[0093] The hindered phenol antioxidant may contain a secondary butyl group and / or a tertiary butyl group as a steric hindering group. The phenol group may be further substituted with a hydrocarbyl group and / or a bridging group connecting to a second aromatic group. Examples of suitable hindered phenol antioxidants include 2,6-di-tert-butylphenol, 4-methyl-2,6-di-tert-butylphenol, 4-ethyl-2,6-di-tert-butylphenol, 4-propyl-2,6-di-tert-butylphenol, 4-butyl-2,6-di-tert-butylphenol, or 4-dodecyl-2,6-di-tert-butylphenol. In one embodiment, the hindered phenol antioxidant may be an ester, such as Irganox® L-135 available from BASF, or an addition product derived from 2,6-di-tert-butylphenol and an alkyl acrylate. The alkyl group may contain from about 1 to about 18, or from about 2 to about 12, or from about 2 to about 8, or from about 2 to about 6, or about 4 carbon atoms. Another commercially available hindered phenol antioxidant may be an ester and may include Ethanox™ 4716 available from Albemarle Corporation.

[0094] Useful antioxidants may include diarylamines and high molecular weight phenols. In one embodiment, the lubricating oil composition may contain a mixture of diarylamines and high molecular weight phenols, such that each antioxidant may be present in an amount sufficient to provide up to about 5 wt. %, based on the final weight of the lubricating oil composition. In one embodiment, the antioxidant may be a mixture of about 0.3 to about 1.5 wt. % diarylamines and about 0.4 to about 2.5 wt. % high molecular weight phenols, based on the final weight of the lubricating oil composition.

[0095] Examples of suitable olefins that can be sulfurized to form sulfurized olefins include propylene, butylene, isobutylene, polyisobutylene, pentene, hexene, heptene, octene, nonene, decene, undecene, dodecene, tridecene, tetradecene, pentadecene, hexadecene, heptadecene, octadecene, nonadecene, eicosene, or mixtures thereof. In one embodiment, hexadecene, heptadecene, octadecene, nonadecene, eicosene, or mixtures thereof, as well as their dimers, trimers, and tetramers, are particularly useful olefins. Alternatively, the olefin can be a Diels-Alder adduct of a diene, such as 1,3-butadiene, and an unsaturated ester, such as butyl acrylate.

[0096] Another class of sulfurized olefins includes sulfurized fatty acids and their esters. The fatty acids are often derived from vegetable or animal oils and typically contain from about 4 to about 22 carbon atoms. Examples of suitable fatty acids and their esters include triglycerides, oleic acid, linoleic acid, palmitoleic acid, or mixtures thereof. Often, the fatty acids are derived from lard oil, tall oil, peanut oil, soybean oil, cottonseed oil, sunflower seed oil, or mixtures thereof. The fatty acids and / or esters may be mixed with an olefin, such as an α-olefin.

[0097] In another alternative embodiment, the antioxidant composition contains a molybdenum-containing antioxidant in addition to the phenolic and / or aminic antioxidants discussed above. When a combination of these three antioxidants is used, preferably the ratio of phenol to amine to molybdenum-containing is (0-2):(0-2):(0-1).

[0098] The one or more antioxidants may be present in a range of from about 0% to about 20%, or from about 0.1% to about 10%, or from about 1% to about 5% by weight of the lubricating oil composition.

[0099] Additional Antiwear Agents: The lubricating oil compositions herein may also optionally contain one or more additional antiwear agents. Examples of suitable additional antiwear agents include, but are not limited to, metal thiophosphates; metal dialkyldithiophosphates; phosphoric acid esters or salts thereof; phosphoric acid esters; phosphites; phosphorus-containing carboxylic acid esters, ethers, or amides; sulfurized olefins; thiocarbamate-containing compounds, such as thiocarbamate esters, alkylene-linked thiocarbamates, and bis(S-alkyldithiocarbamyl) disulfides; and mixtures thereof. A suitable antiwear agent may be molybdenum dithiocarbamate. Phosphorus-containing antiwear agents are more fully described in EP 612839. The metal in the dialkyldithiophosphate salt may be an alkali metal, alkaline earth metal, aluminum, lead, tin, molybdenum, manganese, nickel, copper, titanium, or zinc. A useful antiwear agent may be zinc dialkyldithiophosphate.

[0100] Further examples of suitable antiwear agents include titanium compounds, tartrates, tartrimides, oil-soluble amine salts of phosphorus compounds, sulfurized olefins, phosphites (e.g., dibutyl phosphite), phosphonates, thiocarbamate-containing compounds such as thiocarbamate esters, thiocarbamate amides, thiocarbamic acid ethers, alkylene-linked thiocarbamates, and bis(S-alkyldithiocarbamyl) disulfides. The tartrates or tartrimides may contain alkyl-ester groups, but the total number of carbon atoms on the alkyl group may be at least 8. In one embodiment, the antiwear agent may include citrate.

[0101] The antiwear agent may be present in ranges including from about 0 to about 15 weight percent, or from about 0.01 to about 10 weight percent, or from about 0.05 to about 5 weight percent, or from about 0.1 to about 3 weight percent of the lubricating oil composition.

[0102] Boron-Containing Compounds: The lubricating oil compositions herein may optionally contain one or more boron-containing compounds. Examples of boron-containing compounds include borate esters, borated fatty amines, borated epoxides, borated detergents, and borated dispersants, such as borated succinimide dispersants, as disclosed in U.S. Patent No. 5,883,057. When present, the boron-containing compounds may be used in an amount sufficient to provide up to about 8 wt. %, from about 0.01 to about 7 wt. %, from about 0.05 to about 5 wt. %, or from about 0.1 to about 3 wt. % of the lubricating oil composition.

[0103] Additional Detergents: The lubricating oil composition may optionally further comprise one or more additional neutral, underbased, or overbased detergents, and mixtures thereof. Suitable additional detergent base stocks include phenates, sulfur-containing phenates, sulfonates, calixarates, salixarates, salicylates, carboxylic acids, phosphorus acids, mono- and / or di-thiophosphoric acids, alkylphenols, sulfur-bonded alkylphenol compounds, or methylene-bridged phenols. 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.

[0104] The detergent substrate may be salified with an alkali metal or alkaline earth metal, such as, but not limited to, calcium, magnesium, potassium, sodium, lithium, barium, or mixtures thereof. In some embodiments, the detergent is barium-free. In some embodiments, the detergent may contain trace amounts of other metals, such as magnesium or calcium, in amounts of 50 ppm or less, 40 ppm or less, 30 ppm or less, 20 ppm or less, or 10 ppm or less. Suitable detergents may include alkali metal or alkaline earth metal salts of petroleum sulfonic acids and long-chain mono- or di-alkylaryl sulfonic acids in which the aryl groups are benzyl, tolyl, and xylyl. Examples of suitable detergents include, but are not limited to, calcium phenate, calcium sulfur-containing phenate, calcium sulfonate, calcium calixarate, calcium salixarate, calcium salicylate, calcium carboxylic acid, calcium phosphate, calcium mono- and / or di-thiophosphate, calcium alkyl phenol, calcium sulfur-bound alkyl phenol compound, calcium methylene bridged phenol, magnesium phenate, magnesium sulfur-containing phenate, magnesium sulfonate, magnesium calixarate, magnesium salixarate, magnesium salicylate, magnesium carboxylic acid, magnesium phosphate, magnesium mono- and / or di-thiophosphate, magnesium alkyl phenol, magnesium sulfur-bound alkyl phenol compound, magnesium methylene bridged phenol, sodium phenate, sodium sulfur-containing phenate, sodium sulfonate, sodium calixarate, sodium salixarate, sodium salicylate, sodium carboxylic acid, sodium phosphate, sodium mono- and / or di-thiophosphate, sodium alkyl phenol, sodium sulfur-bound alkyl phenol compound, or sodium methylene bridged phenol.

[0105] Overbased detergent additives are well known in the art and can be alkali or alkaline earth metal overbased detergent additives. Such detergent additives can be prepared by reacting a metal oxide or metal hydroxide with a base material and carbon dioxide gas. The base material is typically an acid, such as an aliphatic-substituted sulfonic acid, aliphatic-substituted carboxylic acid, or aliphatic-substituted phenol.

[0106] The overbased detergent of the lubricating oil composition may have a total base number (TBN) of about 200 mg KOH / gram or greater, or, as a further example, about 250 mg KOH / gram or greater, or about 350 mg KOH / gram or greater, or about 375 mg KOH / gram or greater, or about 400 mg KOH / gram or greater.

[0107] Examples of suitable overbased detergents include, but are not limited to, overbased calcium phenates, overbased calcium sulfur-containing phenates, overbased calcium sulfonates, overbased calcium calixarates, overbased calcium salixarates, overbased calcium salicylates, overbased calcium carboxylic acids, overbased calcium phosphates, overbased calcium mono- and / or di-thiophosphates, overbased calcium alkylphenols, overbased calcium sulfur-bound alkylphenol compounds, overbased calcium methylene-bridged phenols, overbased magnesium phenates, overbased magnesium sulfonates, overbased magnesium calixarates, overbased magnesium salixarates, overbased magnesium salicylates, overbased magnesium carboxylic acids, overbased magnesium phosphates, overbased magnesium mono- and / or di-thiophosphates, overbased magnesium alkylphenols, overbased magnesium sulfur-bound alkylphenol compounds, or overbased magnesium methylene-bridged phenols.

[0108] The overbased calcium phenate detergents have a total base number of at least about 150 mg KOH / g, at least about 225 mg KOH / g, at least about 225 to about 400 mg KOH / g, at least about 225 to about 350 mg KOH / g, or about 230 to about 350 mg KOH / g, all measured by the method of ASTM D-2896. When such detergent compositions are formed in an inert diluent, such as a process oil, usually a mineral oil, the total base number reflects the basicity of the entire composition, including the diluent and any other materials (e.g., accelerators, etc.) that may be included in the detergent composition.

[0109] Overbased detergents may have a metal-to-substrate ratio of 1.1:1 or greater, or 2:1 or greater, or 4:1 or greater, or 5:1 or greater, or 7:1 or greater, or 10:1 or greater. In some embodiments, the detergent is effective in reducing or preventing rust in engines or other automotive components such as transmissions or gears. The detergent may be present in the lubricating composition from about 0 to about 10 wt. %, or from about 0.1 to about 8 wt. %, or from about 1 to about 4 wt. %, or from greater than about 4 wt. % to about 8 wt. %.

[0110] Extreme Pressure Agents: The lubricating oil compositions herein may also optionally contain one or more extreme pressure agents. Oil-soluble extreme pressure (EP) agents include sulfur and chlorosulfur-containing EP agents, chlorinated hydrocarbon EP agents, and phosphorus EP agents. Examples of such EP agents include chlorinated waxes; organic sulfides and polysulfides such as dibenzyl disulfide, bis(chlorobenzyl) disulfide, dibutyl tetrasulfide, sulfurized methyl ester of oleic acid, sulfurized alkylphenols, sulfurized dipentene, sulfurized terpene, and sulfurized Diels-Alder adducts; phosphorus sulfurized hydrocarbons such as the reaction products of phosphorus sulfide with turpentine or methyl oleate; dihydrocarbyl and trihydrocarbyl phosphites, for example, phosphate esters such as dibutyl phosphite, diheptyl phosphite, dicyclohexyl phosphite, pentyl phenyl phosphite; dipentyl phenyl phosphite, tridecyl phosphite, distearyl phosphite, and polypropylene-substituted phenyl phosphites; metal thiocarbamates such as zinc dioctyldithiocarbamate and barium heptylphenol diacid; amine salts of alkyl and dialkyl phosphates, including, for example, the amine salt of the reaction product of a dialkyl dithiophosphate with propylene oxide; and mixtures thereof.

[0111] Friction Modifiers: 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, but may include, but are not limited to, imidazolines, amides, amines, succinimides, alkoxylated amines, alkoxylated ether amines, amine oxides, amidoamines, nitriles, betaines, quaternary amines, imines, amine salts, aminoguanidines, alkanolamides, phosphonates, metal-containing compounds, glycerol esters, sulfurized fatty compounds and olefins, sunflower oil, other naturally occurring vegetable or animal oils, dicarboxylic acid esters, esters or partial esters of polyols with one or more aliphatic or aromatic carboxylic acids, and the like.

[0112] Suitable friction modifiers may contain hydrocarbyl groups selected from linear, branched, or aromatic hydrocarbyl groups, or mixtures thereof, and 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 about 12 to about 25 carbon atoms. In some embodiments, the friction modifier may be a long-chain fatty acid ester. In other embodiments, the long-chain fatty acid ester may be a mono-ester, a di-ester, 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.

[0113] Other suitable friction modifiers may include organic, ashless (metal-free), nitrogen-free organic friction modifiers. Such friction modifiers include esters formed by reacting carboxylic acids and anhydrides with alkanols, and generally may contain polar end groups (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 contain mono-, di-, and tri-esters of oleic acid. Other suitable friction modifiers are described in U.S. Patent No. 6,723,685, the entire contents of which are incorporated herein by reference.

[0114] Aminic friction modifiers may include amines or polyamines. Such compounds may have hydrocarbyl groups that are linear, saturated, unsaturated, or a mixture thereof, and may contain from about 12 to about 25 carbon atoms. Further examples of suitable friction modifiers include alkoxylated amines and alkoxylated ether amines. Such compounds may have hydrocarbyl groups that are linear, saturated, unsaturated, or a mixture thereof. They may contain from about 12 to about 25 carbon atoms. Examples include ethoxylated amines and ethoxylated ether amines.

[0115] The amines and amides may be used as such or in the form of adducts or reaction products with boron compounds such as boron oxide, boron halides, metaborates, boric acid, or mono-, di-, or tri-alkylborates. Other suitable friction modifiers are described in U.S. Patent No. 6,300,291, which is incorporated herein by reference in its entirety.

[0116] Friction modifiers may optionally be present in ranges such as from about 0 to about 10 weight percent, or from about 0.01 to about 8 weight percent, or from about 0.1 to about 4 weight percent.

[0117] Molybdenum-Containing Component: 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 antiwear agents, antioxidants, friction modifiers, or mixtures thereof. The oil-soluble molybdenum compounds may include molybdenum dithiocarbamates, molybdenum dialkyldithiophosphates, molybdenum dithiophosphinates, amine salts of molybdenum compounds, molybdenum xanthates, molybdenum thioxanthates, molybdenum sulfides, molybdenum carboxylates, molybdenum alkoxides, trinuclear organo-molybdenum compounds, and / or mixtures thereof. Molybdenum sulfides include molybdenum disulfide. The molybdenum disulfide may be in the form of a stable dispersion. In one embodiment, the oil-soluble molybdenum compounds may be selected from the group consisting of molybdenum dithiocarbamates, molybdenum dialkyldithiophosphates, amine salts of molybdenum compounds, and mixtures thereof. In one embodiment, the oil-soluble molybdenum compound can be a molybdenum dithiocarbamate.

[0118] Suitable examples of molybdenum compounds that can be used include commercially available materials sold under trade names such as Molyvan® 822™, Molyvan® A, Molyvan® 2000, and Molyvan® 855, and Molyvan® 1055 manufactured by R.T. Vanderbilt Co., Ltd., and Sakura-Lube™ S-165, S-200, S-300, S-310G, S-151, 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. No. 5,650,381, U.S. Reissue Pat. Nos. 37,363 (E1), 38,929 (E1), and 40,595 (E1), the entireties of which are incorporated herein by reference.

[0119] 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, MoOCl, MoOBr, MoOCl, molybdenum trioxide, or similar acidic molybdenum compounds. Alternatively, the composition can provide the molybdenum via molybdenum / sulfur complexes of basic nitrogen compounds, 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.

[0120] Another class of suitable organo-molybdenum compounds is trinuclear molybdenum compounds and mixtures thereof, such as compounds of the formula Mo3SkLnQz, where S represents sulfur, L represents an independently selected ligand whose organic group has 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. There may be at least 21 total carbon atoms among all of the ligand's organic groups, such as 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, incorporated herein by reference in its entirety.

[0121] The oil-soluble molybdenum compound may be present in an amount sufficient to provide from about 0.5 ppm to about 2000 ppm, from about 1 ppm to about 700 ppm, from about 1 ppm to about 550 ppm, from about 5 ppm to about 300 ppm, or from about 20 ppm to about 250 ppm of molybdenum.

[0122] Transition Metal-Containing Compound: In another embodiment, the oil-soluble compound may be a transition metal-containing compound or metalloid. Transition metals may include, but are not limited to, titanium, vanadium, copper, zinc, zirconium, molybdenum, tantalum, tungsten, etc. Suitable metalloids include, but are not limited to, boron, silicon, antimony, tellurium, etc.

[0123] In some embodiments, the oil-soluble transition metal-containing compound may function as an anti-wear agent, a friction modifier, an antioxidant, a deposit control additive, or two or more of these functions. In some embodiments, the oil-soluble transition metal-containing compound may be an oil-soluble titanium compound such as a titanium(IV) alkoxide. Among the titanium-containing compounds that may be used in or for preparing the oil-soluble material in the technology of the present disclosure are various Ti(IV) compounds such as titanium(IV) oxide; titanium(IV) sulfide; titanium(IV) nitrate; titanium(IV) alkoxides, such as titanium methoxide, titanium ethoxide, titanium propoxide, titanium isopropoxide, titanium butoxide, and titanium 2-ethylhexoxide; and other titanium compounds or complexes, such as, but not limited to, titanium phenate; titanium carboxylates, such as titanium(IV) 2-ethyl-1,3-hexanedioate, titanium citrate, or titanium oleate; and titanium(IV) (triethanolaminato)isopropoxide. Other forms of titanium encompassed by the disclosed technology include titanium phosphates, such as titanium dithiophosphates (e.g., dialkyldithiophosphates) and titanium sulfonates (e.g., alkylbenzene sulfonates), or generally reaction products of titanium compounds with various acidic substances to form salts, such as oil-soluble salts. Thus, titanium compounds can be derived from organic acids, alcohols, and glycols, among others. Ti compounds can also exist in dimeric or oligomeric forms containing Ti-O-Ti structures. Such titanium materials are commercially available or can be readily prepared by suitable synthetic techniques apparent to those skilled in the art. They can exist at room temperature as solids or liquids, depending on the particular compound. They can also be provided in solution form in a suitable inert solvent.

[0124] In one embodiment, titanium can be provided as a Ti-modified dispersant, such as a succinimide dispersant. Such materials can be prepared by forming a titanium mixed anhydride between a titanium alkoxide and a hydrocarbyl-substituted succinic anhydride, such as an alkenyl-(or alkyl) succinic anhydride. The resulting titanate-succinate intermediate can be used directly or reacted with any of several materials, such as (a) polyamine-based succinimide / amide dispersants having free condensable —NH functional groups; (b) components of polyamine-based succinimide / amide dispersants, i.e., alkenyl-(or alkyl) succinic anhydrides and polyamines; or (c) hydroxy-containing polyester dispersants prepared by reacting a substituted succinic anhydride with a polyol, aminoalcohol, polyamine, or mixtures thereof. Alternatively, the titanate-succinate intermediate can be reacted with other agents, such as alcohols, amino alcohols, ether alcohols, polyether alcohols or polyols, or fatty acids, and the product can be used directly to impart Ti to lubricants or further reacted with a succinic dispersant as described above. As an example, one part (mole) of tetraisopropyl titanate can be reacted with approximately two parts (mole) of polyisobutene-substituted succinic anhydride at 140-150°C for 5-6 hours to provide a titanium-modified dispersant or intermediate. The resulting material (30 g) can be further reacted with a succinimide dispersant from a polyisobutene-substituted succinic anhydride and polyethylene polyamine mixture (127 grams + diluent oil) at 150°C for 1.5 hours to produce a titanium-modified succinimide dispersant.

[0125] Another titanium-containing compound is titanium alkoxide and C6-C 25 The reaction product may be a reaction product with a carboxylic acid. The reaction product has the following formula:

[0126] [ka] wherein n is an integer selected from 2, 3, and 4, and R is a hydrocarbyl group containing from about 5 to about 24 carbon atoms, or may be represented by the following formula:

[0127] [ka] where m+n=4, n ranges from 1 to 3, R4 is an alkyl moiety having from 1 to 8 carbon atoms, R1 is selected from hydrocarbyl groups containing from about 6 to 25 carbon atoms, and R2 and R3 are the same or different and are selected from hydrocarbyl groups containing from 1 to 6 carbon atoms. Alternatively, the titanium compound may be represented by the following formula:

[0128] [ka] wherein x ranges from 0 to 3; R1 is selected from hydrocarbyl groups containing about 6 to 25 carbon atoms; R2 and R3 are the same or different and are selected from hydrocarbyl groups containing about 1 to 6 carbon atoms; R4 is H or a C6 to C6 25 The carboxylic acid moiety is selected from the group consisting of:

[0129] Suitable carboxylic acids may include, but are not limited to, caproic acid, caprylic acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachic acid, oleic acid, erucic acid, linoleic acid, linolenic acid, cyclohexanecarboxylic acid, phenylacetic acid, benzoic acid, neodecanoic acid, and the like.

[0130] In one embodiment, the oil-soluble titanium compound may be present in the lubricating oil composition in an amount to provide from about 0 to about 3000 ppm by weight of titanium, or from 25 to about 1500 ppm by weight of titanium, or from about 35 ppm to about 500 ppm by weight of titanium, or from about 50 ppm to about 300 ppm.

[0131] Viscosity Index Improvers: The lubricating oil compositions herein may also optionally contain one or more viscosity index improvers. Suitable viscosity index improvers 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. Viscosity index improvers may include star polymers, suitable examples of which are described in U.S. Patent Application Publication No. 2012 / 0101017(A1).

[0132] The 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 improver. Suitable viscosity index improvers may include functionalized polyolefins, such as ethylene-propylene copolymers functionalized with the reaction product of an acylating agent (such as maleic anhydride) and an amine, amine-functionalized polymethacrylates, or esterified maleic anhydride-styrene copolymers reacted with amines.

[0133] The total amount of viscosity index improver and / or dispersant viscosity index improver can be from about 0 to about 20 wt %, from about 0.1 to about 15 wt %, from about 0.1 to about 12 wt %, or from about 0.5 to about 10 wt % of the lubricating oil composition.

[0134] Other optional additives: Other additives may be selected to perform one or more functions required in a lubricating fluid. Furthermore, one or more of the aforementioned additives may be multifunctional and may provide functions in addition to or other than those described herein.

[0135] Lubricating oil compositions according to the present disclosure may optionally contain other performance additives. The other performance additives may be in addition to the specific additives of the present disclosure and / or may include one or more of metal deactivators, viscosity index improvers, detergents, ashless TBN boosters, friction modifiers, antiwear agents, corrosion inhibitors, rust inhibitors, dispersants, dispersant viscosity index improvers, extreme pressure agents, antioxidants, foam suppressants, demulsifiers, emulsifiers, pour point depressants, seal swell agents, and mixtures thereof. Typically, fully formulated lubricating oils will contain one or more of these performance additives.

[0136] Suitable metal deactivators may include derivatives of benzotriazole (typically tolyltriazole), dimercaptothiadiazole derivatives, 1,2,4-triazole, benzimidazole, 2-alkyldithiobenzimidazole, or 2-alkyldithiobenzothiazole; foam suppressors including copolymers of ethyl acrylate, 2-ethylhexyl acrylate, and optionally vinyl acetate; demulsifiers including trialkyl phosphate, polyethylene glycol, polyethylene oxide, polypropylene oxide, and (ethylene oxide-propylene oxide) polymers; pour point depressants including esters of maleic anhydride-styrene, polymethacrylate, polyacrylate, or polyacrylamide.

[0137] Suitable suds suppressors include silicon-based compounds such as siloxanes.

[0138] Suitable pour point depressants may include polymethyl methacrylate or mixtures thereof. The pour point depressant may be present in an amount sufficient to provide from about 0 wt % to about 1 wt %, from about 0.01 wt % to about 0.5 wt %, or from about 0.02 wt % to about 0.04 wt %, based on the final weight of the lubricating oil composition.

[0139] Suitable rust inhibitors can be a single compound or a mixture of compounds that have the property of inhibiting corrosion of ferrous metal surfaces. Non-limiting examples of rust inhibitors useful herein include oil-soluble high molecular weight organic acids such as 2-ethylhexanoic acid, lauric acid, myristic acid, palmitic acid, oleic acid, linoleic acid, linolenic acid, behenic acid, and cerotic acid, as well as oil-soluble polycarboxylic acids, including dimer and trimer acids such as those produced from tall oil fatty acid, oleic acid, and linoleic acid. Other suitable corrosion inhibitors include long-chain alpha- and omega-dicarboxylic acids in the molecular weight range of about 600 to about 3000, and alkenyl succinic acids in which the alkenyl group contains about 10 or more carbon atoms, such as tetrapropenyl succinic acid, tetradecenyl succinic acid, and hexadecenyl succinic acid. Another useful type of acidic corrosion inhibitor is the half ester of an alkenyl succinic acid having about 8 to about 24 carbon atoms in the alkenyl group with an alcohol, such as a polyglycol. The corresponding half amides of such alkenyl succinic acids are also useful. Useful rust inhibitors are high molecular weight organic acids.

[0140] When present, the rust inhibitor may be used in an amount sufficient to provide from about 0 to about 5 wt. %, from about 0.01 to about 3 wt. %, from about 0.1 to about 2 wt. %, based on the final weight of the lubricating oil composition.

[0141] Generally speaking, suitable lubricants containing the neutral to overbased sulfurized alkylphenate products herein may contain additive components in the ranges listed in the table below.

[0142] [Table 2]

[0143] The percentages of each component above represent the weight percent of each component based on the weight of the final lubricating oil composition. The remainder of the lubricating oil composition consists of one or more base oils. 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 blend all of the components simultaneously using an additive concentrate (i.e., additives plus a diluent such as a hydrocarbon solvent). Fully formulated lubricants conventionally contain an additive package, referred to herein as a dispersant / inhibitor package or DI package, that supplies the properties required in the formulation.

[0144] The lubricants herein are configured for use in various types of lubricants, such as automotive lubricants and / or greases, internal combustion engine oils, hybrid engine oils, electric engine lubricants, drivetrain lubricants, transmission lubricants, gear oils, hydraulic lubricants, tractor hydraulic fluids, metal working fluids, turbine engine lubricants, stationary engine lubricants, tractor lubricants, motorcycle lubricants, power steering fluids, clutch fluids, axle fluids, wet brake fluids, and the like. 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 blended diesel / biofuel-fueled engine, a blended gasoline / biofuel-fueled engine, an alcohol-fueled engine, a blended 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 electric or battery power sources. Engines configured in this manner are commonly 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, and engines for motorcycles, automobiles, locomotives, and trucks. The engine may be coupled with a turbocharger.

[0145] The lubricating oil composition for internal combustion engines may be suitable for any engine lubricant, regardless of sulfur, phosphorus, or ash content, calculated as sulfated ash (ASTM D-874) content. The sulfur content of the engine oil lubricant may be about 1 wt. % or less, or about 0.8 wt. % or less, or about 0.5 wt. % or less, or about 0.3 wt. % or less, or about 0.2 wt. % or less. In one embodiment, the sulfur content may range from about 0.001 wt. % to about 0.5 wt. % or about 0.01 wt. % to about 0.3 wt. %. The phosphorus content may be about 0.2 wt. % or less, or about 0.1 wt. % or less, or about 0.085 wt. % or less, or about 0.08 wt. % or less, or even about 0.06 wt. % or less, about 0.055 wt. % or less, or about 0.05 wt. % or less. In one embodiment, the phosphorus content may be about 50 ppm to about 1000 ppm, or about 325 ppm to about 850 ppm. The total sulfated ash content may 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 sulfated ash content may be about 0.05% by weight to about 0.9% by weight, or 0.1% by weight or about 0.2% by weight to about 0.45% by weight. In another embodiment, the sulfur content may be about 0.4% by weight or less, the phosphorus content may be about 0.08% by weight or less, and the sulfated ash content may be about 1% by weight or less. In yet another embodiment, the sulfur content may be about 0.3% by weight or less, the phosphorus content may be about 0.05% by weight or less, and the sulfated ash content may be about 0.8% by weight or less.

[0146] Additionally, the lubricants herein may meet one or more industry specification requirements such as ILSAC GF-3, GF-4, GF-5, GF-6, PC-11, CF, CF-4, CH-4, CK-4, FA-4, CJ-4, CI-4 Plus, CI-4, API SG, SJ, SL, SM, SN, SN PLUS, 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, Mid SAPS, or Dexos1™, Dexos2™, MB-Approval, etc. 229.1, 229.3, 229.5, 229.51 / 229.31, 229.52, 229.6, 229.71, 226.5, 226.51, 228.0 / .1, 228.2 / .3, 228.31, 228.5, 228.51, 228.61, VW 501.01, 502.00, 503.00 / 503.01, 504.00, 505.00, 505.01, 506.00 / 506.01, 507.00, 508.00, 509.00, 508.88, 509.99, BMW Longlife-01, Longlife-01 FE, Longlife-04, Longlife-12 FE, Longlife-14 FE+, Longlife-17 FE+, Porsche A40, C30, Peugeot Citroen Automobiles B71 2290, B71 2294, B71 2295, B71 2296, B71 2297, B71 2300, B71 2302, B71 2312, B71 2007, B71 2008, Renault RN0700, RN0710, RN0720, Ford WSS-M2C153-H, WSS-M2C930-A, WSS-M2C945-A, WSS-M2C913A, WSS-M2C913-B, WSS-M2C913-C, WSS-M2C913-D, WSS-M2C948-B, WSS-M2C948-A, GM 6094-M, Chrysler MS-6395, Fiat 9.55535 G1, G2, M2, N1, N2, Z2, S1, S2, S3, S4, T2, DS1, DSX, GH2, GS1, GSX, CR1, Jaguar Land Rover STJLR.03.5003, STJLR.03.The composition may be suitable to meet original equipment manufacturer specifications, such as STJLR.5004, STJLR.03.5005, STJLR.03.5006, STJLR.03.5007, STJLR.51.5122, or past or future PCMO or HDD specifications not listed 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.

[0147] In one embodiment, the lubricating oil composition is an engine oil, and the lubricating oil composition may have (i) a sulfur content of less than or equal to about 0.5 wt. %, (ii) a phosphorus content of less than or equal to about 0.1 wt. %, and (iii) an ash content, calculated as a sulfated ash content of less than or equal to about 1.5 wt. %.

[0148] In one embodiment, the lubricating oil composition is suitable for a two-stroke or four-stroke marine diesel internal combustion engine. In one embodiment, the marine diesel combustion engine is a two-stroke engine. In some embodiments, the lubricating oil composition is not suitable for a two-stroke or four-stroke marine diesel internal combustion engine for one or more reasons, including, but not limited to, the high sulfur content of fuels used to power marine engines and the high TBN required for engine oils suitable for marine use (e.g., greater than about 40 TBN for engine oils suitable for marine use).

[0149] In some embodiments, the lubricating oil compositions are suitable for use in engines powered by low sulfur fuels, such as fuels containing about 1 to about 5% sulfur. Highway vehicle fuels contain about 15 ppm sulfur (or about 0.0015% sulfur). [Example]

[0150] 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. It is intended that these examples are presented for illustrative purposes only and are not intended to limit the scope of the invention disclosed herein.

[0151] Comparative Example 1 Comparative lubricating composition C1 was evaluated for high temperature deposits using ASTM 6335. Table 2 below shows the detergent and antiwear systems contained in the comparative lubricating composition formulated into a finished lubricant that also contains a dispersant, an antioxidant, an organo-molybdenum additive, an antifoam additive, a friction modifier, an olefin copolymer viscosity modifier, a pour point depressant, a process oil, and a base oil.

[0152] [Table 3]

[0153] In the detergent system of Table 2, the calcium sulfonate had a TBN of about 300 and about 11.9 weight percent calcium, and the magnesium sulfonate had a TBN of about 400 and about 9.6 weight percent magnesium. In the antiwear system, ZDDP A was a zinc dialkyldithiophosphate containing alkyl groups derived from methyl isobutyl carbinol and about 7 weight percent phosphorus, about 14.8 weight percent sulfur, and about 7.8 weight percent zinc. ZDDP B was also a zinc dialkyldithiophosphate but contained alkyl groups derived from ethylhexyl alcohol and about 6 weight percent phosphorus, about 13 weight percent sulfur, and about 6.8 weight percent zinc. This comparative lubricating composition exhibited passing high-temperature deposits (TOEST-33C) of less than about 30 mg, but had a relatively high calculated SASH of 0.8 weight percent.

[0154] The calculated sulfated ash (SASH) for Table 2 above was determined as follows: Comparative Example 1 (CE-1) contained 59 ppmw boron, 1392 ppmw calcium, 371 ppmw magnesium, 50 ppmw molybdenum, and 696 ppmw zinc. To determine the amount of SASH present in CE-1, the following calculation was performed: 59 ppmw of boron x 3.22 = 189.98 1392 ppmw of calcium x 3.4 = 4732.8 371 ppmw of magnesium x 4.95 = 1836.5 50 ppmw of boron x 1.5 = 75 696 ppmw zinc x 1.5 = 1044 (189.98 + 4732.8 + 1836.5 + 75 + 1044) / 10000 = 0.79 weight percent SASH All sulfated ash (SASH) values ​​given in this application were determined using this calculation method.

[0155] Comparative Example 2 To reduce the amount of ash, comparative lubricating compositions were prepared using lower levels of detergent additives to provide lower levels of total metals. Table 3 below shows the detergent and antiwear systems contained in these additional comparative lubricating compositions, which were formulated into finished lubricants containing the same amounts and the same dispersants, antioxidants, organo-molybdenum additives, antifoam additives, friction modifiers, olefin copolymer viscosity modifiers, pour point depressants, process oils, and base oils as the comparative lubricating compositions from Table 2 of Example 1. The detergent and antiwear additives were the same as those described in Example 1.

[0156] [Table 4]

[0157] As shown above in Table 3, calculated sulfated ash was lower for Comparative Samples C2-C4 when the detergent level was reduced, but total high temperature deposits increased to an unacceptable level of approximately 30 mg. These Comparative Samples had phosphorus-to-lubricant TBN ratios of 172 to 635 and phosphorus-to-total detergent metal ratios of 0.55 to 3.87.

[0158] Example 1 Lubricating compositions of the present invention were prepared with lower levels of ash and lower high-temperature deposits by selecting the unique relationships of phosphorus, metals, and TBN as described herein. Table 4 below shows the detergent and antiwear systems contained in these inventive lubricating compositions, which were formulated into finished lubricants containing the same amounts and the same dispersants, antioxidants, organo-molybdenum additives, antifoam additives, friction modifiers, olefin copolymer viscosity modifiers, pour point depressants, process oils, and base oils as the comparative lubricating compositions from Table 2 of Example 1. The detergent and antiwear additives were the same as those described in Example 1.

[0159] [Table 5]

[0160] Inventive Samples I-1 through I-3 demonstrated lower levels of ash, calculated as sulfated ash, and acceptable levels of high-temperature deposits. These inventive samples had phosphorus-to-lubricant TBN ratios of from about 13 to about 89 and phosphorus-to-total detergent metals ratios of from about 0.04 to about 0.3.

[0161] Example 2 Additionally, the lubricating compositions of the present invention were prepared with lower ash levels by reducing the amounts of both the detergent and antiwear components, and had the described relationships of phosphorus, metals, and TBN. Table 5 below shows the detergent and antiwear systems contained in these lubricating compositions of the present invention, which were formulated into finished lubricants containing the same amounts and the same dispersants, antioxidants, organo-molybdenum additives, antifoam additives, friction modifiers, olefin copolymer viscosity modifiers, pour point depressants, process oils, and base oils of the comparative lubricating compositions from Table 2 of Example 1. The detergent and antiwear additives were the same as those described in Example 1.

[0162] [Table 6]

[0163] Inventive Samples I-4 to I-6 demonstrated lower levels of ash, calculated as sulfated ash, and acceptable levels of high-temperature deposits. These inventive samples had phosphorus-to-lubricant TBN ratios of about 63 to about 120 and phosphorus-to-total detergent metals ratios of about 0.34 to about 0.38.

[0164] The graph in Figure 2 shows the phosphorus to lubricant TBN ratio for high temperature deposits for the inventive and comparative samples in Comparative Example 2 and Inventive Examples 1 and 2. The graph in Figure 1 shows the phosphorus to total detergent metal ratio for high temperature deposits for the inventive and comparative samples in Comparative Example 2 and Inventive Examples 1 and 2. Finally, the graph in Figure 3 shows that the calculated levels of sulfated ash per se do not affect high temperature deposits, but only through the selectivity ratios shown in Figures 1 and 2 does low ash formation achieve passing high temperature deposits.

[0165] It should be noted that, as used in this specification and 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 "comprises" and grammatical variations thereof are intended to be open-ended such that the recitation of items in a list does not exclude other similar items that may be substituted for or added to the listed items.

[0166] 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 as being modified in all instances by the term "about." Accordingly, unless indicated to the contrary, the numerical parameters set forth in the following specification and appended claims are approximations that may vary depending upon the desired properties sought to be obtained by the present disclosure. At the very least, and not as an attempt to limit the application of the doctrine of equivalents to the 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.

[0167] 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.

[0168] 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 number of significant digits. Thus, for example, a range of 1 to 4 should be construed as an explicit disclosure of not only the values ​​1, 2, 3, and 4, but also any range of such values.

[0169] It should be 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 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. It is further understood that any range between the endpoints within a broad range is also contemplated herein. Thus, a range of 1 to 4 also means ranges of 1 to 3, 1 to 2, 2 to 4, 2 to 3, etc.

[0170] 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 or specific amount / value in a range for the same component, compound, substituent, or parameter disclosed elsewhere in this application to form a range for that component, compound, substituent, or parameter.

[0171] While particular embodiments have been described, alternatives, modifications, variations, improvements, and substantial equivalents may occur that are not presently anticipated or presently unforeseeable to Applicants or others skilled in the art. Accordingly, the appended claims as filed, and the appended claims as they may be amended, are intended to cover all such alternatives, modifications, variations, improvements, and substantial equivalents.

[0172] The following examples illustrate, but do not limit, the methods and compositions of the present disclosure. Other suitable modifications and adaptations of the variety of 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 by reference in their entirety. Examples 1-6 illustrate different lubricating compositions containing viscosity index improvers containing ethylene and propylene units reacted with a macromonomer alcohol, and methods for making them.

Claims

1. 1. A low ash lubricating composition for reducing high temperature deposits, comprising: one or more base oils of lubricating viscosity; a detergent system providing an amount of a metal to the lubricating composition, the metal being at least one of sodium, calcium, magnesium, or a combination thereof, the detergent system comprising 55 to 75 weight percent of a detergent additive providing calcium and 25 to 45 weight percent of a detergent additive providing magnesium, the detergent system providing 10 to 1500 ppm of calcium and 10 to 500 ppm of magnesium; an antiwear system comprising one or more metal dialkyldithiophosphates derived from one of a primary alcohol, a secondary alcohol, or a combination thereof, and providing an amount of phosphorus to the lubricating composition; the lubricating composition contains 50 to 800 ppm phosphorus from the antiwear system; the ratio of phosphorus (ppm) from the antiwear system to the amount of metal (ppm) from the detergent system is 0.02 to 0.5; the lubricating composition comprises a total amount of metals such that the composition has a calculated sulfated ash content of greater than or equal to 0.1 weight percent and less than 0.8 weight percent; A low ash lubricating composition having less than 30 mg of deposits when the lubricating composition is subjected to the ASTM D6335 High Temperature Deposit Formation Test.

2. 2. The lubricating composition of claim 1, wherein the antiwear system provides 50 to 850 ppm of zinc to the lubricating composition, and the amount of zinc (ppm) from the antiwear system to the total metals (ppm) from the detergent system is less than or equal to 0.

6.

3. 2. The lubricating composition of claim 1, wherein the ratio of the phosphorus (ppm) from the antiwear system to the TBN is less than or equal to 120 and / or the ratio of the phosphorus (ppm) from the antiwear system to the amount of the metal (ppm) from the detergent system is less than or equal to 0.

5.

4. 10. The lubricating composition of claim 1, wherein the lubricating composition contains no more than 1800 ppm of metals from the detergent system.

5. 10. The lubricating composition of claim 1, wherein the antiwear agent system comprises two metal dialkyldithiophosphates, and / or a first zinc dialkyldithiophosphate is derived from a primary alcohol and a second zinc dialkyldithiophosphate is derived from a secondary alcohol.

6. 6. The lubricating composition of claim 5, wherein the antiwear system comprises a majority of the second zinc dialkyldithiophosphate derived from a secondary alcohol, and / or the antiwear system comprises 20 to 30 weight percent of the first zinc dialkyldithiophosphate derived from a primary alcohol and 70 to 80 weight percent of the second zinc dialkyldithiophosphate derived from a secondary alcohol.

7. 2. The lubricating composition of claim 1, wherein the detergent system comprises a calcium sulfonate, calcium phenate, or combination thereof having a total base number of 200 to 500, and / or the detergent system comprises a magnesium sulfonate, magnesium phenate, or combination thereof having a total base number of 200 to 500, and / or the lubricating composition has a total base number of less than 10.

8. 2. The lubricating composition of claim 1, further comprising an amount of zinc provided by the antiwear system, wherein the amount (ppm) of zinc from the antiwear system to the amount (ppm) of total metals from the detergent system is less than or equal to 0.6, and / or the antiwear system provides 50 to 850 ppm of zinc to the lubricating composition.

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