Lubricating composition for reduced high temperature deposits

Abstract

The present disclosure describes blends of detergent and antiwear lubricating additives and lubricants, including such additive blends that are effective in reducing high temperature deposits, and particularly high temperature deposits in low ash compositions.

Description

Technical Field

[0001] The present disclosure relates to additive systems and lubricating compositions, including additive systems configured for reduced high temperature deposits, and in particular lubricating compositions capable of achieving reduced high temperature deposits in low ash formulations. Background Art

[0002] Automobile manufacturers continue to push for improved efficiency and fuel economy, and therefore, the demand for engines, lubricants and their components continues to increase. Today's passenger car engines are usually smaller, lighter and more efficient, and their technology is designed to improve fuel economy, performance and power. These requirements also mean that engine oil performance must be developed to meet the higher demands of such modern engines and their corresponding performance standards related to their unique uses and applications. Due to this stringent requirement for engine oils, lubricant manufacturers usually customize lubricants and their additives to meet certain performance requirements of each unique application.

[0003] For example, the Thermal Oxidation Engine Oil Simulation Test (TEOST-33C) was developed as a lubricant test to evaluate turbocharger coking properties. In this test, the amount of deposits that appear on a test piece, i.e., a deposition rod, is measured when the test lubricant passes through a deposition rod and is heated to about 200° C. to about 500° C. The test was designed in part to predict the high temperature deposit formation tendency of an engine oil when subjected to the increased oxidative stress of a turbocharger and has been an integral part of the API and ILSAC standards for many years.

[0004] Lubricant specifications often include compositional restrictions in terms of permitted levels of sulfated ash, phosphorus and sulfur (so-called SAPS restrictions), and maintaining such restrictions while still meeting the increased demands of the latest lubricant standards is often challenging. For example, for environmental reasons, exhaust gas aftertreatment devices are often fitted to vehicles in order to reduce particulate matter and other various emissions. However, the sulfated ash, sulfur and / or phosphorus concentrations of lubricating oil compositions conventionally used in internal combustion engines may have an adverse effect on such aftertreatment devices, and lubricants are often formulated to minimize sulfated ash, phosphorus and sulfur therein.

[0005] Sulfated ash is a measure of the total weight percentage of ash in a lubricating oil composition. Sulfated ash measurements of lubricating oil compositions are related to the total metal content therein and can be conveniently measured according to ASTM D-874 and / or other commonly used evaluation methods known in the art and as described herein. However, in many cases, changing one component within a lubricating oil composition to improve certain performance characteristics tends to adversely affect one or more other performance characteristics. For example, the main source of ash in a lubricating oil composition is typically a metal detergent additive and / or an anti-wear additive. However, it has been found that reducing the amount of detergent or anti-wear components to reduce the sulfated ash content tends to negatively affect other performance characteristics, and in particular, for example, in the high temperature performance test of TEOST-33C, reduced detergents and / or anti-wear tend to increase deposits. Summary of the invention

[0006] In one method or embodiment, a lubricating composition for reducing high temperature deposits is provided. In one aspect, the lubricating composition comprises one or more base oils of lubricating viscosity; a detergent system that provides an amount of metal to the lubricating composition, wherein the metal is at least one of sodium, calcium, magnesium, or a combination thereof; an antiwear system that comprises one or more metal dialkyl dithiophosphates derived from one of a primary alcohol, a secondary alcohol, or a combination thereof, and provides an amount of phosphorus to the lubricating composition; wherein the total base number (TBN) of the lubricating composition is from about 0.5 to about 20; and wherein the amount of phosphorus from the antiwear system is about 150 or less relative to the TBN of the lubricating composition.

[0007] In other methods, the lubricating composition of the previous paragraph may include optional features or embodiments. These optional features or embodiments may include one or more of the following items in any combination: wherein the amount of phosphorus from the antiwear system is about 120 or less relative to the TBN; and / or wherein the lubricating composition contains no more than about 800 ppm of phosphorus from the antiwear system; and / or wherein the lubricating composition contains no more than about 1800 ppm of metal from the detergent system; and / or wherein the amount of phosphorus from the antiwear system is about 0.5 or less relative to the amount of metal from the detergent system; and / or wherein relative to the lubricant TBN, the amount of phosphorus from the antiwear system is effective so that when subjected to ASTM The lubricating composition comprises no more than about 0.8 wt % calculated sulfated ash and less than about 30 mg of sediment when tested for high temperature deposit formation according to D6335; and / or wherein the detergent system comprises about 55 wt % to about 75 wt % of a detergent additive providing calcium and about 25 wt % to about 45 wt % of a detergent additive providing magnesium; and / or wherein the detergent system provides about 10 ppm to about 1500 ppm of calcium and about 10 ppm to about 500 ppm of magnesium; and / or wherein the antiwear system comprises two metal dialkyl dithiophosphates; and / or wherein the antiwear system comprises two zinc dialkyl thiophosphates, and wherein the first zinc dialkyl dithiophosphate is derived from a primary alcohol and the second zinc dialkyl dithiophosphate is derived from a secondary alcohol; and / or wherein the antiwear system comprises a majority of the second zinc dialkyl dithiophosphate derived from a secondary alcohol; and / or wherein the antiwear system % to about 80 wt % of the second dialkyl dithiophosphate; and / or wherein the detergent system comprises calcium sulfonate, calcium phenate, or a combination thereof having a total base number of 200 to 500; and / or wherein the detergent system comprises magnesium sulfonate, magnesium phenate, or a combination thereof having a total base number of 200 to about 500; and / or wherein the total base number of the lubricating composition is less than about 10; and / or the lubricating composition further comprises an amount of zinc provided by the antiwear system, and wherein the amount of zinc from the antiwear system is about 0.6 or less relative to the amount of total metals from the detergent system; and / or wherein the antiwear system provides about 50 ppm to about 850 ppm of zinc to the lubricating composition; and / or wherein the lubricating composition is a passenger car motor oil.

[0008] In another method or embodiment, a low-ash lubricating composition for reducing high-temperature deposits is provided herein. In various aspects, the low-ash lubricating composition comprises one or more base oils of lubricating viscosity; a detergent system that provides an amount of metal to the lubricating composition, wherein the metal is at least one of sodium, calcium, magnesium, or a combination thereof; an antiwear system that comprises one or more metal dialkyl dithiophosphates derived from one of a primary alcohol, a secondary alcohol, or a combination thereof, and provides an amount of phosphorus to the lubricating composition; and wherein the amount of phosphorus from the antiwear system is about 0.5 or less relative to the amount of metal from the detergent system.

[0009] The low-ash lubricating composition of the previous paragraph may also include one or more optional features or embodiments. These optional features or embodiments may include one or more of the following items in any combination: wherein the lubricating composition comprises no more than about 800 ppm of phosphorus from the antiwear system and no more than about 1800 ppm of metal from the detergent system; and / or wherein the amount of phosphorus from the antiwear system is about 120 or less relative to the TBN; and / or wherein the amount of phosphorus from the antiwear system is effective relative to the lubricant TBN so that when subjected to ASTM The lubricating composition comprises no more than about 0.8 wt % calculated sulfated ash and less than about 30 mg of sediment when tested for high temperature deposit formation according to D6335; and / or wherein the detergent system comprises about 55 wt % to about 75 wt % of a detergent additive providing calcium and about 25 wt % to about 45 wt % of a detergent additive providing magnesium; and / or wherein the detergent system provides about 10 ppm to about 1500 ppm of calcium and about 10 ppm to about 500 ppm of magnesium; and / or wherein the antiwear system comprises two metal dialkyl dithiophosphates; and / or wherein the antiwear system comprises two zinc dialkyl thiophosphates, and wherein the first zinc dialkyl dithiophosphate is derived from a primary alcohol and the second zinc dialkyl dithiophosphate is derived from a secondary alcohol; and / or wherein the antiwear system comprises a majority of the second zinc dialkyl dithiophosphate derived from a secondary alcohol; and / or wherein the antiwear system % to about 80 wt % of the second dialkyl dithiophosphate; and / or wherein the detergent system comprises calcium sulfonate, calcium phenate, or a combination thereof having a total base number of 200 to 500; and / or wherein the detergent system comprises magnesium sulfonate, magnesium phenate, or a combination thereof having a total base number of 200 to about 500; and / or wherein the total base number of the lubricating composition is less than about 10; and / or the lubricating composition further comprises an amount of zinc provided by the antiwear system, and wherein the amount of zinc from the antiwear system is about 0.6 or less relative to the amount of total metals from the detergent system; and / or wherein the antiwear system provides about 50 ppm to about 850 ppm of zinc to the lubricating composition; and / or wherein the lubricating composition is a passenger car motor oil.

[0010] In yet another method or embodiment, a method of lubricating an engine with a lubricating composition that meets the API SP / ILSAC GF-6 standard. In various aspects, the method includes lubricating the engine with a lubricating composition, the lubricating composition comprising one or more base oils of lubricating viscosity; a detergent system, the detergent system providing a certain amount of metal to the lubricating composition, wherein the metal is at least one of sodium, calcium, magnesium, or a combination thereof; an antiwear system, the antiwear system comprising one or more metal dialkyl dithiophosphates derived from one of a primary alcohol, a secondary alcohol, or a combination thereof, and providing a certain amount of phosphorus to the lubricating composition; wherein the total base number (TBN) of the lubricating composition is from about 0.5 to about 20; and wherein the certain amount of phosphorus from the antiwear system is about 150 or less relative to the TBN of the lubricating composition; and wherein when subjected to the high temperature deposit formation test of ASTM D6335, the lubricating composition has a calculated sulfated ash of no more than about 0.8 weight percent and less than about 30 mg of sediment.

[0011] In other methods or embodiments, the method of the preceding paragraph may include any combination of optional features, embodiments or method steps. These optional features, embodiments or steps may include one or more of the following: wherein the lubricating composition comprises no more than about 800 ppm of phosphorus from the antiwear system; and / or wherein the lubricating composition comprises no more than about 1800 ppm of total metals from the detergent system; wherein the detergent system provides about 10 ppm to about 1500 ppm of calcium and about 10 ppm to about 500 ppm of magnesium; and / or wherein the total base number of the lubricating composition is less than about 10; and / or wherein the antiwear system provides about 50 ppm to about 850 ppm of zinc to the lubricating composition, and wherein a certain amount of zinc from the antiwear system is about 0.6 or less relative to a certain amount of total metals from the detergent system; and / or wherein the certain amount of phosphorus from the antiwear system is about 120 or less relative to the TBN; and / or wherein the certain amount of phosphorus from the antiwear system is effective relative to the lubricant TBN so that when subjected to ASTM The lubricating composition comprises no more than about 0.8 wt % calculated sulfated ash and less than about 30 mg of sediment when tested for high temperature deposit formation according to D6335; and / or wherein the detergent system comprises about 55 wt % to about 75 wt % of a detergent additive providing calcium and about 25 wt % to about 45 wt % of a detergent additive providing magnesium; and / or wherein the detergent system provides about 10 ppm to about 1500 ppm of calcium and about 10 ppm to about 500 ppm of magnesium; and / or wherein the antiwear system comprises two metal dialkyl dithiophosphates; and / or wherein the antiwear system comprises two zinc dialkyl thiophosphates, and wherein the first zinc dialkyl dithiophosphate is derived from a primary alcohol and the second zinc dialkyl dithiophosphate is derived from a secondary alcohol; and / or wherein the antiwear system comprises a majority of the second zinc dialkyl dithiophosphate derived from a secondary alcohol; and / or wherein the antiwear system % to about 80 wt % of the second dialkyl dithiophosphate; and / or wherein the detergent system comprises calcium sulfonate, calcium phenate, or a combination thereof having a total base number of 200 to 500; and / or wherein the detergent system comprises magnesium sulfonate, magnesium phenate, or a combination thereof having a total base number of 200 to about 500; and / or wherein the total base number of the lubricating composition is less than about 10; and / or the lubricating composition further comprises an amount of zinc provided by the antiwear system, and wherein the amount of zinc from the antiwear system is about 0.6 or less relative to the amount of total metals from the detergent system; and / or wherein the antiwear system provides about 50 ppm to about 850 ppm of zinc to the lubricating composition; and / or wherein the lubricating composition is a passenger car motor oil.

[0012] In another method or embodiment, there is provided use of any embodiment of the lubricating composition of this disclosure to achieve less than 30 mg of deposit when subjected to the high temperature deposit formation test of ASTM D6335.

[0013] In other embodiments herein, any embodiment of the uses, methods or compositions herein may have a calculated sulfated ash (SASH) of less than about 0.8 wt%, less than about 0.75 wt%, less than about 0.7 wt%, less than about 0.6 wt%, less than about 0.5 wt%, less than about 0.4 wt%, less than about 0.3 wt%, or even less than about 0.2 wt%, calculated by the method set forth below.

[0014] Other embodiments of the disclosure will be apparent to those skilled in the art from consideration of the specification and practice of the invention disclosed herein.The following term definitions are provided to clarify the meaning of certain terms as used herein.

[0015] The terms "oil composition", "lubricating composition", "lubricating oil composition", "lubricating oil", "lubricating 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 fully interchangeable synonymous terms referring to a finished lubricating product comprising a major base oil plus a minor 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," "motor oil concentrate" are considered to be fully interchangeable synonymous terms and refer to that portion of a lubricating oil composition that excludes the bulk 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" relates to metal salts, such as metal salts of sulfonates, carboxylates, salicylates and / or phenolates, in which the content of the metal exceeds the stoichiometric amount. Such salts may have a conversion level exceeding 100% (i.e., they may contain more than 100% of the theoretical amount of metal required to convert the acid into its "normal", "neutral" salt). The expression "metal ratio" is usually abbreviated as MR, which is used to represent the ratio of the total chemical equivalents of the metal in the overbased salt to the chemical equivalents of the metal in the neutral salt, based on known chemical reactivity and stoichiometry. In normal or neutral salts, the metal ratio is one, while in overbased salts, MR is greater than one. They are often referred to as overbased, superbased or superbasic salts, and may be salts of organic sulfuric acid, carboxylic acid, salicylic acid, sulfonic acid and / or phenol.

[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, which is well known to those skilled in the art. Specifically, it refers to a group having a carbon atom directly attached to the rest of the molecule and having predominantly hydrocarbon character. Each hydrocarbyl group is independently selected from a hydrocarbon substituent and a hydrocarbon substituent containing one or more halogen groups, hydroxyl groups, alkoxy groups, mercapto groups, nitro groups, nitroso groups, amino groups, pyridyl groups, furanyl groups, imidazolyl groups, oxygen and nitrogen substitutions, and wherein there are no more than two non-hydrocarbon substituents for every ten carbon atoms in the hydrocarbyl group.

[0020] As used herein, the term "alkylene substituent" or "alkylene group" is used in its ordinary sense, which 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 at two positions in the molecule through carbon atoms and has predominantly hydrocarbon characteristics. Each alkylene group is independently selected from a divalent hydrocarbon substituent, and a substituted divalent hydrocarbon substituent containing the following: a halo group, an alkyl group, an aryl group, an alkaryl group, an aralkyl group, a hydroxyl group, an alkoxy group, a thiol group, a nitro group, a nitroso group, an amino group, a pyridyl group, a furyl group, an imidazolyl group, oxygen and nitrogen, and wherein there are no more than two non-hydrocarbon substituents for every ten carbon atoms in the alkylene group.

[0021] Unless expressly stated otherwise, as used herein, the term "percent by weight" refers to the percentage of the component by weight of the entire composition.

[0022] As used herein, unless expressly stated otherwise, the term "ppmw" means parts per million on a weight basis.

[0023] The terms "soluble", "oil-soluble" or "dispersible" as used herein may, but do not necessarily, mean that the compound or additive is soluble, dissolvable, miscible or capable of being suspended in oil in all proportions. However, the aforementioned terms do mean that they are, for example, soluble, suspendable, dissolvable or stably dispersible in oil to a sufficient extent to exert their intended effect in the environment in which the oil is employed. In addition, if desired, the additional incorporation of other additives may also allow the incorporation of higher levels of a particular additive.

[0024] As used herein, the term "TBN" is used to denote Total Base Number in mg KOH / g as measured by the method of ASTM D2896.

[0025] As used herein, the term "alkyl" refers to a straight chain, branched chain, cyclic and / or substituted saturated chain portion having from about 1 to about 100 carbon atoms. As used herein, the term "alkenyl" refers to a straight chain, branched chain, cyclic and / or substituted unsaturated chain portion having from about 3 to about 10 carbon atoms, and as used herein, the term "aryl" refers to monocyclic and polycyclic aromatic compounds, which may include alkyl, alkenyl, alkaryl, amino, hydroxyl, alkoxy, halogen 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 with, for example, boron, phosphorus, and / or maleic anhydride, and may refer to a dispersant in which a primary and / or secondary amine is 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 US 5,241,003, which is incorporated herein by reference. In contrast, a "non-post-reacted" or "non-post-treated" component has not been subjected to such further processing, reaction, and / or treatment, and in the case of a dispersant, includes an amount of a primary and / or secondary amine.

[0027] The molecular weight of any embodiment herein can be measured using an instrument such as a gel permeation chromatography (GPC) instrument obtained from Waters, and the data can be processed using software such as Waters Empower software. The GPC instrument can be equipped with a Waters separation module and a Waters refractive index detector (or similar optional equipment). GPC operating conditions may include a guard column, 4 Agilent PLgel columns (length 300×7.5 mm; particle size 5μ, and pore size range ), the column temperature is about 40 ° C. Unstabilized HPLC grade tetrahydrofuran (THF) can be used as a solvent with a flow rate of 1.0 mL / min. The GPC instrument can be calibrated with commercially available polystyrene (PS) standards with a narrow molecular weight distribution ranging from 500 g / mol to 380,000 g / mol. For samples with a mass of less than 500 g / mol, the calibration curve can be extrapolated. Samples and PS standards can be dissolved in THF and prepared at a concentration of 0.1 wt % to 0.5 wt % and used without filtering. GPC measurements are also described in US 5,266,223, which is incorporated herein by reference. The GPC method also provides molecular weight distribution information; see, for example, WW Yau, JJ Kirkland and DD Bly, "Modern Size Exclusion Liquid Chromatography", John Wiley and Sons, New York, 1979, which is also 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 metal elements that contribute to the SASH in the lubricant composition, which is adjusted by a factor for each metal type. The metals that contribute to SASH include (together with the adjustment factor) 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 metal elements that are considered to contribute to the sulfated ash present in the lubricating oil composition is multiplied by its corresponding factor described above; then, the products of each metal element / factor adjustment are added, and the sum is divided by 10,000 to calculate the weight percentage of SASH in the lubricating composition. Further details of such calculations are set forth in the Examples below.

[0029] Additional details and advantages of the present disclosure will be partially set forth in the following description, and / or may be learned by practicing the present disclosure. The details and advantages of the present disclosure may be realized and obtained by the elements and combinations specifically pointed out in the appended claims. It should be understood that the above general description and the following detailed description are only exemplary and explanatory, and do not limit the present disclosure as claimed. BRIEF DESCRIPTION OF THE DRAWINGS

[0030] Figure 1 is a plot of the amount of total detergent metal phosphorus versus the amount of high temperature deposits;

[0031] Figure 2 is a graph of the amount of phosphorus in the detergent TBN versus the amount of high temperature deposits; and

[0032] Figure 3 It is a graph of the amount of SASH calculated relative to the high temperature deposits. DETAILED DESCRIPTION

[0033] In one aspect, the present disclosure describes blends of detergent and anti-wear lubricant additives and lubricants, including such additive blends suitable for and / or configured to comply with at least the API SP / ILSAC GF-6 standard. In one method, the lubricating composition effectively reduces high temperature deposits, and in particular high temperature deposits in low ash compositions. As shown in the examples below, reducing additives known to reduce ash levels may be detrimental to high temperature deposits. However, when certain relationships between detergent and anti-wear characteristics are maintained, improved high temperature deposit performance can be achieved in lubricant compositions with low ash levels. For example, the lubricating composition herein comprises a base oil of lubricating viscosity; a detergent system that provides a certain amount of metal to the lubricating composition, and preferably a metal of at least sodium, calcium, magnesium or a combination thereof; an anti-wear system, the anti-wear system comprising one or more metal dialkyl dithiophosphates derived from one of a primary alcohol, a secondary alcohol or a combination thereof, and providing a certain amount of phosphorus to the lubricating composition; and wherein the lubricating composition has a total base number (TBN) of about 0.5 to about 20.

[0034] Uniquely, embodiments of the lubricating compositions herein also include a unique relationship between an amount of phosphorus from the antiwear system relative to the TBN of the total lubricating composition to effectively achieve low high temperature deposits, and in embodiments, low high temperature deposits in the composition also have a low ash level calculated as sulfated ash. In embodiments, the ratio of an amount of phosphorus from the antiwear system in the lubricating composition relative to the TBN of the lubricating composition is about 150 or less, which surprisingly achieves low high temperature deposits, and particularly low high temperature deposits in lubricating compositions that also have low ash levels. In other approaches, the lubricating compositions herein may also have an amount of phosphorus from the antiwear system of about 0.5 or less relative to an amount of metal from the detergent system, and in other approaches, about 0.38 or less in the composition to effectively achieve low high temperature deposits in low ash formulations. For example, such relationships of phosphorus, TBN, and / or detergent metals are effective such that the lubricating compositions herein include less than about 30 mg of deposits when subjected to the high temperature deposit formation test of ASTM D6335 (i.e., TEOST-33C), and at the same time have a calculated sulfated ash of no more than about 0.8 wt % (as calculated according to the description herein). Each of the lubricant components will be described in more detail below.

[0035] Detergent system

[0036] The lubricant composition herein comprises a detergent system that provides a metal source, and preferably sodium, calcium, magnesium or a combination thereof, from a detergent additive such as phenates, sulfonates, salicylates and similar detergents as discussed in more detail below. Suitable detergents and methods for preparing them are described in more detail in a number of patent publications, including US 7,732,390 and references cited therein, which are incorporated herein by reference. The lubricant composition herein may include up to about 3.0 wt % or about 0.01 wt % to about 2.0 wt % of a detergent system, and in other methods, about 0.1 wt % to about 1.5 wt % of a detergent system, as long as the composition includes the relationship of the anti-wear phosphorus to the lubricant TBN or detergent metal discussed further herein.

[0037] As described above and in some methods, the detergent system provides a selected amount of metal, preferably a combination of calcium and magnesium, to the lubricating composition. For example, the detergent system herein provides an amount of metal of up to about 1800ppm, up to about 1700ppmw, up to about 1600ppmw, up to about 1500ppmw, up to about 1400ppmw, up to about 1300ppm metal, up to about 1200ppmw metal, or up to about 1100ppmw metal. In other cases, the detergent system provides at least about 100ppmw of metal, at least about 200ppmw of metal, at least about 300ppmw of metal, or at least about 400ppmw of metal.

[0038] Preferably, the detergent system provides calcium and magnesium. In the method, the detergent system comprises about 55% by weight to about 75% by weight of a detergent additive providing calcium (in other methods, about 60% by weight to about 70% by weight) and about 25% by weight to about 45% by weight of a detergent additive providing magnesium (in other methods, about 30% by weight to about 40% by weight). In other embodiments, the detergent system may also provide about 10ppm to about 1500ppm of calcium and about 10ppm to about 500ppm of magnesium to the lubricant composition. In some methods, calcium and magnesium are both provided by a sulfonate detergent additive or a phenate detergent additive (preferably a sulfonate detergent additive) having a TBN of 0 to about 500, and in other methods, a high alkaline detergent additive having a TBN of about 180 to about 500, about 200 to about 450, or about 300 to about 425.

[0039] Generally speaking, the detergent matrix herein can be salted with an alkali metal or alkaline earth metal, such as but not limited to calcium and magnesium as discussed above, but the detergent can also be salted with potassium, sodium, lithium, barium, zinc or mixtures thereof, as long as the detergent system meets the total metal and, in an optional approach, the calcium and magnesium requirements as described herein. In one approach, suitable detergents in the system can include alkali or alkaline earth metal salts of petroleum sulfonic acids and long chain mono- or dialkyl aryl sulfonic acids, such as calcium or magnesium salts, wherein 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, low-base / neutral and / or high-base forms of calcium phenate, sulfur-containing calcium phenate, calcium sulfonate, calcium calixarate, calcium salicyclic acid, calcium salicylate, calcium carboxylate, calcium phosphate, calcium monothiophosphate and / or dithiophosphate, calcium alkylphenate, sulfur-coupled alkylphenate calcium compounds, methylene-bridged calcium phenate, magnesium phenate, sulfur-containing magnesium phenate, magnesium sulfonate, magnesium calixarate, magnesium salicyclic acid, magnesium salicylate, magnesium carboxylate, magnesium phosphate, magnesium monothiophosphate and / or dithiophosphate, magnesium alkylphenate, sulfur-coupled alkylphenate magnesium compounds, methylene-bridged magnesium phenate, sodium phenate, sulfur-containing sodium phenate, sodium sulfonate, sodium calixarate, sodium salicyclic acid, sodium salicylate, sodium carboxylate, sodium phosphate, sodium monothiophosphate and / or dithiophosphate, sodium alkylphenate, sulfur-coupled sodium alkylphenate compounds, or methylene-bridged sodium phenate.

[0040] The detergent may also be neutral to highly basic, and preferably highly basic detergent. Highly basic detergent additives are well known in the art and may be alkali metal or alkaline earth metal highly basic detergent additives. Such detergent additives may be prepared by reacting metal oxides or metal hydroxides with substrates and carbon dioxide gas. The substrate is typically an acid, such as an acid such as an aliphatic substituted sulfonic acid, an aliphatic substituted carboxylic acid or an aliphatic substituted phenol.

[0041] As understood, the term "overbased" refers to metal salts, such as but not limited to metal salts of sulfonic acids, carboxylic acids, salicylic acids and / or phenols, in which a certain amount of metal present exceeds the stoichiometric amount. The conversion level of such salts may exceed 100% (i.e., it may include 100% of the theoretical amount of metal required to convert the acid into its "standard", "neutral" salt). The expression "metal ratio" is usually abbreviated as MR, which can be used to represent the ratio of the total chemical equivalents of the metal in the overbased salt to the chemical equivalents of the metal in the neutral salt, based on known chemical reactivity and stoichiometry. In normal or neutral salts, MR is one, and in overbased salts MR is greater than one. They are often referred to as overbased, superbased or superbasic salts, and may be salts of organic sulfuric acid, carboxylic acid, or phenol.

[0042] As used herein, the term "TBN" is used to represent the total base number in mg KOH / g as measured by the ASTM D2896 method. The total base number (TBN) of the overbased detergent of the lubricating oil composition may be greater than 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 metal to matrix ratio of the overbased detergent may be 1.1:1, or 2:1, or 4:1, or 5:1, or 7:1, or 10:1.

[0043] Examples of suitable overbased detergents include, but are not limited to, overbased calcium phenate, overbased sulfur-containing calcium phenate, overbased calcium sulfonate, overbased calcium calixarate, overbased calcium salicylate, overbased calcium carboxylate, overbased calcium phosphate, overbased calcium monothiophosphate and / or dithiophosphate, overbased calcium alkyl phenate, overbased sulfur-coupled alkyl phenate calcium compounds, overbased methylene-bridged calcium phenate, overbased magnesium phenate, overbased sulfur-containing magnesium phenate, overbased magnesium sulfonate, overbased magnesium calixarate, overbased magnesium salicylate, overbased magnesium carboxylate, overbased magnesium phosphate, overbased magnesium monothiophosphate and / or dithiophosphate, overbased magnesium alkyl phenate, overbased sulfur-coupled alkyl phenate magnesium compounds, or overbased methylene-bridged magnesium phenate.

[0044] The detergent may also be a low-base or even neutral detergent. For example, if used in the system herein, a low-base or neutral detergent typically has a TBN of at most 175 mg KOH / g, at most 150 mg KOH / g, at most 100 mg KOH / g, or at most 50 mg KOH / g. Low-base / neutral detergents may include calcium-containing or magnesium-containing detergents. Examples of suitable low-base / neutral detergents include, but are not limited to, calcium sulfonate, calcium phenate, calcium salicylate, magnesium sulfonate, magnesium phenate, and / or magnesium salicylate.

[0045] In embodiments, the detergent system comprises a combination of calcium sulfonate and magnesium sulfonate, but is not necessarily limited to such detergent combinations. In methods, the calcium sulfonate of the detergent system herein is preferably an overbased detergent, and in methods, has a total base number of about 200 to about 500, and in other methods, a total base number of about 300 to about 450. In other methods, the magnesium sulfonate of the detergent system herein is preferably also an overbased detergent with a total base number of about 200 to about 500, and in other methods, about 300 to about 425.

[0046] Anti-wear system

[0047] The lubricating composition herein also includes an anti-wear system combined with the detergent system discussed above. Among other features, the anti-wear system provides a mixture of anti-wear metals and phosphorus that effectively achieves friction performance and surprising high temperature deposit performance when balanced relative to the detergent system characteristics. The lubricating composition herein may include up to about 3.0 wt % of the anti-wear system, or about 0.01 wt % to about 2.0 wt %, and in other methods, about 0.1 wt % to about 1.5 wt % of the anti-wear system, as long as the composition includes the relationship of the anti-wear phosphorus to the lubricant TBN or detergent metal discussed further herein.

[0048] In the method, the anti-wear system comprises a mixture of two or more metal dihydrocarbyl dithiophosphate compounds, such as but not limited to two or more zinc dihydrocarbyl dithiophosphate compounds (ZDDP). Suitable metal dithiophosphates, such as ZDDP, can each include about 5% to about 10% by weight of metal (in other methods, about 6% to about 9% by weight of metal, wherein the metal is preferably zinc), and about 8% to about 18% by weight of sulfur (in other methods, about 12% to about 18% by weight of sulfur, or about 8% to about 15% by weight of sulfur). Metal dithiophosphates, such as ZDDP, also include about 5% to about 10% by weight of phosphorus. Suitable metal dihydrocarbyl dithiophosphates can be any one of dihydrocarbyl dithiophosphate metal salts, wherein the metal can be an alkali metal, an alkaline earth metal, aluminum, lead, tin, molybdenum, manganese, nickel, copper, titanium, zirconium, zinc or a combination thereof. However, the metal is preferably zinc.

[0049] When the phosphorus-containing compound of the anti-wear system is ZDDP, the alkyl group on the ZDDP can be derived from primary alcohol, secondary alcohol and / or their mixture. For example, the primary alcohol suitable for forming the alkyl group of ZDDP includes but is not limited to ethyl hexanol, butanol and / or C6 and higher primary alcohols. The secondary alcohol suitable for forming the alkyl group of ZDDP includes but is not limited to methyl isobutyl carbinol, isopropanol or their mixture. In some cases, the alkyl group of ZDDP can be derived from a mixture of primary and secondary alcohols, such as 2-ethyl hexanol (primary), isobutyl alcohol (primary) and isopropanol (secondary). For example, and in one embodiment, a ZDDP additive in the anti-wear system includes about alkyl groups derived from C6 to C8 primary alcohols and especially ethyl hexanol. In other embodiments, the second ZDDP of the anti-wear system includes all alkyl groups derived from secondary alcohols, such as methyl isobutyl carbinol, etc. In one method, the anti-wear system of this article includes a mixture of metal dialkyl dithiophosphates (preferably zinc dialkyl dithiophosphates) derived from primary and secondary alcohols. In embodiments, the weight ratio of primary alcohol to secondary alcohol of 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 other approaches, about 0.3:1 to about 0.4:1, as discussed in more detail below.

[0050] Examples of suitable ZDDPs include, but are not limited to: O,O-di(C 1-14 -alkyl) dithiophosphate zinc; (mixed O,O-bis(sec-butyl and isooctyl)) dithiophosphate zinc; O,O-bis(branched and straight chain C 3-8 -alkyl) zinc dithiophosphate; O,O-bis(2-ethylhexyl) zinc dithiophosphate; O,O-bis(mixed isobutyl and amyl) zinc dithiophosphate; mixed O,O-bis(1,3-dimethylbutyl and isopropyl) zinc dithiophosphate; O,O-diisooctyl zinc dithiophosphate; O,O-dibutyl zinc dithiophosphate; mixed O,O-bis(2-ethylhexyl and isobutyl and isopropyl) dithiophosphate; O,O-bis(dodecylphenyl) zinc dithiophosphate; O,O-diisodecyl zinc dithiophosphate; O-(6-methylheptyl) -O-(1-methylpropyl) zinc dithiophosphate; O-(2-ethylhexyl)-O-(isobutyl) zinc dithiophosphate; O,O-diisopropyl zinc dithiophosphate; (mixed hexyl and isopropyl) zinc dithiophosphate; (mixed O-(2-ethylhexyl) and O-isopropyl) zinc dithiophosphate; O,O-dioctyl zinc dithiophosphate; O,O-diamyl zinc dithiophosphate; O-(2-methylbutyl)-O-(2-methylpropyl) zinc dithiophosphate; and O-(3-methylbutyl)-O-(2-methylpropyl) zinc dithiophosphate.

[0051] In other embodiments, each of the phosphorus-containing compounds in the anti-wear system of the present invention may have a structure of Formula I

[0052]

[0053] 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 anti-wear system can contain two compounds of formula I structure. In each compound, as required, R can be ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, amyl, n-hexyl, isohexyl, n-octyl, decyl, dodecyl, octadecyl, 2-ethylhexyl, phenyl, butylphenyl, cyclohexyl, methylcyclopentyl, propenyl, butenyl, to meet the selection ratio of primary alcohol and secondary alcohol in the above-mentioned anti-wear system. In some embodiments, the number of carbon atoms in each R group in the above-mentioned formula I is generally about 3 or greater, about 4 or greater, about 6 or greater or about 8 or greater. Each R group can average 3 to 8 carbons. The total number of carbon atoms in the R group can 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.

[0054] In other approaches, the zinc dialkyl dithiophosphate of the antiwear system has the sulfur-zinc coordination arrangement of the phosphorus compound in the antiwear system shown under the chemical structure of Formula II, which is interchangeable with the above Formula I. It should also be understood that the structures shown in Formulas I and II can exist as monomers, dimers, trimers, or oligomers (such as tetramers).

[0055]

[0056] In some embodiments, each phosphorus-containing compound of the antiwear system has a structure of Formula I, wherein A is zinc, and the combined total amount of the compounds within the antiwear system provides about 70 ppm to about 800 ppm phosphorus (and in other methods, about 250 ppm to about 800 ppm phosphorus) and about 50 ppm to about 850 ppm zinc to the lubricant composition. As described above, the antiwear system comprises a mixture of zinc dialkyl dithiophosphates. Preferably, the antiwear system may include at least two zinc dialkyl dithiophosphates, wherein the first zinc dialkyl dithiophosphate is derived only from primary alcohols, and the second zinc dialkyl dithiophosphate is derived from secondary alcohols. Preferably, the antiwear system comprises a majority of secondary zinc dialkyl dithiophosphates derived only from secondary alcohols, such as where the weight ratio of primary alcohols to secondary alcohols that form ZDDP in the antiwear mixture (i.e., all compounds of 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 from secondary alcohols, and about 20% to about 30% of the alkyl groups in the antiwear mixture are from primary alcohols). In other methods, the ratio of primary alcohol to secondary alcohol forming the ZDDP in the antiwear mixture is at least about 0.25:1.0 to about 0.5:1.0, and in other methods, from about 0.3:1 to about 0.4:1.

[0057] In the method, the lubricating composition herein provides an amount of phosphorus, and in embodiments, has an anti-wear system that provides no more than about 800 ppm of phosphorus to the lubricating composition. In other methods, the anti-wear system provides no more than about 700 ppm of phosphorus, no more than about 500 ppm of phosphorus, no more than 400 ppm of phosphorus, or no more than about 300 ppm of phosphorus. In other methods, the anti-wear system provides at least about 50 ppm of phosphorus, at least about 75 ppm of phosphorus, or at least about 100 ppm of phosphorus.

[0058] In other methods, the lubricating composition herein provides an amount of anti-wear metal (preferably zinc), and in embodiments, has an anti-wear system that provides no more than about 850 ppm of zinc to the lubricating composition. In other methods, the anti-wear system provides no more than about 800 ppm of zinc, no more than about 700 ppm of zinc, no more than 500 ppm of zinc, or no more than about 400 ppm of zinc. In other methods, the anti-wear 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 composition herein comprises an amount of zinc provided by the anti-wear system relative to an amount of total metal from the detergent system of about 0.6 or less.

[0059] The metal dihydrocarbyl dithiophosphate salts can be prepared according to known techniques, namely firstly reacting one or more alcohols or phenols with P 2 S 5The reaction forms a dihydrocarbyl dithiophosphoric acid (DDPA), which is then neutralized with a metal compound such as zinc oxide. For example, DDPA can be prepared by reacting a mixture of primary and secondary alcohols with P 2 S 5 In this case, the DDPA contains alkyl groups derived from both primary and secondary alcohols. Alternatively, multiple DDPAs can be prepared, wherein the alkyl groups on one DDPA are completely derived from secondary alcohols, and the alkyl groups on another DDPA are completely derived from primary alcohols. The DDPAs are then blended together to form a mixture of DDPAs having alkyl groups derived from primary and secondary alcohols.

[0060] Lubricating oil composition

[0061] The above-described detergent system and antiwear system may be combined with one or more additional optional additives, 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 the method, the lubricating oil composition comprises about 50 weight percent or more of the base oil blend, about 60 weight percent or more, about 70 weight percent or more, or about 80 weight percent or more to about 95 weight percent or less, about 90 weight percent or less, about 85 weight percent or less of the base oil blend, the blend being further discussed below.

[0062] As described above, the lubricating oil composition comprises a unique relationship between the phosphorus provided by the antiwear system and: (i) the TBN of the total lubricating composition, (ii) the amount of total detergent metal (preferably calcium and / or magnesium), and / or (iii) two ratios effective to reduce and / or maintain low levels of high temperature deposits, and particularly in lubricating compositions having low ash levels calculated as sulfated ash, such as lubricating compositions having no more than about 0.8 weight percent calculated as sulfated ash.

[0063] For example, the total lubricating composition herein preferably has a total base number (TBN) of about 0.5 to about 20 (in other approaches, about 0.5 to about 10), and in the case of the above-mentioned detergent system and anti-wear system, the specific relationship of the amount of phosphorus from the anti-wear system relative to the TBN of the lubricating composition is about 150 or less, or in other embodiments, the amount of phosphorus from the anti-wear system relative to the lubricant TBN is 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 other embodiments, the amount of phosphorus from the anti-wear 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). Under such conditions, the lubricating compositions herein have less than about 30 mg of deposits when subjected to the High Temperature Deposit Formation Test (TEOST-33C) of ASTM D6335, and, in the case of low-ash compositions, include no more than about 0.8 wt. % calculated sulfated ash (or about 0.1 to about 0.8 wt. % calculated sulfated ash).

[0064] Base oil blends The base oil used in the lubricating oil composition herein may be an oil of lubricating viscosity and is selected from any one of the base oils of Group I to Group V as specified in the American Petroleum Institute (API) Base Oil Interchangeability Guidelines. The five types of base oils are as follows:

[0065] Table 1

[0066]

[0067] Class I, Class II and Class III are mineral oil processing raw materials.Class IV base oil contains real synthetic molecule species, and these synthetic molecule species are prepared by the polymerization of olefinically unsaturated hydrocarbons.Many Class V base oils are also real synthetic products, and can include diesters, polyol esters, polyalkylene glycols, alkylated aromatic compounds, polyphosphates, polyvinyl ethers and / or polyphenylene oxides etc., but can also be naturally occurring oils, such as vegetable oils.It should be noted that although Class III base oil derives from mineral oil, the strict processing of these fluid experiences causes their physical properties to be very similar to some real synthetic oils, such as PAO.Therefore, the oil that derives from Class III base oil can be called synthetic fluid in industry.The II+ class can include high viscosity index Class II.

[0068] The base oil blend used in the disclosed lubricating oil composition can be a mineral oil, an animal oil, a vegetable oil, a synthetic oil, a synthetic oil blend or a mixture thereof. Suitable oils can be derived from hydrocracked, hydrogenated, hydrofined, unrefined, refined and re-refined oils and mixtures thereof.

[0069] Unrefined oils are those oils derived from natural, mineral or synthetic sources with little or no further purification. Refined oils are similar to unrefined oils, except that they have been subjected to one or more purification steps, which may result in improvements in one or more properties. Examples of suitable purification techniques are solvent extraction, secondary distillation, acid or base extraction, filtration, percolation, etc. Refining to edible quality oils may or may not be useful. Edible oils may also be referred to as white oils. In some embodiments, the lubricating oil composition does not contain edible oils or white oils.

[0070] Re-refined oils are also called reclaimed oils or reprocessed oils. Similar to refined oils, these oils are obtained using the same or similar processes. Typically these oils are further processed by techniques directed to the removal of spent additives and oil breakdown products.

[0071] Mineral oil can comprise the oil obtained by drilling or the oil from plant and animal or their any mixture.For example, this type of oil can include but not limited to castor oil, lard, olive oil, peanut oil, corn oil, soybean oil and linseed oil, and mineral lubricating oil, such as liquid petroleum and solvent-treated or acid-treated paraffin, cycloalkane or mixed paraffin-cycloalkane type mineral lubricating oil.If necessary, this type of oil can be partially or completely hydrogenated.The oil deriving from coal or shale can also be applicable.

[0072] Useful synthetic lubricating oils may include hydrocarbon oils such as polymerized, oligomeric or copolymerized olefins (e.g., polybutene, polypropylene, propylene isobutylene copolymers); poly(1-hexene), poly(1-octene), 1-decene trimers or oligomers, such as poly(1-decene), such materials are generally referred to as alpha-olefins, and mixtures thereof; alkyl-benzenes (e.g., dodecylbenzene, tetradecylbenzene, dinonylbenzene, di-(2-ethylhexyl)-benzene); polyphenyls (e.g., biphenyl, terphenyl, alkylated polyphenyls); diphenylalkanes, alkylated diphenylalkanes, alkylated diphenyl ethers and alkylated diphenyl sulfides and derivatives, analogs and homologs thereof or mixtures thereof. Polyalpha-olefins are typically hydrogenated materials.

[0073] Other synthetic lubricating oils include polyol esters, diesters, liquid esters (e.g., diethyl esters of toluene phosphate, trioctyl phosphate and decanephosphonic acid) or polytetrahydrofurans containing phosphoric acid. Synthetic oils can be produced by Fischer-Tropsch reaction and can generally be Fischer-Tropsch hydrocarbons or waxes of hydroisomerization. In one embodiment, oil can be prepared by Fischer-Tropsch gas-liquid synthesis procedures and other gas-liquid oils.

[0074] The major amount of base oil included in the lubricating composition may be selected from Group I, Group II, Group III, Group IV, Group V, and combinations of two or more of the foregoing, and wherein the major amount of the base oil is different from the base oil resulting from providing an additive component or a viscosity index improver in the composition. In another embodiment, the major amount of base oil included in the lubricating composition may be selected from Group II, Group III, Group IV, Group V, and combinations of two or more of the foregoing, and wherein the major amount of the base oil is different from the base oil resulting from providing an additive component or a viscosity index improver in the composition.

[0075] The oil of lubricating viscosity may be present in an amount that is the remainder remaining after the total amount of performance additives (including viscosity index improvers and / or pour point depressants and / or other top treatment additives) is subtracted from 100 wt %. For example, the oil of lubricating viscosity that may be present in the finished fluid may be a major amount, such as greater than about 50 wt %, greater than about 60 wt %, greater than about 70 wt %, greater than about 80 wt %, greater than about 85 wt %, or greater than about 90 wt %.

[0076] Optional additives :

[0077] The lubricating oil compositions herein may also include a number of optional additives in combination with the dispersant system, antioxidant system and antiwear system discussed above as needed to meet performance criteria, as long as the described relationship of nitrogen and nitrogen source is maintained. Those optional additives are described in the following paragraphs.

[0078] Optional dispersant: The lubricating oil composition may optionally include 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 being mixed into the lubricating oil composition and they generally do not provide any ash when added to the lubricant. Ashless dispersants are characterized by polar groups attached to relatively high molecular weight hydrocarbon chains. Typical ashless dispersants include N-substituted long chain alkenyl succinimides. Examples of N-substituted long chain alkenyl succinimides include polyisobutylene succinimides, wherein the number average molecular weight of the polyisobutylene substituent is in the range of about 350 to about 50,000 or to about 5,000 or to 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(ethylene amines).

[0079] Preferred amines are selected from polyamines and hydroxylamines. Examples of polyamines that may be used include, but are not limited to, diethylenetriamine (DETA), triethylenetetramine (TETA), tetraethylenepentamine (TEPA) and higher homologues such as pentaethylaminehexamine (PEHA) and the like.

[0080] Suitable heavy polyamines are mixtures of polyalkylene-polyamines containing small amounts of lower polyamine oligomers such as TEPA and PEHA (pentaethylenehexamine) but predominantly oligomers having 6 or more nitrogen atoms per molecule, 2 or more primary amines and more extensive branching than conventional polyamine mixtures. Heavy polyamines preferably include polyamine oligomers containing 7 or more nitrogen atoms per molecule and 2 or more primary amines per molecule. Heavy polyamines contain greater than 28 wt% (e.g., >32 wt%) total nitrogen and an equivalent weight of primary amine groups of 120-160 g / equivalent.

[0081] In some processes, suitable polyamines are generally referred to as PAMs and contain a mixture of ethyleneamines, with TEPA and pentaethylenehexamine (PEHA) being the major portion of the polyamine, typically less than about 80%.

[0082] Typically, PAM has 8.7-8.9 milliequivalents of primary amine per gram (equivalent weight per primary amine equivalent is 115-112 grams) and a total nitrogen content of about 33-34 weight percent. A heavy fraction of PAM oligomers that is almost free of TEPA and contains only very little PEHA but contains mainly oligomers with more than 6 nitrogen atoms and more extensive branching can produce a dispersant with improved dispersibility.

[0083] In one embodiment, the present disclosure further comprises at least one polyisobutylene succinimide dispersant derived from polyisobutylene having a number average molecular weight in the range of about 350 to about 50,000 or to about 5000 or to about 3000 as determined by GPC. The polyisobutylene succinimide may be used alone or in combination with other dispersants.

[0084] In some embodiments, polyisobutylene (when included) can 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 PIBs are also referred to as highly reactive PIBs ("HR-PIBs"). HR-PIBs having a number average molecular weight in the range of about 800 to about 5000 as determined by GPC are suitable for use in embodiments of the present disclosure. Conventional PIBs typically have a terminal double bond content of less than 50 mol%, less than 40 mol%, less than 30 mol%, less than 20 mol%, or less than 10 mol%.

[0085] HR-PIBs with a number average molecular weight in the range of about 900 to about 3000 as determined by GPC may be suitable. Such HR-PIBs are commercially available or may be synthesized by polymerizing isobutylene in the presence of a non-chlorinated catalyst such as boron trifluoride, as described in U.S. Pat. No. 4,152,499 to Boerzel et al. and U.S. Pat. No. 5,739,355 to Gateau et al. When used in the aforementioned thermal olefin reaction, HR-PIBs may increase the conversion rate in the reaction, as well as reduce the amount of sediment formation, due to enhanced reactivity. Suitable methods are described in U.S. Pat. No. 7,897,696.

[0086] In one embodiment, the present disclosure further comprises at least one dispersant derived from polyisobutylene succinic anhydride ("PIBSA"). The PIBSA may have an average of between about 1.0 and about 2.0 succinic acid moieties per polymer.

[0087] The % activity of the alkenyl or alkyl succinic anhydride can be determined using chromatographic techniques. This method is described in columns 5 and 6 of US Patent No. 5,334,321.

[0088] The percent conversion of the polyolefin was calculated from the % activity using the equations in columns 5 and 6 of US Patent No. 5,334,321.

[0089] Unless otherwise indicated, all percentages are by weight and all molecular weights are number average molecular weights as determined by gel permeation chromatography (GPC) using commercially available polystyrene standards with number average molecular weights ranging from 180 to about 18,000 as calibration reference.

[0090] In one embodiment, the dispersant may be derived from polyalphaolefin (PAO) succinic anhydride. In one embodiment, the dispersant may be derived from olefin maleic anhydride copolymers. For example, the dispersant may be described as polyPIBSA. In embodiments, the dispersant may be derived from anhydrides grafted to ethylene-propylene copolymers.

[0091] A suitable class of nitrogen-containing dispersants can be derived from olefin copolymers (OCPs), more specifically ethylene-propylene dispersants, which can be grafted with maleic anhydride. A more complete list of nitrogen-containing compounds that can react with functionalized OCPs is described in U.S. Pat. Nos. 7,485,603; 7,786,057; 7,253,231; 6,107,257; and 5,075,383; and / or is commercially available.

[0092] A class of suitable dispersants may 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.

[0093] A class of suitable dispersants may also be high molecular weight esters or half ester amides. Suitable dispersants may also be post-treated by conventional methods by reaction with any of a variety of agents. Among these are boron, urea, thiourea, dimercaptothiadiazoles, carbon disulfide, aldehydes, ketones, carboxylic acids, hydrocarbon-substituted succinic anhydrides, maleic anhydride, nitriles, epoxides, carbonates, cyclic carbonates, hindered phenolic esters, and phosphorus compounds. US 7,645,726; US 7,214,649; and US 8,048,831 are incorporated herein by reference in their entirety.

[0094] In addition to carbonate and boric acid post-treatments, both 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 to 29 of U.S. Patent No. 5,241,003, incorporated herein by reference. Such treatments include treatment with: inorganic phosphorous acid or anhydrates (e.g., U.S. Patent Nos. 3,403,102 and 4,648,980); organic phosphorus compounds (e.g., U.S. Patent No. 3,502,677); phosphorus pentasulfide; boron compounds such as those mentioned above (e.g., U.S. Patent Nos. 3,178,663 and 4,652,387); carboxylic acids, polycarboxylic acids, anhydrides and / or acid halides (e.g., U.S. Patent Nos. 3,708,522 and 4,948, 386); epoxides, 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. Nos. 3,312,619; 3,865,813; and GB 1,065,595); organic sulfonic acids (e.g., U.S. Pat. No. 3,189,544 and GB 2,140,811); alkenyl cyanides (e.g., U.S. Pat. Nos. 3,278,550 and 3,366,569); diketenes (e.g., U.S. Pat. No. 3,546,243); diisocyanates (e.g., U.S. Pat. No. 3,573,205); alkane sultones (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. 3,954,63 9); 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. GB 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. 4,614,603 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 GB 2,440,811); hydroxy-protected chlorodicarbonyloxy compounds (e.g., U.S. Pat. No. 4,614,522); lactams, thiolactams, thiolactones or dithiolactones (e.g., U.S. Pat. Nos. 4,614,603 and 4,666,460); cyclic carbamates, cyclic thiocarbamates or cyclic dithiocarbamates (e.g., U.S. Pat. Nos. 4,663,062 and 4,666,459); hydroxy aliphatic carboxylic acids (e.g., U.S. Pat. Nos. 4,482,464; 4,521,318; 4,713,189); oxidants ( For example, U.S. Pat. No. 4,379,064); combinations of phosphorus pentasulfide and polyalkylene polyamines (for example, U.S. Pat. No. 3,185,647); combinations of carboxylic acids or aldehydes or ketones and sulfur or sulfur chloride (for example, U.S. Pat. Nos. 3,390,086; 3,470,098); combinations of hydrazine and carbon disulfide (for example, U.S. Pat. No. 3,519,564); combinations of aldehydes and phenols (for example, U.S. Pat. Nos. 3,649,229; 5,030,249; 5,039,307); combinations of aldehydes and O-diesters of dithiophosphoric acids (for example, U.S. Pat. Nos. 3,865, 740); a combination of a hydroxyaliphatic carboxylic acid and boric acid (e.g., U.S. Pat. No. 4,554,086); a combination of a hydroxyaliphatic carboxylic acid, then formaldehyde and phenol (e.g., U.S. Pat. No. 4,636,322); a combination of a hydroxyaliphatic carboxylic acid and then an aliphatic dicarboxylic acid (e.g., U.S. Pat. No. 4,663,064); a combination of formaldehyde and phenol and then glycolic acid (e.g., U.S. Pat. No. 4,699,724); a combination of a hydroxyaliphatic carboxylic acid or oxalic acid, and then a diisocyanate (e.g., U.S. Pat. No. 4,713,191); an inorganic acid or anhydride of phosphorus or a portion thereof or Combinations of all sulfur analogs with boron compounds (e.g., U.S. Pat. No. 4,857,214); combinations of organic diacids, then unsaturated fatty acids, then nitrosoaromatic amines, optionally followed by boron compounds, and then glycolating agents (e.g., U.S. Pat. No. 4,973,412); combinations of aldehydes and triazoles (e.g., U.S. Pat. No. 4,963,278); combinations of aldehydes and triazoles, then boron compounds (e.g., U.S. Pat. No. 4,981,492); combinations of cyclic lactones and boron compounds (e.g., U.S. Pat. Nos. 4,963,275 and 4,971,711). The patents mentioned above are incorporated herein in their entirety. ;

[0095] Suitable dispersants may have a TBN of about 10 mg KOH / g to about 65 mg KOH / g dispersant on an oil-free basis, which is comparable to about 5 TBN to about 30 TBN if measured on a dispersant sample containing about 50% diluent oil. TBN is measured by the method of ASTM D2896.

[0096] In further embodiments, the optional dispersant additive may be a hydrocarbyl-substituted succinamide or succinimide dispersant. In the method, the hydrocarbyl-substituted succinamide or succinimide dispersant is derived from a hydrocarbyl-substituted acylating agent reacted with a polyalkylene polyamine, and 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 measured by GPC using polystyrene as a calibration reference.

[0097] In some methods, the polyalkylene polyamine used to form the dispersant has the formula

[0098]

[0099] wherein each R and R' is independently a divalent C1 to C6 alkylene linking group, each R 1 and R 2 are independently hydrogen, a C1 to 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 between 0 and 8. In other methods, 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.

[0100] The optional dispersant, if present, can be used in an amount sufficient to provide up to about 20 wt % based on the final weight of the lubricating oil composition. Another amount of dispersant that can be used can be about 0.1 wt % to about 15 wt %, or about 0.1 wt % to about 10 wt %, or about 0.1 wt % to about 8 wt %, or about 1 wt % to about 10 wt %, or about 1 wt % to about 8 wt %, or about 1 wt % to about 6 wt %, based on the final weight of the lubricating oil composition. In some embodiments, the lubricating oil composition utilizes a mixed dispersant system. A single type of dispersant or a mixture of two or more types of dispersants can be used in any desired ratio.

[0101] Additional antioxidants The lubricating oil composition herein may also optionally contain one or more additional antioxidants. Antioxidant compounds are known and include, for example, phenates, phenate sulfides, sulphurized olefins, phosphosulfurized terpenes, sulphurized esters, aromatic amines, alkylated diphenylamines (e.g., nonyldiphenylamine, dinonyldiphenylamine, octyldiphenylamine, dioctyldiphenylamine), phenyl-α-naphthylamine, alkylated phenyl-α-naphthylamine, hindered non-aromatic amines, phenols, hindered phenols, oil-soluble molybdenum compounds, macromolecular antioxidants or mixtures thereof. The antioxidant compounds may be used alone or in combination.

[0102] Hindered phenol antioxidants may contain sec-butyl and / or tert-butyl groups as sterically hindered groups. The phenolic group may be further substituted with a hydrocarbyl group and / or a bridging group connected to a second aromatic group. Examples of suitable hindered phenol antioxidants include 2,6-di-tert-butylphenol, 4-methyl-2,6-di-tert-butylphenol, 4-ethyl-2,6-di-tert-butylphenol, 4-propyl-2,6-di-tert-butylphenol or 4-butyl-2,6-di-tert-butylphenol, or 4-dodecyl-2,6-di-tert-butylphenol. In one embodiment, the hindered phenol antioxidant may be an ester and may include, for example, Irganox®, which may be purchased from BASF. TM L-135 or the addition product derived from 2,6-di-tert-butylphenol and an alkyl acrylate, wherein 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 1,6-di-tert-butylphenol, available from Albemarle Corporation. TM 4716.

[0103] 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 weight percent based on the final weight of the lubricating oil composition. In an embodiment, the antioxidant may be a mixture of about 0.3 weight percent to about 1.5 weight percent diarylamine and about 0.4 weight percent to about 2.5 weight percent high molecular weight phenol based on the final weight of the lubricating oil composition.

[0104] The example of suitable olefins that can be sulfurized to form sulfurized olefins includes propylene, butylene, isobutylene, polyisobutylene, pentene, hexene, heptene, octene, nonene, decene, undecene, dodecene, tridecene, tetradecene, pentadecene, hexadecene, heptadecene, octadecene, nineteendecene, eicosene or its mixture. In one embodiment, hexadecene, heptadecene, octadecene, nineteendecene, eicosene or its mixture, and its dimer, trimer and tetramer are particularly suitable olefins. Alternatively, the olefin can be a diene (such as 1,3-butadiene) and an unsaturated ester (such as butyl acrylate) Diels-Alder adduct (Diels-Alder adduct).

[0105] Another class of sulphurized olefins includes sulphurized fatty acids and esters thereof. Fatty acids are usually obtained from vegetable oils or animal oils and usually contain about 4 to about 22 carbon atoms. Examples of suitable fatty acids and esters thereof include triglycerides, oleic acid, linoleic acid, palmitoleic acid or mixtures thereof. Usually, fatty acids are obtained from lard, pine oil, peanut oil, soybean oil, cottonseed oil, sunflower oil or mixtures thereof. Fatty acids and / or esters can be mixed with olefins such as alpha-olefins.

[0106] In another alternative embodiment, in addition to the phenolic and / or aminic antioxidants discussed above, the antioxidant composition also contains a platinum-containing antioxidant. When a combination of these three antioxidants is used, preferably, the ratio of phenolic antioxidant to aminic antioxidant to platinum-containing antioxidant is (0 to 2):(0 to 2):(0 to 1).

[0107] The one or more antioxidants may be present in a range from about 0 wt % to about 20 wt %, or from about 0.1 wt % to about 10 wt %, or from about 1 wt % to about 5 wt % of the lubricating oil composition.

[0108] Additional anti-wear agents :The lubricating oil composition herein may also optionally contain one or more additional anti-wear agents. Examples of suitable additional anti-wear agents include, but are not limited to, metal thiophosphates; metal dialkyl dithiophosphates; phosphates or their salts; phosphate esters; phosphites; phosphorus-containing carboxylates, ethers or amides; sulfurized olefins; compounds containing thiocarbamates, including thiocarbamates, alkylene coupled thiocarbamates and bis(S-alkyldithiocarbamoyl) disulfides; and mixtures thereof. A suitable anti-wear agent may be molybdenum dithiocarbamates. Phosphorus-containing anti-wear agents are more fully described in European Patent 612 839. The metal in the dialkyl dithiophosphate may be an alkali metal, an alkaline earth metal, aluminum, lead, tin, molybdenum, manganese, nickel, copper, titanium or zinc. A suitable anti-wear agent may be zinc dialkyl dithiophosphate.

[0109] Yet another example of a suitable antiwear agent includes titanium compounds, tartrates, tartrimides, oil-soluble amine salts of phosphorus compounds, sulphurized olefins, phosphites (such as dibutyl phosphite), phosphonates, thiocarbamate-containing compounds (such as thiocarbamates, thiocarbamate amides, thiocarbamate ethers, alkylene coupled thiocarbamates and bis(S-alkyldithiocarbamoyl)disulfides). The tartrate or tartrimide may contain an alkyl ester group, wherein the total number of carbon atoms in the alkyl group may be at least 8. In one embodiment, the antiwear agent may include a citrate ester.

[0110] The antiwear agent may be present in a range comprising about 0 wt % to about 15 wt %, or about 0.01 wt % to about 10 wt %, or about 0.05 wt % to about 5 wt %, or about 0.1 wt % to about 3 wt % of the lubricating oil composition.

[0111] Boron compounds :The lubricating oil composition 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. Pat. No. 5,883,057. The boron-containing compound, if present, may be used in an amount sufficient to provide up to about 8 weight %, about 0.01 weight % to about 7 weight %, about 0.05 weight % to about 5 weight %, or about 0.1 weight % to about 3 weight % of the lubricating oil composition.

[0112] Additional detergent The lubricating oil composition may optionally further comprise one or more additional neutral, low-base or high-base detergents and mixtures thereof. Suitable additional detergent bases include benzoates, sulfur-containing benzoates, sulfonates, calixformates, salicylates, salicylates, carboxylic acids, phosphoric acids, monothiophosphoric acids and / or dithiophosphoric acids, alkylphenols, sulfur-coupled alkylphenol compounds or methylene-bridged phenols. Suitable detergents and methods for their preparation are described in more detail in a number of patent publications, including US 7,732,390 and references cited therein.

[0113] The detergent matrix can be salified with 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 does not contain barium. In some embodiments, the detergent can contain trace amounts of other metals such as magnesium or calcium, such as 50ppm or less, 40ppm or less, 30ppm or less, 20ppm or less or 10ppm or less. Suitable detergents can include alkali metal or alkaline earth metal salts of petroleum sulfonic acid and long-chain mono- or dialkyl aryl sulfonic acids, wherein the aryl groups are benzyl, tolyl and xylyl. Examples of suitable detergents include, but are not limited to, calcium phenates, sulfur-containing calcium phenates, calcium sulfonates, calcium calixarates, calcium salixarates, calcium salicylates, calcium carboxylates, calcium phosphates, calcium monothiophosphates and / or dithiophosphates, calcium alkylphenates, sulfur-coupled alkylphenate calcium compounds, methylene-bridged calcium phenates, magnesium phenates, sulfur-containing magnesium phenates, magnesium sulfonates, magnesium calixarates, magnesium salixarates, magnesium salicylates, magnesium carboxylates, magnesium phosphates, magnesium monothiophosphates and / or dithiophosphates, magnesium alkylphenates, sulfur-coupled alkylphenate magnesium compounds, methylene-bridged magnesium phenates, sodium phenates, sulfur-containing sodium phenates, sodium sulfonates, sodium calixarates, sodium salixarates, salixarates), sodium salicylates, sodium carboxylates, sodium phosphates, sodium monothiophosphates and / or sodium dithiophosphates, sodium alkylphenols, sulfur-coupled sodium alkylphenol compounds, or methylene-bridged sodium phenols.

[0114] Overbased detergent additives are well known in the art and can be alkali metal or alkaline earth metal overbased detergent additives. Such detergent additives can be prepared by reacting a metal oxide or metal hydroxide with a substrate and carbon dioxide gas. The substrate is typically an acid, such as an acid such as an aliphatic substituted sulfonic acid, an aliphatic substituted carboxylic acid, or an aliphatic substituted phenol.

[0115] 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 other examples, 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.

[0116] Examples of suitable overbased detergents include, but are not limited to, overbased calcium phenate, overbased sulfur-containing calcium phenate, overbased calcium sulfonate, overbased calcium calixarate, overbased calcium salicylate, overbased calcium carboxylate, overbased calcium phosphate, overbased calcium monothiophosphate and / or dithiophosphate, overbased calcium alkyl phenate, overbased sulfur-coupled alkyl phenate calcium compounds, overbased methylene-bridged calcium phenate, overbased magnesium phenate, overbased sulfur-containing magnesium phenate, overbased magnesium sulfonate, overbased magnesium calixarate, overbased magnesium salicylate, overbased magnesium carboxylate, overbased magnesium phosphate, overbased magnesium monothiophosphate and / or dithiophosphate, overbased magnesium alkyl phenate, overbased sulfur-coupled alkyl phenate magnesium compounds, or overbased methylene-bridged magnesium phenate.

[0117] The total base number of the overbased calcium phenate detergent is at least about 150 mg KOH / g, at least about 225 mg KOH / g, at least about 225 mg KOH / g to about 400 mg KOH / g, at least about 225 mg KOH / g to about 350 mg KOH / g, or about 230 mg KOH / g to about 350 mg KOH / g, all as measured by the method of ASTM D-2896. When such detergent compositions are formed in an inert diluent (e.g., process oil, typically mineral oil), the total base number reflects the alkalinity of the overall composition, which includes the diluent and any other materials that may be contained in the detergent composition (e.g., promoters, etc.).

[0118] The metal to matrix ratio of the overbased detergent may be 1.1:1, or 2:1, or 4:1, or 5:1, or 7:1, or 10:1. In some embodiments, the detergent is effective in reducing or preventing rust in the engine or other automotive parts such as transmissions or gears. The detergent may be present in the lubricating composition at about 0 wt % to about 10 wt %, or about 0.1 wt % to about 8 wt %, or about 1 wt % to about 4 wt %, or greater than about 4 wt % to about 8 wt %.

[0119] Extreme Pressure AgentsThe lubricating oil composition herein may also optionally contain one or more extreme pressure agents. Extreme pressure (EP) agents soluble in oil include sulfur-containing and chlorine-containing sulfur-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 bisdibenzyl disulfide, bis(chlorobenzyl) disulfide, dibutyl tetrasulfide, sulfurized methyl oleate, sulfurized alkylphenols, sulfurized dipentenes, sulfurized terpenes, sulfurized Diels-Alder adducts; phosphosulfurized hydrocarbons such as the reaction product of phosphorus sulfide with turpentine or methyl oleate; phosphites such as dialkyl phosphites and trialkyl phosphites, for example, dibutyl phosphite, diheptyl phosphite, dicyclohexyl phosphite, amylphenyl phosphite; diamylphenyl phosphite, tridecyl phosphite, distearyl phosphite, and polypropylene-substituted phenyl phosphites; metal thiocarbamates such as zinc dioctyldithiocarbamate and barium heptylphenol dioate; amine salts of alkyl and dialkyl phosphoric acids, including, for example, amine salts of the reaction product of dialkyldithiophosphoric acids with propylene oxide; and mixtures thereof.

[0120] Friction modifiers The lubricating oil composition herein may also optionally contain one or more friction modifiers. Suitable friction modifiers may include metal-containing and metal-free friction modifiers and may include, but are not limited to, imidazolines, amides, amines, succinimides, alkoxylated amines, alkoxylated ether amines, amine oxides, amidoamines, nitriles, betaines, quaternary amines, imines, amine salts, aminoguanidines, alkanolamides, phosphonates, metal-containing compounds, glycerides, sulfurized fatty compounds and olefins, sunflower oil, other naturally occurring plant or animal oils, dicarboxylic acid esters, esters or partial esters of polyols, and one or more aliphatic or aromatic carboxylic acids, and the like.

[0121] Suitable friction modifiers may contain a hydrocarbyl group selected from a linear, branched or aromatic hydrocarbyl group or a mixture thereof, and may be saturated or unsaturated. The hydrocarbyl group may be composed of carbon and hydrogen or heteroatoms, such as sulfur or oxygen. The hydrocarbyl group may be in the range of about 12 to about 25 carbon atoms. In some embodiments, the friction modifier may be a long-chain fatty acid ester. In another embodiment, the long-chain fatty acid ester may be a monoester or a diester or a (tri) glyceride. The friction modifier may be a long-chain fatty amide, a long-chain fatty ester, a long-chain fatty epoxide derivative or a long-chain imidazoline.

[0122] Other suitable friction modifiers may include organic, ashless (metal-free), nitrogen-free organic friction modifiers. Such friction modifiers may include esters formed by reacting carboxylic acids and anhydrides with alkanols, and generally contain polar end groups (e.g., carboxyl or hydroxyl groups) covalently bonded to oleophilic hydrocarbon chains. An example of an organic ashless, nitrogen-free friction modifier is generally known as glyceryl monooleate (GMO), which may contain monoesters, diesters, and triesters of oleic acid. Other suitable friction modifiers are described in U.S. Pat. No. 6,723,685, which is incorporated herein by reference in its entirety.

[0123] Amine friction modifiers can include amines or polyamines. Such compounds can have straight chain, saturated or unsaturated hydrocarbon groups, or mixtures thereof, and can contain from about 12 to about 25 carbon atoms. Other examples of suitable friction modifiers include alkoxylated amines and alkoxylated ether amines. Such compounds can have straight chain, saturated or unsaturated hydrocarbon groups, or mixtures thereof. They can contain from about 12 to about 25 carbon atoms. Examples include ethoxylated amines and ethoxylated ether amines.

[0124] The amines and amides can 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-alkyl borate esters. Other suitable friction modifiers are described in U.S. Pat. No. 6,300,291, which is incorporated herein by reference in its entirety.

[0125] Friction modifiers may optionally be present in a range such as from about 0 wt % to about 10 wt %, or from about 0.01 wt % to about 8 wt %, or from about 0.1 wt % to about 4 wt %.

[0126] Molybdenum-containing components :The lubricating oil composition herein may also optionally contain one or more molybdenum-containing compounds. The oil-soluble molybdenum compound may have the functional properties of an antiwear agent, an antioxidant, a friction modifier, or a mixture thereof. The oil-soluble molybdenum compound may include molybdenum dithiocarbamates, molybdenum dialkyl dithiophosphates, molybdenum dithiophosphinates, amine salts of molybdenum compounds, molybdenum xanthates, molybdenum thioxanthates, molybdenum sulfides, molybdenum carboxylates, molybdenum alkoxides, trinuclear organic molybdenum compounds, and / or mixtures thereof. Molybdenum sulfides include molybdenum disulfide. Molybdenum disulfide may be in the form of a stable dispersion. In one embodiment, the oil-soluble molybdenum compound may be selected from the group consisting of molybdenum dithiocarbamates, molybdenum dialkyl dithiophosphates, amine salts of molybdenum compounds, and mixtures thereof. In one embodiment, the oil-soluble molybdenum compound may be molybdenum dithiocarbamates.

[0127] Suitable examples of molybdenum compounds that may be used include commercial materials sold under trade names such as: 822 TM , A. 2000 and 855 and 1055, and Sakura-Lube available from Adeka Corporation TM S-165, S-200, S-300, S-310G, S-151, S-525, S-600, S-700 and S-710, and mixtures thereof. Suitable molybdenum components are described in US 5,650,381; US ​​RE 37,363 E1; US ​​RE 38,929 E1; and US RE 40,595 E1, the entireties of which are incorporated herein by reference.

[0128] In addition, the molybdenum compound can be an acidic molybdenum compound. Including molybdic acid, ammonium molybdate, sodium molybdate, potassium molybdate and other alkali metal salts of molybdate and other molybdenum salts, such as sodium hydrogen molybdate, MoOCl4, MoO2Br2, Mo2O3Cl6, molybdenum trioxide or similar acidic molybdenum compounds. Alternatively, these compositions can provide molybdenum through molybdenum / sulfur complexes of basic nitrogen compounds, such as, for example, U.S. Patent Nos. 4,263,152; 4,285,822; 4,283,295; 4,272,387; 4,265,773; 4,261,843; 4,259,195 and 4,259,194; and WO 94 / 06897, the entire contents of which are incorporated herein by reference.

[0129] Another class of suitable organomolybdenum compounds are trinuclear molybdenum compounds, such as those having the formula Mo3SkLnQz and mixtures thereof, wherein S represents sulfur, L represents an independently selected ligand having an organic group having a sufficient number of carbon atoms to render the compound soluble or dispersible in oil, n is 1 to 4, k varies in the range of 4 to 7, Q is selected from the group of neutral electron donating compounds, such as water, amines, alcohols, phosphines, and ethers, and z ranges from 0 to 5 and includes non-stoichiometric values. There may be a total of at least 21 carbon atoms, such as at least 25, at least 30, or at least 35 carbon atoms, in the organic groups of all ligands. Additional suitable molybdenum compounds are described in U.S. Pat. No. 6,723,685, the entirety of which is incorporated herein by reference.

[0130] The oil-soluble molybdenum compound may be present in an amount sufficient to provide about 0.5 ppm to about 2000 ppm, about 1 ppm to about 700 ppm, about 1 ppm to about 550 ppm, about 5 ppm to about 300 ppm, or about 20 ppm to about 250 ppm of molybdenum.

[0131] Compounds containing transition metals In another embodiment, the oil-soluble compound may be a compound containing a transition metal or a metalloid. The transition metal may include, but is 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.

[0132] In one embodiment, the oil-soluble transition metal-containing compound may function as an antiwear agent, a friction modifier, an antioxidant, a deposit control additive, or more than one of these functions. In one embodiment, 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 the disclosed technology or may be used to prepare the oil-soluble materials of the disclosed technology are various Ti (IV) compounds, such as titanium (IV) oxide; titanium (IV) sulfide; titanium (IV) nitrate; titanium (IV) alkoxides, such as titanium methoxide, titanium ethoxide, titanium propoxide, titanium isopropoxide, titanium butoxide, 2-ethylhexyl titanium; and other titanium compounds or complexes, including but not limited to titanium phenolates; titanium carboxylates, such as 2-ethyl-1-3-adipate titanium (IV) or titanium citrate or titanium oleate; and (triethanolamine) isopropoxide titanium (IV). Other forms of titanium encompassed within the disclosed technology include titanium phosphates, such as titanium dithiophosphates (e.g., titanium dialkyl dithiophosphates), and titanium sulfonates (e.g., titanium alkylbenzene sulfonates), or generally, the reaction products of titanium compounds reacting with various acidic materials to form salts (e.g., oil-soluble salts). Titanium compounds can therefore be derived from organic acids, alcohols, and glycols in particular. Ti compounds can also exist in dimerized or oligomeric forms, containing Ti--O--Ti structures. Such titanium materials are commercially available or can be easily prepared by appropriate synthesis techniques that are readily known to those skilled in the art. It exists in solid or liquid form at room temperature, depending on the specific compound. It can also be provided in the form of a solution in a suitable inert solvent.

[0133] In one embodiment, titanium can be supplied as a Ti-modified dispersant, such as a succinimide dispersant. Such materials can be prepared by forming a titanium mixed anhydride between 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 it can be reacted with any of a number of materials, such as (a) a polyamine-based succinimide / amide dispersant having free, condensable --NH functional groups; (b) components of a polyamine-based succinimide / amide dispersant, i.e., an alkenyl-(or alkyl-) succinic anhydride and a polyamine, (c) a hydroxyl-containing polyester dispersant prepared by reacting a substituted succinic anhydride with a polyol, an amino alcohol, a polyamine, or a mixture thereof. Alternatively, the titanate-succinate intermediate can be reacted with other reagents, such as alcohols, amino alcohols, ether alcohols, polyether alcohols or polyols or fatty acids, and the product thereof can be used directly to impart Ti to the lubricant, or additionally, reacted with a succinic acid dispersant as described herein. As an example, 1 part (by mole) of tetraisopropyl titanate can be reacted with about 2 parts (by mole) of polyisobutylene-substituted succinic anhydride at 140° C.-150° C. for 5 to 6 hours to provide a titanium-modified dispersant or intermediate. The resulting material (30 g) can be further reacted with a succinimide dispersant and a polyethylene polyamine mixture (127 g + diluent oil) from a polyisobutylene-substituted succinic anhydride at 150° C. for 1.5 hours to produce a titanium-modified succinimide dispersant.

[0134] Another titanium-containing compound can be a titanium alkoxide and a C 6 To C 25 The reaction product of carboxylic acid. The reaction product can be represented by the following formula:

[0135]

[0136] 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 is represented by the formula:

[0137]

[0138] Where m+n=4 and n is in the range of 1 to 3, R 4 is an alkyl moiety having 1 to 8 carbon atoms, R 1 is selected from hydrocarbon groups containing from about 6 to 25 carbon atoms, and R 2 and R 3 The same or different and selected from hydrocarbon groups containing about 1 to 6 carbon atoms, or the titanium compound can be represented by the following formula:

[0139]

[0140] Where x is in the range of 0 to 3, R 1is selected from hydrocarbon groups containing from about 6 to 25 carbon atoms, R 2 and R 3 are the same or different and are selected from hydrocarbon groups containing about 1 to 6 carbon atoms, and R 4 Choose from H, or C 6 To C 25 A group consisting of carboxylic acid moieties.

[0141] Suitable carboxylic acids may include, but are not limited to, caproic acid, caprylic acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, oleic acid, erucic acid, linoleic acid, linolenic acid, cyclohexanecarboxylic acid, phenylacetic acid, benzoic acid, neodecanoic acid, and the like.

[0142] In embodiments, the oil soluble titanium compound may be present in the lubricating oil composition in an amount providing 0 ppm to 3000 ppm by weight titanium, or 25 ppm to about 1500 ppm by weight titanium, or about 35 ppm to 500 ppm by weight titanium, or about 50 ppm to about 300 ppm by weight.

[0143] Viscosity Index Improver :The lubricating oil composition herein may also optionally contain one or more viscosity index improvers. Suitable viscosity index improvers may include polyolefins, olefin copolymers, ethylene / propylene copolymers, polyisobutylene, hydrogenated styrene-isoprene polymers, styrene / maleic acid ester copolymers, hydrogenated styrene / butadiene copolymers, hydrogenated isoprene polymers, alpha-olefin maleic anhydride copolymers, polymethacrylates, polyacrylates, polyalkylstyrenes, hydrogenated alkenyl aryl conjugated diene copolymers, or mixtures thereof. Viscosity index improvers may include star polymers, and suitable examples are described in U.S. Publication No. 20120101017A1.

[0144] The lubricating oil compositions herein may optionally contain one or more dispersant viscosity index improvers in addition to or in place of the viscosity index improvers. Suitable viscosity index improvers may include functionalized polyolefins, for example, ethylene-propylene copolymers that have been functionalized with the reaction product of an acylating agent (such as maleic anhydride) and an amine; polymethacrylates functionalized with amines, or esterified maleic anhydride-styrene copolymers reacted with amines.

[0145] Viscosity Index Improvers and / or Dispersants The total amount of viscosity index improvers can be from about 0 wt % to about 20 wt %, from about 0.1 wt % to about 15 wt %, from about 0.1 wt % to about 12 wt %, or from about 0.5 wt % to about 10 wt % of the lubricating oil composition.

[0146] Other optional additivesOther additives may be selected to perform one or more functions required of the lubricating fluid. In addition, one or more of the additives mentioned may be multifunctional and provide functions other than or different from the functions specified herein.

[0147] Lubricating oil compositions according to the present disclosure may optionally include other performance additives. Other performance additives may be additives other than the specified additives of the present disclosure and / or may include one or more of the following: metal passivators, viscosity index improvers, detergents, ashless TBN promoters, friction modifiers, antiwear agents, corrosion inhibitors, rust inhibitors, dispersants, dispersant viscosity index improvers, extreme pressure agents, antioxidants, foam inhibitors, demulsifiers, emulsifiers, pour point depressants, seal swell agents and mixtures thereof. Typically, a fully formulated lubricating oil will contain one or more of these performance additives.

[0148] Suitable metal deactivators may include derivatives of benzotriazole (typically tolyltriazole), dithiothiadiazole derivatives, 1,2,4-triazole, benzimidazole, 2-alkyldithiobenzimidazole or 2-alkyldithiobenzothiazole; foam inhibitors including copolymers of ethyl acrylate and 2-ethylhexyl acrylate and optionally vinyl acetate; demulsifiers including trialkyl phosphates, polyethylene glycol, polyethylene oxide, polypropylene oxide and (ethylene oxide-propylene oxide) polymers; pour point depressants including esters of maleic anhydride-styrene, polymethacrylates, polyacrylates or polyacrylamides.

[0149] Suitable foam suppressors include silicon-based compounds such as siloxanes.

[0150] Suitable pour point depressants may include polymethyl methacrylate or mixtures thereof. The pour point depressant may be present in an amount sufficient to provide about 0 wt % to about 1 wt %, about 0.01 wt % to about 0.5 wt %, or about 0.02 wt % to about 0.04 wt % based on the final weight of the lubricating oil composition.

[0151] Suitable rust inhibitors can be single compounds or compound mixtures having the characteristics of inhibiting corrosion of iron metal surfaces. Non-limiting examples of useful rust inhibitors 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; and oil-soluble polycarboxylic acids including dimer acid and trimer acid, such as those produced by pine oil fatty acid, oleic acid, and linoleic acid. Other suitable corrosion inhibitors include long-chain α, ω-dicarboxylic acids with a molecular weight ranging from about 600 to about 3000, and alkenyl succinic acids in which the alkenyl group contains about 10 or more carbon atoms, such as tetrapropylene succinic acid, tetradecene succinic acid, and hexadecene succinic acid. Another type of acidic corrosion inhibitor available is a half ester of alkenyl succinic acid and alcohol (such as polyethylene glycol) having about 8 to about 24 carbon atoms in the alkenyl group. The corresponding half amides of such alkenyl succinic acids are also useful. Useful rust inhibitors are high molecular weight organic acids.

[0152] Rust inhibitors, if present, may be used in amounts sufficient to provide from about 0 wt % to about 5 wt %, from about 0.01 wt % to about 3 wt %, from about 0.1 wt % to about 2 wt %, based on the final weight of the lubricating oil composition.

[0153] Generally speaking, suitable lubricants including the neutral to overbased and sulfurized phenol alkyl ester products herein may include additive components within the ranges listed in the table below.

[0154] Table 2: Suitable lubricating compositions

[0155]

[0156] The percentage of each component above represents the weight percentage 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 to formulate the composition described herein can be blended into the base oil individually or in various sub-combinations. However, it may be appropriate to blend all components simultaneously using an additive concentrate (i.e., additives plus diluents, such as hydrocarbon solvents). A fully formulated lubricant typically contains an additive package, referred to herein as a dispersant / inhibitor package or DI package, which will supply the desired features in the formulation.

[0157] Lubricants herein are configured to be used in various types of lubricants, such as automotive lubricants and / or greases, internal combustion engine oils, hybrid engine oils, electric engine lubricants, transmission 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 crushing fluids, etc. Suitable engine types may include, but are not limited to, heavy-duty diesel engines, passenger cars, light diesel engines, medium-speed diesel engines, or marine engines. The internal combustion engine may be a diesel fuel engine, a gasoline fuel engine, a natural gas fuel engine, a biofuel engine, a mixed diesel / biofuel fuel engine, a mixed gasoline / biofuel fuel engine, an alcohol fuel engine, a mixed gasoline / alcohol fuel engine, a compressed natural gas (CNG) fuel 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 a power source or a battery power source. Such a constructed engine is generally referred to as a hybrid engine. The internal combustion engine may be a 2-stroke, 4-stroke, or rotary engine. Suitable internal combustion engines include marine diesel engines (such as inland boats), aviation piston engines, low load diesel engines and motorcycle, automobile, locomotive and truck engines.The engine may be coupled to a turbocharger.

[0158] The lubricating oil composition for internal combustion engines can be applicable to any engine lubricant, regardless of sulfur, phosphorus or ash calculated with sulfated ash (ASTM D-874) content. The sulfur content of the engine oil lubricant can be about 1 weight % or less, or about 0.8 weight % or less, or about 0.5 weight % or less, or about 0.3 weight % or less, or about 0.2 weight % or less. In one embodiment, the sulfur content can be in the range of about 0.001 weight % to about 0.5 weight %, or about 0.01 weight % to about 0.3 weight %. The phosphorus content can be about 0.2 weight % or less, or about 0.1 weight % or less, or about 0.085 weight % or less, or about 0.08 weight % or less, or even about 0.06 weight % or less, about 0.055 weight % or less, or about 0.05 weight % or less. In one embodiment, the phosphorus content can be about 50ppm to about 1000ppm, or about 325ppm to about 850ppm. The total sulfated ash content can be about 2 wt % or less, or about 1.5 wt % or less, or about 1.1 wt % or less, or about 1 wt % or less, or about 0.8 wt % or less, or about 0.5 wt % or less. In one embodiment, the sulfated ash content can be about 0.05 wt % to about 0.9 wt %, or about 0.1 wt % or about 0.2 wt % to about 0.45 wt %. In another embodiment, the sulfur content can be about 0.4 wt % or less, the phosphorus content can be about 0.08 wt % or less, and the sulfated ash can be about 1 wt % or less. In yet another embodiment, the sulfur content can be about 0.3 wt % or less, the phosphorus content can be about 0.05 wt % or less, and the sulfated ash can be about 0.8 wt % or less.

[0159] In addition, the lubricants of the present description may be suitable for meeting 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-4Plus, 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 original equipment manufacturer specifications, such as Dexos 1. TM 、Dexos2 TM,MB-Approval 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-01FE, Longlife-04, Longlife-12FE, Longlife-14FE+, Longlife-17FE+, Porsche A40, C30, Peugeot Automobiles B712290, 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 9.55535G1, G2, M2, N1, N2, Z2, S1, S2, S3, S4, T2, DS1, DSX, GH2, GS1, GSX, CR1, Jaguar Land Rover STJLR.03.5003, STJLR.03.5004, STJLR.03.5005, STJLR.03.5006, STJLR.03.5007, STJLR.51.5122, or any past or future PCMO or HDD specification not mentioned herein. In some embodiments, for passenger car motor oil (PCMO) applications, the amount of phosphorus in the finished fluid is 1000 ppm or less, or 900 ppm or less, or 800 ppm or less.

[0160] In one embodiment, the lubricating oil composition is an engine oil, wherein the lubricating oil composition may have (i) a sulfur content of about 0.5 wt % or less, (ii) a phosphorus content of about 0.1 wt % or less, and (iii) an ash content calculated as sulfated ash content of about 1.5 wt % or less.

[0161] In one embodiment, the lubricating oil composition is suitable for use in a 2-stroke or 4-stroke marine diesel internal combustion engine. In one embodiment, the marine diesel internal combustion engine is a 2-stroke engine. In some embodiments, the lubricating oil composition is not suitable for use in a 2-stroke or 4-stroke marine diesel internal combustion engine for one or more reasons, including but not limited to the high sulfur content of the fuel used to power the marine engine and the high TBN required for a marine-suitable engine oil (e.g., above about 40 TBN in a marine-suitable engine oil).

[0162] In some embodiments, the lubricating oil composition is suitable for use in engines powered by low sulfur fuels, such as fuels containing from about 1 to about 5% sulfur. Highway vehicle fuel contains about 15 ppm sulfur (or about 0.0015% sulfur).

[0163] Example

[0164] The following examples are illustrations of exemplary embodiments of the present disclosure. In these examples, and elsewhere in this application, unless otherwise stated, all ratios, parts and percentages are by weight. It is intended to present these examples only for illustrative purposes, and is not intended to limit the scope of the invention disclosed herein.

[0165] Comparative Example 1

[0166] Comparative lubricating composition C1 was evaluated for high temperature deposits using ASTM 6335. Table 2 below shows the detergent system and antiwear system included in the comparative lubricating composition, which was formulated into a finished lubricant and also included a dispersant, an antioxidant, an organo-molybdenum additive, a defoaming additive, a friction modifier, an olefin copolymer viscosity modifier, a pour point dispersant, a processing oil, and a base oil.

[0167] Table 2: Comparative Lubricating Composition (C1)

[0168]

[0169] In the detergent system of Table 2, the calcium sulfonate has a TBN of about 300 and about 11.9 wt % calcium, and the magnesium sulfonate has a TBN of about 400 and about 9.6 wt % magnesium. In the antiwear system, ZDDP A is a zinc dialkyl dithiophosphate and includes an alkyl group derived from methyl isobutyl carbinol and includes about 7 wt % phosphorus, about 14.8 wt % sulfur, and about 7.8 wt % zinc. ZDDP B is also a zinc dialkyl dithiophosphate, but includes an alkyl group derived from ethyl hexanol and includes about 6 wt % phosphorus, about 13 wt % sulfur, and about 6.8 wt % zinc. Although this comparative lubricating composition exhibits less than about 30 mg (TOEST-33C) of through high temperature deposits, it has a relatively high calculated SASH of 0.8 wt %.

[0170] The calculated sulfated ash (SASH) content in Table 2 above was determined as follows: Comparative Example 1 (CE-1) included 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:

[0171] 59 ppmw of boron x 3.22 = 189.98

[0172] 1392 ppmw calcium x 3.4 = 4732.8

[0173] 371 ppmw magnesium x 4.95 = 1836.5

[0174] 50ppmw boron x 1.5 = 75

[0175] 696ppmw zinc x 1.5 = 1044

[0176] (189.98+4732.8+1836.5+75+1044) / 10000 = 0.79% SASH by weight

[0177] This calculation method was used to determine all sulfated ash (SASH) values ​​given in this application.

[0178] Comparative Example 2

[0179] In order 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 system and anti-wear system included in these further comparative lubricating compositions, which were formulated into finished lubricants, including the same amounts and the same dispersant, antioxidant, organo-molybdenum additive, defoaming additive, friction modifier, olefin copolymer viscosity modifier, pour point dispersant, process oil and base oil of the comparative lubricating composition of Table 2 in Example 1. The detergent additive and anti-wear additive are the same as described in Example 1.

[0180] Table 3: Lubricating compositions of the present invention

[0181]

[0182] As shown in Table 3 above, as the detergent level decreased, total high temperature deposits increased to an unacceptable level of about 30 mg, despite lower calculated sulfated ash in the comparative samples of C2 and C4. These comparative samples had a phosphorus to lubricant TBN ratio of 172 to 635 and a phosphorus to total detergent metal ratio of 0.55 to 3.87.

[0183] Example 1

[0184] By selecting the unique relationship of phosphorus, metals and TBN as described herein, lubricating compositions of the present invention are prepared with lower ash levels and lower high temperature deposits. Table 4 below shows the detergent system and anti-wear system included in these lubricating compositions of the present invention, which are formulated into finished lubricants, including the same amounts and the same dispersant, antioxidant, organo-molybdenum additive, defoaming additive, friction modifier, olefin copolymer viscosity modifier, pour point dispersant, process oil and base oil of the comparative lubricating composition of Table 2 in Example 1. The detergent additive and anti-wear additive are the same as described in Example 1.

[0185] Table 4

[0186]

[0187] Inventive samples I-1 to I-3 show lower ash levels calculated as sulfated ash and acceptable high temperature deposit levels. These inventive samples have a phosphorus to lubricant TBN ratio of about 13 to about 89 and a phosphorus to total detergent metal ratio of about 0.04 to about 0.3.

[0188] Example 2

[0189] Based on the relationship between phosphorus, metals and TBN, lubricating compositions of the present invention with lower ash levels were prepared by reducing the amount of detergent system and anti-wear components. Table 5 below shows the detergent system and anti-wear system included in these lubricating compositions of the present invention, which were formulated into finished lubricants, including the same amounts and the same dispersant, antioxidant, organo-molybdenum additive, defoaming additive, friction modifier, olefin copolymer viscosity modifier, pour point dispersant, process oil and base oil of the comparative lubricating composition of Table 2 in Example 1. The detergent additive and anti-wear additive are the same as described in Example 1.

[0190] Table 5

[0191]

[0192] Inventive samples 1-4 to 1-6 show lower ash levels calculated as sulfated ash and acceptable high temperature deposit levels. These inventive samples have a phosphorus to lubricant TBN ratio of about 63 to about 120 and a phosphorus to total detergent metal ratio of about 0.34 to about 0.38.

[0193] Figure 2 The graph shows the ratio of phosphorus to lubricant TBN in Comparative Example 2 and Examples 1 and 2 of the present invention relative to high temperature deposits of the present invention and comparative samples. Figure 1 The graph of shows the ratio of phosphorus to total detergent metals in Comparative Example 2 and Inventive Examples 1 and 2 relative to the high temperature deposits of the Inventive and Comparative samples. Finally, Figure 3 The plot shows that the calculated level of sulfated ash itself has no effect on high temperature deposits, but only through Figure 1 and Figure 2 The selection ratio shown in the figure shows that low ash formation can only be achieved through high temperature deposition.

[0194] 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 affirmatively limited to one referent. Thus, for example, reference to "an antioxidant" includes two or more different antioxidants. The term "comprising" and its grammatical variations as used herein are intended to be non-limiting, such that recitation of items in a list does not exclude other similar items that can be substituted or added to the listed items.

[0195] For purposes of this specification and the appended claims, unless otherwise indicated, all numbers and other numerical values ​​used in the specification and claims indicating quantities, percentages or ratios should be understood to be modified in all cases by the term "about". Therefore, unless otherwise indicated, the numerical parameters set forth in the following specification and the appended claims are approximate values ​​that may vary depending on the desired properties sought to be obtained by the present disclosure. At a minimum, and without attempting to limit the application of the doctrine of equivalents to the scope of the claims, each numerical parameter should at least be interpreted in light of the number of reported significant figures and by applying ordinary rounding techniques.

[0196] It should be understood that each component, compound, substituent or parameter disclosed herein should be interpreted as disclosed for use alone or in combination with one or more of each of the other components, compounds, substituents or parameters disclosed herein.

[0197] It should be further understood that each range disclosed herein should be interpreted as a disclosure of each specific value within the disclosed range with the same number of significant figures. Thus, for example, a range of 1 to 4 should be interpreted as an explicit disclosure of the values ​​1, 2, 3, and 4, as well as any range of such values.

[0198] It should be further understood that each lower limit of each scope disclosed herein should be interpreted as being disclosed in combination with each upper limit of each scope disclosed herein for the same component, compound, substituent or parameter and each specific value in each scope. Therefore, the disclosure should be interpreted as being disclosed by combining each lower limit of each scope with each upper limit of each scope or with each specific value in each scope, or by combining each upper limit of each scope with each specific value in each scope. That is, it should also be further understood that any scope between the endpoint values ​​in a wide range is also discussed herein. Therefore, the scope of 1 to 4 also means the scope of 1 to 3, 1 to 2, 2 to 4, 2 to 3, etc.

[0199] In addition, a specific amount / value of a component, compound, substituent or parameter disclosed in this specification or the examples should be interpreted as a disclosure of a lower or upper limit of a range, and therefore can be combined with any other lower or upper limit or specific amount / value of a range for the same component, compound, substituent or parameter disclosed elsewhere in this disclosure to form a range for that component, compound, substituent or parameter.

[0200] Although specific embodiments have been described, alternatives, modifications, variations, improvements, and substantial equivalents that are not currently foreseen or may not currently be foreseen may occur to applicants or other persons skilled in the art. Therefore, the appended claims as filed and as they may be amended are intended to cover all such alternatives, modifications, variations, improvements, and substantial equivalents.

[0201] The following examples are illustrative and non-limiting of the methods and compositions of the present disclosure. Other suitable modifications and adjustments of various conditions and parameters commonly encountered in the art and apparent to those skilled in the art are within the spirit and scope of the present disclosure. All patents and publications cited herein are incorporated herein by reference in their entirety. Examples 1 to 6 illustrate different lubricating compositions comprising viscosity index improvers and methods for their preparation, which viscosity index improvers comprise ethylene units and propylene units reacted with macromonomer alcohols.

Claims

1. A lubricating composition for reducing high-temperature deposits, the lubricating composition comprising: one or more base oils of lubricating viscosity; a detergent system that provides an amount of a metal to the lubricating composition, wherein the metal is at least one of sodium, calcium, magnesium, or a combination thereof, wherein the detergent system comprises 55% to 75% by weight of a calcium-providing detergent additive and 25% to 45% by weight of a magnesium-providing detergent additive; 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; wherein the total base number (TBN) of the lubricating composition is from 0.5 to 20; wherein the ratio of phosphorus from the antiwear system relative to the TBN of the lubricating composition is 150 or less; wherein the lubricating composition comprises a total amount of metals such that the composition has a calculated sulfated ash of no more than 0.8 weight percent; and wherein the lubricating composition has less than 30 mg of deposit when subjected to the high temperature deposit formation test of ASTM D6335.

2. The lubricating composition of claim 1, wherein the ratio of phosphorus from the antiwear system relative to the TBN is 120 or less.

3. The lubricating composition of claim 2, wherein the lubricating composition comprises no more than 800 ppm phosphorus from the antiwear system.

4. The lubricating composition of claim 3, wherein the lubricating composition comprises no more than 1800 ppm of metals from the detergent system.

5. The lubricating composition of claim 1, wherein the ratio of phosphorus from the antiwear system relative to the amount of metal from the detergent system is 0.5 or less.

6. The lubricating composition of claim 1, wherein the detergent system provides 10 ppm to 1500 ppm calcium and 10 ppm to 500 ppm magnesium.

7. The lubricating composition of claim 1, wherein the antiwear system comprises two metal dialkyl dithiophosphates.

8. The lubricating composition of claim 1, wherein the antiwear system comprises two zinc dialkyl dithiophosphates, and wherein the first zinc dialkyl dithiophosphate is derived from a primary alcohol and the second zinc dialkyl dithiophosphate is derived from a secondary alcohol.

9. The lubricating composition of claim 8, wherein the antiwear system comprises the second zinc dialkyl dithiophosphate derived primarily from a secondary alcohol.

10. The lubricating composition of claim 9, wherein 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.

11. The lubricating composition of claim 1 , wherein the detergent system comprises calcium sulfonate, calcium phenate, or a combination thereof having a total base number of 200 to 500.

12. The lubricating composition of claim 11, wherein the detergent system comprises a magnesium sulfonate, a magnesium phenate, or a combination thereof having a total base number of 200 to 500.

13. The lubricating composition of claim 1, wherein the total base number of the lubricating composition is less than 10.

14. The lubricating composition of claim 1 further comprising an amount of zinc provided by the antiwear system, and wherein the amount of zinc from the antiwear system relative to the amount of total metals from the detergent system is 0.6 or less.

15. The lubricating composition of claim 14, wherein the antiwear system provides 50 ppm to 850 ppm of zinc to the lubricating composition.

16. The lubricating composition of claim 1, wherein the lubricating composition is a passenger car motor oil.

17. A low-ash lubricating composition for reducing high-temperature deposits, the lubricating composition comprising: one or more base oils of lubricating viscosity; a detergent system that provides an amount of a metal to the lubricating composition, wherein the metal is at least one of sodium, calcium, magnesium, or a combination thereof, wherein the detergent system comprises 55% to 75% by weight of a calcium-providing detergent additive and 25% to 45% by weight of a magnesium-providing detergent additive; 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; wherein the ratio of phosphorus from said antiwear system to said amount of metal from said detergent system is 0.5 or less; wherein the lubricating composition comprises a total amount of metals such that the composition has a calculated sulfated ash of no more than 0.8 weight percent; and wherein the lubricating composition has less than 30 mg of deposit when subjected to the high temperature deposit formation test of ASTM D6335.

18. The low-ash lubricating composition of claim 17, wherein the lubricating composition comprises no more than 800 ppm phosphorus from the antiwear system and no more than 1800 ppm metals from the detergent system.

19. A method for lubricating an engine with a lubricating composition meeting API SP / ILSAC GF-6 standards, the method comprising lubricating the engine with a lubricating composition comprising one or more base oils of lubricating viscosity; a detergent system that provides an amount of metal to the lubricating composition, wherein the metal is at least one of sodium, calcium, magnesium, or a combination thereof, wherein the detergent system comprises 55% to 75% by weight of a detergent additive that provides calcium and 25% to 45% by weight of a detergent additive that provides magnesium; an antiwear system that comprises one or more metal dialkyl dithiophosphates derived from one of a primary alcohol, a secondary alcohol, or a combination thereof, and provides an amount of phosphorus to the lubricating composition; wherein the lubricating composition has a total base number (TBN) of 0.5 to 20; and wherein the ratio of phosphorus from the antiwear system relative to the TBN of the lubricating composition is 150 or less; and wherein the lubricating composition has a total amount of metals such that when subjected to the high temperature deposit formation test of ASTM D6335, the lubricating composition has no more than 0.8 wt. % calculated sulfated ash and less than 30 mg of sediment.

20. The method of claim 19, wherein the lubricating composition comprises no more than 800 ppm phosphorus from the antiwear system.

21. The method of claim 19, wherein the lubricating composition comprises no more than 1800 ppm total metals from the detergent system.

22. The method of claim 19, wherein the detergent system provides from 10 ppm to 1500 ppm calcium and from 10 ppm to 500 ppm magnesium.

23. The method of claim 19, wherein the total base number of the lubricating composition is less than 10.

24. The method of claim 19, wherein the antiwear system provides 50 ppm to 850 ppm zinc to the lubricating composition, and wherein the amount of zinc from the antiwear system relative to the amount of total metals from the detergent system is 0.6 or less.

Images