Dispersant and detergent systems for improved motor oil performance

Abstract

To provide a passenger car motor oil lubricant composition suitable for improving at least one of deposits, sludge, oxidation, and wear.SOLUTION: A passenger car motor oil lubricant composition comprises: a blend of base oils with lubricant viscosity comprising one or more API Group II base oils, and one or more API Group III base oils and / or one or more API Group IV base oils; an oil-soluble nitrogen-containing dispersant additive comprising (i) at least one boronated oil-soluble nitrogen-containing dispersant additive, and (ii) at least one non-boronated oil-soluble nitrogen-containing dispersant additive; and a metal-containing detergent additive comprising (i) at least one calcium-containing detergent additive, and (ii) at least one magnesium-containing detergent additive, wherein a ratio of dispersant boron, dispersant nitrogen, and dispersant TBN of the passenger car motor oil lubricant composition, as defined by the dispersant formula B / (N*TBN), is less than 0.25.SELECTED DRAWING: Figure 1

Description

[Technical field]

[0001] The present disclosure relates to additive packages for lubricating compositions, particularly dispersant and detergent systems for improved performance in passenger car motor oil lubricating compositions. [Background technology]

[0002] Automotive manufacturers continue to seek improvements in efficiency, fluid life, and fuel economy, which in turn increases the requirements for engines, lubricants, and their components. These requirements also mean that engine oil performance must evolve to meet the higher demands of such modern engines and their corresponding performance standards associated with their unique uses and applications. With such stringent demands on engine oils, lubricant manufacturers often tailor lubricants and their additives to meet certain performance requirements for the industry and / or manufacturer's applications. Typically, industry standards and / or automotive manufacturers require certain performance standards where a lubricant designed for one use or application may not meet all performance specifications of a different use or application.

[0003] The American Petroleum Institute (API) classifies base stocks for lubricants into five groups, with API Groups I, II, and III defining mineral oil base stocks classified by saturates, sulfur, and viscosity index. API Group IV relates to polyalphaolefin base stocks, and API Group V includes all other base stocks. In the context of mineral oil base stocks, it is generally understood that the performance that mineral oil base stocks provide to lubricants increases from Group I to Group III, where API Group III base stocks are more favorable in terms of quality, and Group I and Group II base stocks tend to provide one or more performance losses under modern industrial performance tests. Thus, the trend in the lubricant industry has been to use more API Group III base stocks when formulating lubricants to meet the stringent demands of today's industrial and automotive standards. Summary of the Invention

[0004] The present disclosure relates to passenger car motor oil lubricating compositions suitable for improving at least one of deposits, sludge, oxidation, and wear. In one approach or embodiment, the passenger car motor oil lubricating composition comprises a blend of base oils of lubricating viscosity, comprising one or more API Group II base oils and one or more API Group III base oils, and / or one or more API Group IV base oils; an oil-soluble nitrogen-containing dispersant additive comprising: (i) at least one boronated oil-soluble nitrogen-containing dispersant additive; and (ii) at least one non-boronated oil-soluble nitrogen-containing dispersant additive, the oil-soluble nitrogen-containing dispersant additive providing an amount of dispersant boron (B), an amount of dispersant nitrogen (N), and a dispersant total base number (TBN) to the passenger car motor oil lubricating composition; and a metal-containing detergent additive comprising: (i) at least one calcium-containing detergent additive; and (ii) at least one magnesium-containing detergent additive, the dispersant formula B / (N *The ratio of dispersant boron, dispersant nitrogen, and dispersant TBN, as defined by the dispersant formula B / (N * The total biomass number (TBN) is less than 0.2.

[0005] In other embodiments or approaches, the passenger car motor oil lubricating composition of the preceding paragraph can be combined with the optional features or embodiments in any combination. These optional features or embodiments include one or more of the following: the base oil blend comprises at least about 25 wt.% of one or more API Group II base oils; and / or the base oil blend comprises at least about 50 wt.% of one or more API Group II base oils; and / or the base oil blend is from about 25 to about 80 wt.% of one or more API Group II base oils and from about 20 to about 75 wt.% of one or more API Group III base oils; and / or the oil soluble nitrogen-containing dispersant additive provides the passenger car motor oil lubricating composition with not more than about 250 ppm of dispersant boron; and / or the oil soluble nitrogen-containing dispersant additive provides the passenger car motor oil lubricating composition with not more than about 20 ... meets ASTM the oil-soluble nitrogen-containing dispersant additive has a dispersant TBN of from about 1.0 to about 1.28 mg KOH / g, as measured in accordance with D2896; and / or the at least one boronated oil-soluble nitrogen-containing dispersant additive provides a maximum of about 230 ppm of dispersant boron, and the nitrogen-containing dispersant additive provides a maximum of 700 ppm of dispersant nitrogen; the at least one boronated oil-soluble nitrogen-containing dispersant additive provides a maximum of about 200 ppm of dispersant boron, and the nitrogen-containing dispersant additive provides a maximum of 650 ppm of dispersant nitrogen; and / or the metal-containing detergent additive has an amount of calcium. and / or the metal-containing detergent additive has a weight ratio of calcium soap to magnesium soap of up to about 1.6:1; and / or the metal-containing detergent additive has a weight ratio of calcium soap to magnesium soap of up to about 1.4:1; the metal-containing detergent additive is substantially free of detergent additives providing phenate soaps; and / or the passenger car motor oil lubricating composition has an average engine sludge (AES) of at least about 7.6 Merit as measured in accordance with ASTM D8256; and / or the passenger car motor oil lubricating composition has an average engine sludge (AES) of at least 5.0 Merit as measured in accordance with GMW-17043.and / or the lubricating composition has an average weighted piston deposit of less than 3; and / or further comprises a viscosity index improver having a Shear Stability Index (SSI) of less than 50 as measured in accordance with ASTM D6278; and / or the viscosity index improver is a non-dispersant viscosity index improver selected from polyolefins, olefin copolymers, ethylene / propylene copolymers, polyisobutenes, hydrogenated styrene-isoprene polymers, styrene / maleic ester copolymers, hydrogenated styrene / butadiene copolymers, hydrogenated isoprene polymers, alpha-olefin maleic anhydride copolymers, polymethacrylates, polyacrylates, polyalkylstyrenes, hydrogenated alkenyl aryl conjugated diene copolymers, and mixtures thereof; and / or the lubricating composition has a sulfated ash (SASH) content of about 0.9 weight percent or less as measured in accordance with ASTM D874; and / or the lubricating composition has a SASH content of about 0.9 weight percent or less as measured in accordance with ASTM D874; have a sulfated ash (SASH) content of about 0.8% by weight or less, as measured in accordance with D874; and / or further comprise one or more metal dihydrocarbyl dithiophosphate compounds, the hydrocarbyl groups of which are derived from a mixture of secondary and primary alcohols, the ratio of primary alcohol to secondary alcohol being about 0.3:1 to about 0.6:1; and / or the average number of carbon atoms in the hydrocarbyl groups per primary alcohol is about 0.6:1 or less.

[0006] In another approach or embodiment, the present disclosure provides a method of lubricating an internal combustion engine with a passenger car motor oil, wherein the passenger car motor oil is any embodiment or approach described in this summary.

[0007] In another approach or embodiment, the present disclosure also provides a passenger car motor oil lubricating composition comprising a blend of base oils of lubricating viscosity comprising one or more API Group II base oils and one or more API Group III base oils and / or one or more API Group IV base oils; an oil-soluble nitrogen-containing dispersant additive comprising: (i) at least one boronated oil-soluble nitrogen-containing dispersant additive, and (ii) at least one non-boronated oil-soluble nitrogen-containing dispersant additive, the oil-soluble nitrogen-containing dispersant additive providing an amount of dispersant boron (B), an amount of dispersant nitrogen (N), and a dispersant total base number (TBN) to the passenger car motor oil lubricating composition; and a metal-containing detergent additive comprising: (i) at least one calcium-containing detergent additive, and (ii) at least one magnesium-containing detergent additive, the dispersant formula B / (N * The ratio of dispersant boron, dispersant nitrogen, and dispersant TBN, as defined by the dispersant formula B / (N * and / or to achieve an average weighted piston deposit count of at least 5.3 Merit as measured in accordance with GMW-17043. [Brief description of the drawings]

[0008] [Figure 1] 1 is a graph of average Weighted Piston Deposit (WPD) according to GMW17043 based on weight % of API Group II and Group III base oils in the base oil blend. [Diagram 2] 1 is a graph of average engine sludge (AES) according to ASTM D8256 in 5W-30 passenger car motor oils based on the weight percent of API Group II and Group III base oils in the base oil blend; [Diagram 3]1 is a graph of average engine sludge (AES) according to ASTM D8256 in 0W-20 passenger car motor oils based on the weight percent of API Group II and Group III base oils in the base oil blend; DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0009] This disclosure relates to passenger car motor oils, and in particular to passenger car motor oils that contain increased amounts of API Group II base stocks and still achieve superior performance with respect to deposits, sludge, oxidation, and / or wear according to modern industry performance tests. Surprisingly, it has been discovered that the performance degradation when using less desirable API Group II base oils can be overcome when the selected relationships of boron, nitrogen, and total base number (TBN) provided by oil-soluble nitrogen-containing dispersant additives in lubricating oils are carefully controlled when combined with the less desirable API Group II base oils in a base oil blend.

[0010] In particular, the passenger car motor oil lubricating compositions herein comprise a blend of base oils having lubricating viscosity comprising one or more API Group II base oils in combination with one or more API Group III base oils and / or one or more API Group IV base oils. Preferably, the blend of base oils may comprise at least about 25 wt.% of one or more API Group II base oils, at least about 50 wt.% of one or more API Group II base oils, and more preferably, from about 25 to about 80 wt.% of API Group II base oils and from about 20 to about 75 wt.% of API Group III base oils. Although API Group II base oils have been available for many years, recent requirements of modern engine performance testing, such as the oxidation and deposit test of GMW-17043, the sequence VH engine test of ASTM D8256, which are often required by industry and / or automotive manufacturers, mean that higher levels of API Group II base oils can no longer meet the increased performance demands of these new standards.

[0011] Surprisingly, however, even with higher levels of the less desirable API Group II base oil, the dispersant formula B / (N * It has been found that any performance degradation from the base oil can be overcome when the ratio of dispersant boron (B), dispersant nitrogen (N), and dispersant total base number (TBN), as defined by the total base number (TBN), is about 0.25 or less, preferably about 0.2 or less. In other approaches, the dispersants herein also provide about 250 ppm or less of boron, about 230 ppm or less of boron, or about 200 ppm or less of boron to the passenger car motor oil lubricating composition. The passenger car motor oil lubricating composition herein, even when it contains, for example, a blend of API Group II base oil with API Group III and / or Group IV base oil, still exhibits an average engine sludge (AES) rating of at least about 7.6 Merit according to ASTM D8256, and an average weighted piston deposit (WPD) rating of at least about 5.3 Merit as measured according to GMW-17043.

[0012] Dispersant System The dispersant system of the passenger car motor oil lubricating compositions herein comprises one or more oil-soluble nitrogen-containing compounds. Preferably, the dispersant system comprises (i) at least one or more boronated oil-soluble nitrogen-containing dispersant additives, and (ii) at least one non-boronated oil-soluble nitrogen-containing dispersant additive, the detergent system additives being combined to define the total amount of dispersant boron (B), the total amount of dispersant nitrogen (N), and the dispersant total base number (TBN as measured by ASTM D2896). As noted above, to achieve performance when combined with API Group II base oils, the lubricants herein are formulated according to the formula B / (N * The ratio of dispersant boron (B), dispersant nitrogen (N), and dispersant TBN, as defined by the total boron dioxide (TBN), is less than about 0.25, preferably less than about 0.2, or from about 0.1 to about 0.25, or from about 0.12 to about 0.2.

[0013] In some approaches, the dispersant system provides up to about 250 ppm boron, up to about 230 ppm boron, or up to about 200 ppm boron. In other approaches, the dispersant system may provide from about 100 ppm to about 250 ppm boron, from about 100 ppm to about 230 ppm boron, or from about 100 ppm to about 200 ppm boron.

[0014] In other approaches, the dispersant systems herein may also provide up to about 700 ppm nitrogen, up to about 680 ppm nitrogen, or up to about 650 ppm nitrogen. In other approaches, the dispersant systems herein may provide from about 500 ppm to about 700 ppm nitrogen, from about 500 ppm to about 680 ppm nitrogen, or from about 500 ppm to about 650 ppm nitrogen.

[0015] In yet another approach, the dispersant system herein has a total base number (TBN), as measured according to ASTM D2896, of from about 1.0 to about 1.28 mg KOH / g, or in other approaches, from about 1.0 to about 1.25 mg KOH / g, or from about 1.1 to about 1.2 mg KOH / g.

[0016] Preferably, the borated and non-borated oil-soluble nitrogen-containing compounds of the dispersant system are polyisobutylene succinimide dispersants derived from polyisobutylene having a number average molecular weight of at least about 350, preferably polyisobutylene succinimide dispersants derived from polyisobutylene having a number average molecular weight of from about 1,000 to about 5,000, from about 1,200 to about 3,000, or from about 1,200 to about 2,600. In one approach, the dispersant system herein comprises a blend of (i) at least one borated polyisobutylene succinimide dispersant derived from polyisobutylene having a number average molecular weight of less than 2,000, preferably from about 1,000 to about 1,800, and (ii) at least one non-borated polyisobutylene succinimide dispersant derived from polyisobutylene having a number average molecular weight of more than 2,000, preferably from about 2,000 to about 3,000.

[0017] Oil-soluble nitrogen-containing dispersants are often referred to as ashless dispersants because they do not contain ash-forming metals prior to mixing with the lubricating composition and do not normally contribute to ash when added to the lubricant. Ashless dispersants are characterized in that a polar group is attached to a relatively high molecular weight hydrocarbon chain. Typical ashless dispersants include nitrogen (N-) substituted long chain alkenyl succinimides. Examples of nitrogen substituted long chain alkenyl succinimides include polyisobutylene succinimides having a number average molecular weight of the polyisobutylene substituent in the range of about 350 to about 50,000, or about 5,000, or about 3,000, or about 2,000 to about 3,000, as measured by GPC. As mentioned above, the molecular weight of the polyisobutylene substituent can vary depending on whether the dispersant is boronated or non-boronated. Succinimide dispersants and their preparation are disclosed, for example, in U.S. Patent No. 7,897,696 and U.S. Patent No. 4,234,435, which are incorporated herein by reference. The alkenyl substituents may be prepared from polymerizable monomers containing from about 2 to about 16, or from about 2 to about 8, or from about 2 to about 6 carbon atoms. Succinimide dispersants are typically imides formed from polyamines, typically poly(ethyleneamines).

[0018] In the approach, the preferred amine for the dispersant can be selected from polyamines and hydroxylamines. Examples of polyamines that can be used include, but are not limited to, diethylenetriamine (DETA), triethylenetetramine (TETA), tetraethylenepentamine (TEPA), and higher homologs such as pentaethylaminehexamine (PEHA). In some approaches, so-called heavy polyamines can be used, which are mixtures of polyalkylene-polyamines that contain small amounts of lower polyamine oligomers such as TEPA and PEHA (pentaethylenehexamine), but mainly oligomers with 6 or more nitrogen atoms, 2 or more primary amines per molecule, and more extensive branching than conventional polyamine mixtures. Heavy polyamines preferably include polyamine oligomers that contain 7 or more nitrogen atoms per molecule and have 2 or more primary amines per molecule.

[0019] In some embodiments, when included, polyisobutylene (PIB) is a preferred reactant for forming the dispersant and may have a terminal double bond content of greater than 50 mol%, greater than 60 mol%, greater than 70 mol%, greater than 80 mol%, or greater than 90 mol%. Such PIB is also referred to as highly reactive PIB ("HR-PIB"). HR-PIB having a number average molecular weight in the range of about 800 to about 5000 as determined by GPC is suitable for use in embodiments of the present disclosure. Conventional PIB typically has a terminal double bond content of less than 50 mol%, less than 40 mol%, less than 30 mol%, less than 20 mol%, or less than 10 mol%.

[0020] HR-PIB having a number average molecular weight ranging from about 900 to about 3,000, preferably from about 2,000 to about 3,000, as determined by GPC, may be suitable. Such HR-PIB may be commercially available or may be synthesized by polymerization of isobutene in the presence of a non-chlorinated catalyst such as boron trifluoride, as described in U.S. Pat. Nos. 4,152,499 and 5,739,355. When used in the aforementioned thermal ene reaction, HR-PIB may result in higher conversion in the reaction and less precipitate formation due to increased reactivity. A suitable method is described in U.S. Pat. No. 7,897,696. In one embodiment, the present disclosure further includes at least one dispersant derived from polyisobutylene succinic anhydride ("PIBSA"). The PIBSA may have an average of about 1.0 to about 2.0 succinic acid moieties per polymer.

[0021] As mentioned above, the dispersant system herein includes a blend of post-treated and non-post-treated dispersants. For example, some of the dispersants herein may not include any post-treatment, such as post-treatment with boron, urea, thiourea, dimercaptothiadiazole, carbon disulfide, aldehydes, ketones, carboxylic acids, hydrocarbon-substituted succinic anhydrides, maleic anhydride, nitriles, epoxides, carbonates, cyclic carbonates, hindered phenol esters, and phosphorus compounds. Other dispersants may be post-treated by reaction with any of a variety of agents by conventional methods. Suitable post-treatment agents include boron, urea, thiourea, dimercaptothiadiazole, carbon disulfide, aldehydes, ketones, carboxylic acids, hydrocarbon-substituted succinic anhydrides, maleic anhydride, nitriles, epoxides, carbonates, cyclic carbonates, hindered phenol esters, and phosphorus compounds. (See, e.g., U.S. Pat. Nos. 7,645,726, 7,214,649, 8,048,831, and 5,241,003, all of which are incorporated by reference in their entireties.) Preferably, at least one of the dispersants in the dispersant system herein is post-treated with a boron compound.

[0022] When post-treated with boron, the boron compound used as the post-treating reagent can be selected from boron oxide, boron halides, boric acid, and esters of boric acid in an amount to provide from about 0.1 atomic percentage of boron per mole of nitrogen composition to about 20 atomic percentages of boron for each atomic percentage of nitrogen used. Dispersants post-treated with boron can contain from about 0.05 to about 2.0 weight percent, or in other approaches, from about 0.05 to about 0.7 weight percent, of boron, based on the total weight of the borate dispersant.

[0023] In another approach, when a carboxylic acid post-treating agent is used, it may be optionally used with either the boronated or non-boronated dispersants herein, and the carboxylic acid post-treating agent may be a saturated or unsaturated mono-, di-, or poly-carboxylic acid. Examples of carboxylic acids include, but are not limited to, maleic acid, fumaric acid, succinic acid, and naphthalic diacids (e.g., 1,8-naphthalic diacid). Anhydrides may also be used as post-treating reagents and may be selected from the group consisting of mono-unsaturated anhydrides (e.g., maleic anhydride), alkyl or alkylene substituted cyclic anhydrides (e.g., succinic anhydride or glutamic anhydride), and aromatic carboxylic anhydrides (including naphthalic anhydride, e.g., 1,8-naphthalic anhydride).

[0024] In one embodiment, when a process for post-treating a dispersant is used, the process for post-treating a dispersant includes first forming a succinimide product as described above, and then further reacting the succinimide product with a post-treating agent, such as a boron compound, such as boric acid. In some cases, the dispersants herein may be post-treated with more than one post-treating agent. For example, a dispersant may be post-treated with a boron compound, such as boric acid, and also with an anhydride, such as maleic anhydride and / or 1,8-naphthalic anhydride.

[0025] In embodiments, the passenger car motor oil lubricant combinations herein may contain up to about 10% by weight of individual or combined dispersant additives, or in other approaches, from about 0.1 to about 8% by weight, from about 0.2 to about 6% by weight, or from about 0.2 to about 5% by weight of individual or total dispersant additives. In some embodiments, the dispersant systems herein may have more non-boronated dispersants than boronated dispersants, and the weight ratio of dispersant boron to dispersant nitrogen may be less than 0.3:1, less than about 0.28:1, or less than about 0.25:1. In other approaches, the dispersant systems may have a weight ratio of dispersant boron to dispersant nitrogen of from about 0.15:1 to 0.3:1, from about 0.18:1 to about 0.28:1, or from about 0.2:1 to about 0.25:1.

[0026] Detergents The passenger car motor oil lubricating compositions herein also include a detergent system having one or more metal-containing detergent additives that provide at least about 0.25 wt. % soap to the lubricant. In one approach, the detergent system includes metal-containing detergent additives of (i) at least one calcium-containing detergent additive that provides an amount of calcium soap to the lubricant, and (ii) at least one magnesium-containing detergent additive that provides an amount of magnesium soap to the lubricant. In some approaches, the detergent system provides more calcium soap than magnesium soap to the passenger car motor oil lubricating composition. In other approaches, the metal-containing detergent additives herein may have a weight ratio of calcium soap to magnesium soap of up to about 1.6:1, in other approaches up to about 1.4:1, or from about 1.1:1 to about 1.6:1, or from about 1.2:1 to about 1.4:1.

[0027] In some approaches, the detergent systems herein are substantially free of metal-containing phenate detergents, and thus the detergent systems herein provide the lubricant with substantially no phenate soaps or no phenate soaps. As used herein, "substantially free" generally means no more than about 0.1 wt.%, no more than about 0.05 wt.%, no more than about 0.01 wt.%, or functional amounts of phenate detergents or phenate soaps.

[0028] In one approach or embodiment, the one or more detergent additives include a calcium-containing detergent additive, more preferably a sulfonate-based calcium-providing detergent additive. The one or more detergent additives may also include a magnesium-containing detergent additive, more preferably a sulfonate-based magnesium detergent additive. These selected detergent additives have a total base number (TBN) of at least about 3 mg KOH / g, at least about 4 mg KOH / g, at least about 5 mg KOH / g, or at least about 6 mg KOH / g, as measured according to ASTM D2896, and in another approach or embodiment, the detergents herein provide the lubricant with a TBN of about 10 mg KOH / g or less.

[0029] Suitable detergents and methods for their preparation are described in more detail in numerous patent publications, such as U.S. Patent No. 7,732,390 and the references cited therein, which are incorporated herein by reference. The passenger car motor oil lubricating compositions herein may contain from about 0.1 to about 5 weight percent of each and / or total detergent additive, in other approaches from about 0.15 to about 3 weight percent, and in yet other approaches from about 0.15 to 2.6 weight percent of each and / or total detergent additive, so long as the detergent additive meets the calcium content, magnesium content, and / or soap content described herein.

[0030] In general, suitable detergents in the lubricants herein (meeting the stated calcium content, magnesium content, and / or soap content requirements) may include linear or branched alkali or alkaline earth metal salts, e.g., calcium, sodium, or magnesium, of petroleum sulfonic acids, and long chain mono- or dialkylaryl sulfonic acids in which the aryl groups are benzyl, tolyl, and xylyl, and / or various phenates or derivatives of phenates. Examples of suitable detergents include underbased / neutral and overbased variations of the following detergents, in addition to the requisite amounts of sulfonate soaps listed above: calcium phenate, calcium sulfur-containing phenate, calcium sulfonate, calcium calixarate, calcium salixarate, calcium salicylate, calcium carboxylic acid, calcium phosphate, calcium mono- and / or di-thiophosphate, calcium alkyl phenol, calcium sulfur-bound alkyl phenol compounds, calcium methylene bridged phenol, magnesium phenate, magnesium sulfur-containing phenate, magnesium sulfonate, magnesium calixar ... mu salixarate, magnesium salicylate, magnesium carboxylic acid, magnesium phosphate, magnesium mono- and / or di-thiophosphate, magnesium alkylphenol, magnesium sulfur-bound alkylphenol compound, magnesium methylene bridged phenol, sodium phenate, sodium sulfur-containing phenate, sodium sulfonate, sodium calixarate, sodium salixarate, sodium salicylate, sodium carboxylic acid, sodium phosphate, sodium mono- and / or di-thiophosphate, sodium alkylphenol, sodium sulfur-bound alkylphenol compound, or sodium methylene bridged phenol.

[0031] As will be appreciated, overbased detergent additives are well known in the art and may be alkali or alkaline earth metal overbased detergent additives. Such detergent additives may be prepared by reacting a metal oxide or metal hydroxide with a substrate and carbon dioxide gas. The substrate is typically an acid, such as an aliphatic substituted sulfonic acid, an aliphatic substituted carboxylic acid, or an aliphatic substituted phenol.

[0032] The term "overbased" refers to metal salts in which the amount of metal present exceeds the stoichiometric amount, for example, metal salts of sulfonates, carboxylates, salicylates, and / or phenates. Such salts may have a conversion level of more than 100% (i.e., such salts may contain more than 100% of the theoretical amount of metal required to convert the acid into its "standard salt", "neutral salt"). The expression "metal ratio", often abbreviated as MR, is used to indicate the ratio of the total chemical equivalents of metal in an overbased salt to the chemical equivalents of metal in a neutral salt, according to known chemical reactivity and stoichiometry. In standard or neutral salts, the MR is 1, and in overbased salts, the MR is greater than 1. They are generally referred to as overbased, hyperbased, or superbased salts and may be salts of organic sulfur acids, carboxylic acids, or phenols.

[0033] As used herein, the term "TBN" is used to represent a total base number in units of "mgKOH / g" as measured by the method of ASTM D2896. The detergent may be neutral or overbased. For example, the low-based or neutral detergent herein may have a total base number (TBN) of up to about 250 mgKOH / g, as described above. The overbased detergent that may be provided in the passenger car motor oil and / or finished lubricant formulation herein may have a total base number (TBN) of about 250 mgKOH / g or more, or about 300 mgKOH / g or more, or about 350 mgKOH / g or more, or about 375 mgKOH / g or more, or about 400 mgKOH / g or more. The overbased detergent may have a metal to substrate ratio of 1.1:1 or less, or 2:1 or less, or 4:1 or less, or 5:1 or less, or 7:1 or less, or 10:1 or less, or 12:1 or less, or 15:1 or less, or 20:1 or less.

[0034] Examples of suitable overbased detergents include, but are not limited to, overbased calcium phenate, overbased calcium sulfur-containing phenate, overbased calcium sulfonate, overbased calcium calixarate, overbased calcium salixarate, overbased calcium salicylate, overbased calcium carboxylic acid, overbased calcium phosphate, overbased calcium mono- and / or di-thiophosphate, overbased calcium alkylphenol, overbased calcium sulfur-bound alkylphenol compound, overbased calcium methylene bridged phenol, overbased magnesium phenate, overbased magnesium sulfur-containing phenate, overbased magnesium sulfonate, overbased magnesium calixarate, overbased magnesium salixarate, overbased magnesium salicylate, overbased magnesium carboxylic acid, overbased magnesium phosphate, overbased magnesium mono- and / or di-thiophosphate, overbased magnesium alkylphenol, overbased magnesium sulfur-bound alkylphenol compound, or overbased magnesium methylene bridged phenol. Preferably, the detergents are magnesium and calcium sulfonates and are substantially free of phenate detergents, as described above. More preferably, the detergents of the present invention are overbased magnesium and calcium sulfonates.

[0035] In other embodiments, the TBN of the detergents herein may reflect the neat or undiluted version of the detergent component. For example, the fluids herein may include overbased calcium sulfonate or calcium sulfonate as a neat additive having a TBN of about 300 to about 450, and in other approaches about 380 to about 420.

[0036] In some approaches or embodiments, the detergent systems herein provide the lubricant with at least about 0.25% soap by weight, more preferably from about 0.25% to about 0.4% soap by weight. In some approaches, the soap content is from about 50% to about 60% calcium-based soap and from about 40% to about 60% magnesium-based soap. In other approaches, the metal-containing detergent additives herein may have a weight ratio of calcium soap to magnesium soap of up to about 1.6:1, in other approaches up to about 1.4:1, or from about 1.1:1 to about 1.6:1, or from about 1.2:1 to about 1.4:1.

[0037] Soap content generally refers to the amount of neutral organic acid salts and reflects the cleaning ability or cleaning power of the detergent and its ability to lift dirt. The soap content of a lubricant can be determined by ASTM D3712. Further discussion of the determination of soap content can be found in the relevant portions of FUELS AND LUBRICANTS HANDBOOK, TECHNOLOGY, PROPERTIES, PERFORMANCE, AND TESTING, George Totten, editor, ASTM International, 2003, which are incorporated herein by reference.

[0038] Viscosity index improver The passenger car motor oil lubricant compositions herein may optionally contain one or more viscosity index improvers. Preferably, if any viscosity index improver is used, the viscosity index improver has a shear stability index (SSI) of less than about 50 as measured according to ASTM D6278. In other approaches, the viscosity index improvers of the compositions herein, if used, have an SSI of about 40 or less, about 35 or less, or about 30 or less, and in some approaches, have an SSI of about 25 to about 50, about 25 to about 40, or about 25 to about 25.

[0039] Suitable viscosity index improvers may include polyolefins, olefin copolymers, ethylene / propylene copolymers, polyisobutene, hydrogenated styrene-isoprene polymers, styrene / maleic acid ester copolymers, hydrogenated styrene / butadiene copolymers, hydrogenated isoprene polymers, alpha-olefin maleic anhydride copolymers, polymethacrylates, polyacrylates, polyalkylstyrenes, hydrogenated alkenylaryl conjugated diene copolymers, or mixtures thereof. Viscosity index improvers may include star polymers, suitable examples of which are described in U.S. Patent Application Publication No. 2012 / 0101017(A1).

[0040] Preferably, the viscosity index improver is a non-dispersant viscosity index improver; however, the lubricating oil compositions herein may also optionally contain one or more dispersant viscosity index improvers in addition to the non-dispersant viscosity index improver. Suitable viscosity index improvers may include functionalized polyolefins, such as ethylene-propylene copolymers functionalized with the reaction product of an acylating agent (such as maleic anhydride) and an amine; amine-functionalized polymethacrylates, or esterified maleic anhydride-styrene copolymers reacted with amines.

[0041] The total amount of viscosity index improver and / or dispersant viscosity index improver can be from about 0 to about 20 wt.%, from about 0.1 to about 15 wt.%, from about 0.1 to about 12 wt.%, or from about 0.5 to about 10 wt.%, based on the weight of the passenger car motor oil lubricating composition herein.

[0042] Metal dihydrocarbyl dithiophosphate compounds The passenger car motor oil lubricating compositions herein may optionally contain one or more metal dihydrocarbyl dithiophosphate compounds, such as, but not limited to, zinc dihydrocarbyl dithiophosphate compounds (ZDDP). When one or more metal dihydrocarbyl dithiophosphate compounds are used, the metal dihydrocarbyl dithiophosphate compounds may provide up to about 1,000 ppm phosphorus to the lubricant, up to about 900 ppm phosphorus, or up to about 800 ppm phosphorus, or at least about 200 ppm phosphorus to the lubricant package. When one or more metal dihydrocarbyl dithiophosphate compounds are used in the lubricants herein, the hydrocarbyl groups of the metal dihydrocarbyl dithiophosphate compounds are preferably derived from a mixture of secondary and primary alcohols, with the ratio of primary to secondary alcohol being from about 0.3:1 to about 0.6:1. In another approach, the average number of carbon atoms in the hydrocarbyl groups per primary alcohol can be up to about 0.6:1, preferably from about 0.3:1 to about 0.6:1.

[0043] Suitable metal dihydrocarbyl dithiophosphate compounds, such as ZDDP, may contain 5 to about 10 weight percent metal (e.g., about 6 to about 9 weight percent metal, such as zinc) and about 8 to about 18 weight percent sulfur (e.g., about 12 to about 18 weight percent sulfur, or about 8 to about 15 weight percent sulfur). Suitable metal dihydrocarbyl dithiophosphate compounds may include dihydrocarbyl dithiophosphate metal salts, where the metal may be an alkali metal, alkaline earth metal, aluminum, lead, tin, molybdenum, manganese, nickel, copper, titanium, zirconium, zinc, or combinations thereof. Preferably, the metal is zinc.

[0044] When the metal dihydrocarbyl dithiophosphate compound is used in the passenger car motor oil herein, the alkyl groups on the metal dihydrocarbyl dithiophosphate compound may be derived from a primary alcohol, a secondary alcohol, a phenol, but preferably from a mixture of primary and secondary alcohols. For example, the hydrocarbyl groups may be derived from a mixture of primary and secondary alcohols, including 2-ethylhexanol, methyl isobutyl carbinol (MIBC), isobutanol, and isopropanol. For example, about 60 mole % or more of the alkyl groups may be derived from a primary alcohol (such as, but not limited to, 2-ethylhexanol and / or isobutyl alcohol), and about 40 mole % or less of the alkyl groups may be derived from a secondary alcohol (such as, but not limited to, isopropyl alcohol, methyl isobutyl carbinol, etc., and / or combinations thereof). In an optional approach, all of the alkyl groups on the metal dihydrocarbyl dithiophosphate compound may be derived from a primary alcohol, such as 2-ethylhexanol or others described below. In another optional approach, all of the alkyl groups on the metal dihydrocarbyl dithiophosphate compound may be derived from a secondary alcohol (such as, but not limited to, isopropyl alcohol, or methyl isobutyl carbinol).

[0045] In one approach, the metal dihydrocarbyl dithiophosphate compound of the lubricants herein may be a blend of two ZDDP compounds containing about 40 to about 60 mole percent ethylhexanol and about 40 to about 60 mole percent methyl isobutyl carbinol, and may contain about 6 to about 10 weight percent phosphorus, about 6 to about 9 weight percent zinc, and about 12 to about 18 weight percent sulfur. In another approach, the metal dihydrocarbyl dithiophosphate compound of the passenger car motor oil may be one or more ZDDP compounds derived from 80 to 100 mole percent 2-ethylhexyl alcohol or 80 to 100 mole percent methyl isobutyl carbinol, and may contain about 6 to about 10 weight percent phosphorus, about 6 to about 9 weight percent zinc, and about 12 to about 18 weight percent sulfur. Most preferably, the ZDDP compound of the present invention is a blend of ZDDP compounds, one having 100 mole percent primary alcohol and the other having 100 mole percent secondary alcohol.

[0046] Generally, subject to the above limitations, the metal dihydrocarbyl dithiophosphate compounds of passenger car motor oils may be derived from an alcohol selected from, but not limited to, 2-ethylhexanol, methylheptanol, heptanol, octanol, nonanol, decanol, dodecanol, and / or their isovariants. Examples of suitable metal dihydrocarbyl dithiophosphate compounds include zinc O,O-di(C 8~14 zinc O,O-bis(6-ethylhexyl)dithiophosphate; zinc O,O-dioctyldithiophosphate; zinc O,O-dipentyldithiophosphate; zinc O-(2-methylbutyl)-O-(2-methylpropyl)dithiophosphate; and zinc O-(3-methylbutyl)-O-(2-methylpropyl)dithiophosphate, or combinations thereof.

[0047] In some approaches or embodiments, the metal dihydrocarbyl dithiophosphate compounds suitable for the passenger car motor oils herein have Formula I:

[0048] [ka] (Note that each R in formula I may independently have a structure containing 6-18 carbon atoms, or 6-12 carbon atoms, or about 8-10 carbon atoms, provided that each phosphorus atom has an average of at least 14 total carbons, preferably at least 8 total carbons, or 8-16 total carbons per phosphorus atom). For example, each R may independently be ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl, amyl, n-hexyl, i-hexyl, n-octyl, decyl, dodecyl, octadecyl, 2-ethylhexyl, phenyl, butylphenyl, cyclohexyl, methylcyclopentyl, propenyl, or butenyl. The number of carbon atoms in each R group in the above formula is generally about 3 or more, about 4 or more, about 6 or more, or about 8 or more. Each R group may have an average of 6-10 carbons, preferably 8-10 carbons. Preferably, each R may be a straight or branched chain, C8 or 2-ethylhexyl group, C3 or isopropyl group, and / or C4 or isobutyl group. 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. When the metal dihydrocarbyl dithiophosphate compound has the structure shown in formula I and A is zinc, the compound may have about 4 to about 9 weight percent phosphorus and about 6 to about 9 weight percent zinc, and a zinc to phosphorus ratio of about 1.0 to about 1.5.

[0049] In some approaches or embodiments, it is understood in the art that a more accurate representation of the sulfur-zinc coordination array can be represented by the symmetrical array shown below, and that the chemical structure of formula II that may be used herein is interchangeable with formula I shown above. It is also understood that the structures shown in formulas I and II can exist as monomers, dimers, trimers, or oligomers (e.g., tetramers).

[0050] [ka]

[0051] Dihydrocarbyl dithiophosphate metal salts can be prepared according to known techniques, typically by first forming dihydrocarbyl dithiophosphoric acid (DDPA) by reacting one or more alcohols or phenols with P2S5, and then neutralizing the formed DDPA with a metal compound such as zinc oxide. For example, DDPA can be produced by reacting a mixture of alcohols containing a suitable amount of primary alcohol (and a suitable blend of primary and secondary alcohols, if necessary) with P2S5. In this case, the DDPA contains alkyl groups derived primarily from primary alcohols, or from both primary and secondary alcohols, as necessary to meet the required primary alcohol content in the final product. Alternatively, multiple DDPAs can be prepared, with the alkyl groups on one DDPA derived entirely from secondary alcohols and the alkyl groups on another DDPA derived entirely from primary alcohols. The DDPAs are then blended together to form a mixture of DDPAs with alkyl groups that meet the primary alcohol content described above.

[0052] As noted above, passenger car motor oils can contain blends of metal dihydrocarbyl dithiophosphate compounds derived from primary alcohols and / or secondary alcohols. In one approach, the finished lubricants herein can contain from about 1 to about 5 weight percent of the metal dihydrocarbyl dithiophosphate compounds.

[0053] Base oil or base oil blend: As mentioned above, the base oil herein may be an oil of lubricating viscosity and may be selected from any of API Group I-V base oils as defined in the American Petroleum Institute (API) Base Oil Interchangeability Guidelines, and is preferably a blend of one or more API Group II base oils in combination with API Group III and / or Group IV base oils. More preferably, the base oil is a blend having at least about 25 wt% API Group II base oil, at least about 50 wt% API Group II base oil, or a blend of about 25 to about 80 wt% API Group II base oil in combination with about 20 to about 75 wt% API Group III base oil. In some embodiments, the base oil system herein may have a KV100 of about 2 to about 20 cSt in some approaches or embodiments involving blends of Group II base oils with Group III and / or Group IV base oils, about 5 to about 15 cSt in other approaches, about 8 to about 15 cSt, and about 10 to about 15 cSt in still other approaches. As is well known, the five base oil groups are generally as shown in Table 1 below.

[0054] [Table 1]

[0055] Group I, Group II, and Group III are mineral oil process feedstocks. Group IV base oils contain true synthetic molecular species produced by polymerization of olefinically unsaturated hydrocarbons. Many Group V base oils are also true synthetic products and may include diesters, polyol esters, polyalkylene glycols, alkylated aromatics, polyphosphate esters, polyvinyl ethers, and / or polyphenyl ethers, etc., but may also be natural oils, such as vegetable oils. It should be noted that Group III base oils are derived from mineral oils, but the rigorous processing these fluids undergo makes their physical properties very similar to some true synthetic oils, such as PAOs. Thus, oils derived from Group III base oils may be referred to as synthetic fluids in the industry. Group II+ may include high viscosity index Group II.

[0056] The base oil blends used in the disclosed lubricating oil compositions can be mineral oils, animal oils, vegetable oils, synthetic oils, synthetic oil blends, or mixtures thereof. Suitable oils can be derived from hydrocracked, hydrogenated, hydrofinished, unrefined, refined, and rerefined oils, and mixtures thereof.

[0057] Unrefined oils are derived from natural, mineral, or synthetic sources with little or no further purification treatment. Refined oils are similar to unrefined oils, except that they have been treated with one or more purification steps that may result in the improvement of one or more properties. Examples of suitable purification techniques are solvent extraction, secondary distillation, acid or base extraction, filtration, percolation, etc. Oils refined to edible quality may or may not be useful. Edible oils may also be called white oils. In some embodiments, the lubricating oil composition does not include edible oils or white oils.

[0058] Rerefined oils are also known as reclaimed or reprocessed oils. These oils are obtained similarly to refined oils using the same or similar processes. Often these oils are further processed by techniques directed to the removal of spent additives and oil breakdown products.

[0059] Mineral oils may include oils obtained by drilling, or oils obtained from plants and animals, or any mixture thereof. For example, such oils may include, but are not limited to, castor oil, lard oil, olive oil, peanut oil, corn oil, soybean oil, and linseed oil, as well as mineral lubricating oils, such as liquid petroleum oils, and solvent- or acid-treated mineral lubricating oils of the paraffinic, naphthenic, or mixed paraffinic-naphthenic types. Such oils may be partially or fully hydrogenated, if desired. Oils derived from coal or shale may also be useful.

[0060] Useful synthetic lubricating oils may include hydrocarbon oils such as polymerized, oligomerized, or interpolymerized olefins (e.g., polybutylene, polypropylene, propylene isobutylene copolymers); poly(1-hexene), poly(1-octene), trimers or oligomers of 1-decene, such as poly(1-decene) (such materials are often referred to as alpha-olefins), and mixtures thereof; alkyl-benzenes (e.g., dodecylbenzene, tetradecylbenzene, dinonylbenzene, di-(2-ethylhexyl)-benzene); polyphenyls (e.g., biphenyl, terphenyl, alkylated polyphenyls); diphenylalkanes, alkylated diphenylalkanes, alkylated diphenyl ethers, and alkylated diphenyl sulfides, and derivatives, analogs, and homologs thereof, or mixtures thereof. The polyalphaolefins are typically hydrogenated materials.

[0061] Other synthetic lubricating oils include polyol esters, diesters, liquid esters of phosphorus-containing acids (e.g., tricresyl phosphate, trioctyl phosphate, and the diethyl ester of decane phosphonic acid), or polymeric tetrahydrofurans. Synthetic oils may be produced by the Fischer-Tropsch reaction, but typically are hydroisomerized Fischer-Tropsch hydrocarbons or waxes. In one embodiment, the oils may be prepared by the Fischer-Tropsch gas-liquid synthesis procedure, as well as other gas-liquid oils.

[0062] A major amount of base oil included in the lubricating composition may be selected from the group consisting of Group I, Group II, Group III, Group IV, Group V, and combinations of two or more of the foregoing, but the major amount of base oil is other than the base oil resulting from the provision of an additive component or viscosity index improver in the composition. In another embodiment, a major amount of base oil included in the lubricating composition may be selected from the group consisting of Group II, Group III, Group IV, Group V, and combinations of two or more of the foregoing, but the major amount of base oil is other than the base oil resulting from the provision of an additive component or viscosity index improver in the composition.

[0063] The amount of oil of lubricating viscosity present may be the remainder remaining after subtracting the sum of the amounts of performance additives, including viscosity index improver(s) and / or pour point depressants and / or other top treat additives, from 100% by weight. For example, the oil of lubricating viscosity may be present in the final fluid in a "major amount," such as greater than about 50% by weight, greater than about 60% by weight, greater than about 70% by weight, greater than about 80% by weight, greater than about 85% by weight, or greater than about 90% by weight.

[0064] As generally used herein, the terms "oil composition," "lubricating composition," "lubricating oil composition," "lubricating oil," "lubricant composition," "lubricant," and "lubricant" are considered to be synonymous and fully interchangeable terms and refer to a passenger car motor oil lubrication product containing a major amount of a base oil component having the blending amounts set forth above, plus minor amounts of detergents and other optional components, which may preferably be API GF-6.

[0065] Optional Additives: The passenger car motor oil lubricating compositions herein may also contain a number of optional additives in combination with the above-mentioned detergent and dispersant systems as necessary to meet performance criteria, which optional additives are described in the following paragraphs.

[0066] Other dispersants: The lubricating oil composition may optionally contain one or more other dispersants or mixtures thereof. Dispersants are often referred to as ashless dispersants because they do not contain ash-forming metals prior to mixing with the lubricating oil composition and do not normally contribute ash when added to the lubricant. Ashless dispersants are characterized by having 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 in which the number average molecular weight of the polyisobutylene substituent ranges from about 350 to about 50,000, or from about 5,000, or from about 3,000, as measured by GPC. Succinimide dispersants and their preparation are disclosed, for example, in U.S. Pat. No. 7,897,696 or U.S. Pat. No. 4,234,435. The alkenyl substituent may be prepared from polymerizable monomers containing from about 2 to about 16, or from about 2 to about 8, or from about 2 to about 6 carbon atoms. Succinimide dispersants are typically imides formed from polyamines, typically poly(ethyleneamines).

[0067] 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 homologs such as pentaethylaminehexamine (PEHA).

[0068] Suitable heavy polyamines are mixtures of polyalkylene-polyamines containing small amounts of lower polyamine oligomers such as TEPA and PEHA (pentaethylenehexamine), but primarily oligomers with 6 or more nitrogen atoms, 2 or more primary amines per molecule, and more extensive branching than conventional polyamine mixtures. Heavy polyamines preferably include polyamine oligomers containing 7 or more nitrogen atoms per molecule and having 2 or more primary amines per molecule. Heavy polyamines contain greater than 28% by weight (e.g., greater than 32% by weight) total nitrogen and an equivalent weight of 120 to 160 g of primary amine groups per equivalent.

[0069] In some approaches, suitable polyamines, commonly known as PAM, contain a mixture of ethyleneamines, with TEPA and pentaethylenehexamine (PEHA) being the major portion of the polyamine, usually less than about 80%.

[0070] Typically, PAM has 8.7-8.9 milliequivalents of primary amine per gram (115-112 milliequivalents per equivalent of primary amine) and a total nitrogen content of about 33-34% by weight. Heavier cuts of PAM oligomers that are substantially free of TEPA and contain only small amounts of PEHA, but contain primarily oligomers with more than six nitrogen atoms and more extensive branching, may produce dispersants with improved dispersancy.

[0071] In some embodiments, 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 5,000, or to about 3,000, as determined by GPC. The polyisobutylene succinimide may be used alone or in combination with other dispersants.

[0072] In some embodiments, when polyisobutylene is included, the polyisobutylene may have a terminal double bond content of greater than 50 mol%, greater than 60 mol%, greater than 70 mol%, greater than 80 mol%, or greater than 90 mol%. Such PIB is also referred to as highly reactive PIB ("HR-PIB"). HR-PIB having a number average molecular weight in the range of about 800 to about 5000 as determined by GPC is suitable for use in embodiments of the present disclosure. Conventional PIB typically has a terminal double bond content of less than 50 mol%, less than 40 mol%, less than 30 mol%, less than 20 mol%, or less than 10 mol%.

[0073] HR-PIB having a number average molecular weight in the range of about 900 to about 3000 as determined by GPC may be suitable. Such HR-PIB is commercially available or can be synthesized by polymerization of isobutene in the presence of a non-chlorinated catalyst such as boron trifluoride, as described in U.S. Patent No. 4,152,499 to Boerzel, et al. and U.S. Patent No. 5,739,355 to Gateau, et al. When HR-PIB is used in the thermal ene reaction, it may result in higher conversion during the reaction and less precipitate formation due to increased reactivity. A suitable method is described in U.S. Patent No. 7,897,696.

[0074] In one embodiment, the present disclosure further comprises at least one dispersant derived from polyisobutylene succinic anhydride ("PIBSA"), which may have an average of about 1.0 to about 2.0 succinic acid moieties per polymer.

[0075] The percent actives of the alkenyl or alkyl succinic anhydride can be determined using chromatographic techniques, which are described in U.S. Patent No. 5,334,321, columns 5 and 6.

[0076] Polyolefin conversion is calculated from the percent actives using the formula in columns 5 and 6 of US Pat. No. 5,334,321.

[0077] Unless otherwise specified, 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 (having number average molecular weights of 180 to about 18,000) as calibration standards.

[0078] In one embodiment, the dispersant may be derived from polyalphaolefin (PAO) succinic anhydride. In one embodiment, the dispersant may be derived from an olefin maleic anhydride copolymer. As an example, the dispersant may be described as poly-PIBSA. In one embodiment, the dispersant may be derived from an anhydride grafted to an ethylene-propylene copolymer.

[0079] A suitable class of nitrogen-containing dispersants may be derived from olefin copolymers (OCPs), more specifically ethylene-propylene dispersants that may be grafted with maleic anhydride. A more complete list of nitrogen-containing compounds that may be reacted with functionalized OCPs is described in U.S. Patent Nos. 7,485,603, 7,786,057, 7,253,231, 6,107,257, and 5,075,383, and / or is commercially available.

[0080] One class of suitable dispersants may also be Mannich bases. Mannich bases are materials formed by 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.

[0081] A suitable class of dispersants may also be high molecular weight esters or half ester amides. Suitable dispersants may also be post-treated by reaction with any of a variety of agents by conventional methods. Among these are boron, urea, thiourea, dimercaptothiadiazole, carbon disulfide, aldehydes, ketones, carboxylic acids, hydrocarbon-substituted succinic anhydrides, maleic anhydrides, nitriles, epoxides, carbonates, cyclic carbonates, hindered phenol esters, and phosphorus compounds. U.S. Patent No. 7,645,726, U.S. Patent No. 7,214,649, and U.S. Patent No. 8,048,831 are incorporated herein by reference in their entirety.

[0082] In addition to the carbonate and boric acid post-treatments, any of the compounds may be post-treated or further post-treated with a variety of post-treatments designed to improve or impart different properties. Such post-treatments include those summarized in columns 27-29 of U.S. Pat. No. 5,241,003, which is incorporated herein by reference. Such treatments include treatment with inorganic phosphoric acids or anhydrides (e.g., U.S. Pat. Nos. 3,403,102 and 4,648,980); organic phosphorus compounds (e.g., U.S. Pat. No. 3,502,677); phosphorus pentasulfide; boron compounds as already mentioned above (e.g., U.S. Pat. Nos. 3,178,663 and 4,652,387); carboxylic acids, polycarboxylic acids, anhydrides, and / or acid halides (e.g., U.S. Pat. Nos. 3,708,522 and 4,912,522); and / or carboxylic acids such as carboxylic acids, polycarboxylic acids, anhydrides, and / or acid halides (e.g., U.S. Pat. Nos. 3,708,522 and 4,912,522). 48,386; epoxides, polyepoxyates or thioepoxides (e.g., U.S. Pat. Nos. 3,859,318 and 5,026,495); aldehydes or ketones (e.g., U.S. Pat. No. 3,458,530); carbon disulfide (e.g., U.S. Pat. No. 3,256,185); glycidol (e.g., U.S. Pat. No. 4,617,137); urea, thiourea, or guanidine (e.g., U.S. Pat. No. 3,312,61 9, 3,865,813, and British Patent No. 1,065,595; organic sulfonic acids (e.g., U.S. Pat. No. 3,189,544 and British Patent No. 2,140,811); alkenyl cyanides (e.g., U.S. Pat. Nos. 3,278,550 and 3,366,569); diketenes (e.g., U.S. Pat. No. 3,546,243); diisocyanates (e.g., U.S. Pat. No. 3,573,205); alkanesuls t (e.g., U.S. Pat. No. 3,749,695); 1,3-dicarbonyl compounds (e.g., U.S. Pat. No. 4,579,675); sulfates of alkoxylated alcohols or phenols (e.g., U.S. Pat. No. 3,954,639); cyclic lactones (e.g., U.S. Pat. Nos. 4,617,138; 4,645,515; 4,668,246; 4,963,275; and 4,971,711);Cyclic carbonates or thiocarbonates, linear monocarbonates or polycarbonates, or chloroformates (e.g., U.S. Pat. Nos. 4,612,132, 4,647,390, 4,648,886, 4,670,170); nitrogen-containing carboxylic acids (e.g., U.S. Pat. No. 4,971,598 and British Patent No. 2,140,811); hydroxy-protected chlorodicarbonyloxy compounds (e.g., U.S. Pat. No. 4,614,522); lactams, thiolactams, thiolactones, or dithiolactones (e.g., U.S. Pat. No. 4,612,132, 4,647,390, 4,648,886, 4,670,170); Nos. 4,614,603 and 4,666,460; cyclic carbonates or thiocarbonates, linear monocarbonates or polycarbonates, or chloroformates (e.g., U.S. Pat. Nos. 4,612,132, 4,647,390, 4,646,860, and 4,670,170); nitrogen-containing carboxylic acids (e.g., U.S. Pat. No. 4,971,598 and British Patent No. 2,440,811); hydroxy-protected chlorodicarbonyloxy compounds (e.g., U.S. Pat. No. 4,614,522); lactams, thiocarbonates, etc. olactams, thiolactones, or dithiolactones (e.g., U.S. Pat. Nos. 4,614,603 and 4,666,460); cyclic carbamates, cyclic thiocarbamates, or cyclic dithiocarbamates (e.g., U.S. Pat. Nos. 4,663,062 and 4,666,459); hydroxyaliphatic carboxylic acids (e.g., U.S. Pat. Nos. 4,482,464; 4,521,318; and 4,713,189); oxidizing agents (e.g., U.S. Pat. No. 4,379,064); combinations of phosphorus pentasulfide and polyalkylene polyamines (e.g., U.S. Pat. Nos. 4,379,064); , U.S. Pat. No. 3,185,647; combinations of carboxylic acids or aldehydes or ketones and sulfur or sulfur chlorides (e.g., U.S. Pat. Nos. 3,390,086, 3,470,098); combinations of hydrazine and carbon disulfide (e.g., U.S. Pat. No. 3,519,564); combinations of aldehydes and phenols (e.g., U.S. Pat. Nos. 3,649,229, 5,030,249, 5,039,307); combinations of aldehydes and O-diesters of dithiophosphoric acids (e.g., U.S. Pat. No. 3,865,740);Combinations of hydroxyaliphatic carboxylic acids and boric acid (e.g., U.S. Pat. No. 4,554,086); combinations of hydroxyaliphatic carboxylic acids followed by formaldehyde and phenols (e.g., U.S. Pat. No. 4,636,322); combinations of hydroxyaliphatic carboxylic acids and then aliphatic dicarboxylic acids (e.g., U.S. Pat. No. 4,663,064); combinations of formaldehyde and phenols and then glycolic acid (e.g., U.S. Pat. No. 4,699,724); combinations of hydroxyaliphatic carboxylic acids or oxalic acid followed by a diisocyanate (e.g., U.S. Pat. No. 4,713,191); inorganic acids or anhydrides of phosphorus. or a combination of its partial or total sulfur analogue and a boron compound (e.g., U.S. Pat. No. 4,857,214); a combination of an organic diacid, followed by an unsaturated fatty acid, followed by a nitrosoaromatic amine, optionally followed by a boron compound, and then a glycosylation agent (e.g., U.S. Pat. No. 4,973,412); a combination of an aldehyde and a triazole (e.g., U.S. Pat. No. 4,963,278); a combination of an aldehyde and a triazole, followed by a boron compound (e.g., U.S. Pat. No. 4,981,492); a combination of a cyclic lactone and a boron compound (e.g., U.S. Pat. Nos. 4,963,275 and 4,971,711). The above-mentioned patents are hereby incorporated in their entirety;

[0083] The TBN of suitable dispersants may be from about 10 to about 65 mg KOH / g on an oil-free basis, which equates to about 5 to about 30 TBN when measured on a dispersant sample containing about 50% diluent oil. TBN is measured by the method of ASTM D2896.

[0084] In yet another embodiment, the optional dispersant additive may be a hydrocarbyl-substituted succinamide or succinimide dispersant. In some approaches, the hydrocarbyl-substituted succinamide or succinimide dispersant may be derived from a hydrocarbyl-substituted acylating agent reacted with a polyalkylene polyamine, where 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 the calibration standard.

[0085] In some approaches, the polyalkylene polyamine used to form the dispersant has the following formula:

[0086] [ka] where each R and R' is independently a divalent C1-C6 alkylene linker, and each R1 and R2 is independently hydrogen, a C1-C6 alkyl group, or together with the nitrogen atom to which they are attached form a 5- or 6-membered ring optionally fused to one or more aromatic or non-aromatic rings, and n is an integer from 0 to 8. In another approach, the polyalkylene polyamine is selected from the group consisting of a mixture of polyethylene polyamines having an average of 5 to 7 nitrogen atoms, triethylenetetramine, tetraethylenepentamine, and combinations thereof.

[0087] Dispersants, when present, may be used in an amount sufficient to provide up to about 20% by weight, based on the final weight of the lubricating oil composition. Alternative amounts of dispersants that may be used may be from about 0.1 to about 15% by weight, or from about 0.1 to about 10% by weight, or from about 0.1 to about 8% by weight, or from about 1 to about 10% by weight, or from about 1 to about 8% by weight, or from about 1 to about 6% by weight, 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 or a mixture of two or more types of dispersants in any desired ratio may be used.

[0088] Other antioxidants: The lubricating oil compositions herein may also optionally contain one or more antioxidants. Antioxidant compounds are known and include, for example, phenates, phenate sulfides, sulfurized olefins, phosphosulfurized terpenes, sulfurized esters, aromatic amines, alkylated diphenylamines (e.g., nonyldiphenylamine, di-nonyldiphenylamine, octyldiphenylamine, di-octyldiphenylamine), phenyl-alpha-naphthylamines, alkylated phenyl-alpha-naphthylamines, hindered non-aromatic amines, phenols, hindered phenols, oil-soluble molybdenum compounds, polymeric antioxidants, or mixtures thereof. The antioxidant compounds may be used alone or in combination.

[0089] The hindered phenol antioxidant may contain secondary butyl and / or tertiary butyl groups as steric hindrance groups. The phenol group may be further substituted with a hydrocarbyl group and / or a bridging group that connects to another 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, but may include, for example, Irganox™ L-135 available from BASF or an addition product derived from 2,6-di-tert-butylphenol and an alkyl acrylate. Additionally, 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, which may be an ester, may include Ethanox™ 4716 available from Albemarle Corporation.

[0090] Useful antioxidants may include diarylamines and high molecular weight phenols. In one embodiment, the lubricating oil composition may contain a mixture of diarylamines and high molecular weight phenols, such that each antioxidant may be present in an amount sufficient to provide up to about 5 wt. %, based on the final weight of the lubricating oil composition. In one embodiment, the antioxidant may be a mixture of about 0.3 to about 1.5 wt. % diarylamines and about 0.4 to about 2.5 wt. % high molecular weight phenols, based on the final weight of the lubricating oil composition.

[0091] Examples of suitable olefins that can be sulfurized to form sulfurized olefins include propylene, butylene, isobutylene, polyisobutylene, pentene, hexene, heptene, octene, nonene, decene, undecene, dodecene, tridecene, tetradecene, pentadecene, hexadecene, heptadecene, octadecene, nonadecene, eicosene, or mixtures thereof. In one embodiment, hexadecene, heptadecene, octadecene, nonadecene, eicosene, or mixtures thereof, as well as their dimers, trimers, and tetramers, are particularly useful olefins. Alternatively, the olefins can be Diels-Alder adducts of dienes such as 1,3-butadiene and unsaturated esters such as butyl acrylate.

[0092] Another class of sulfurized olefins includes sulfurized fatty acids and their esters. The fatty acids are often derived from vegetable or animal oils and typically contain from about 4 to about 22 carbon atoms. Examples of suitable fatty acids and their esters include triglycerides, oleic acid, linoleic acid, palmitoleic acid, or mixtures thereof. Often, the fatty acids are derived from lard oil, tall oil, peanut oil, soybean oil, cottonseed oil, sunflower seed oil, or mixtures thereof. The fatty acids and / or esters may be mixed with olefins, such as α-olefins.

[0093] In another alternative embodiment, the antioxidant composition contains a molybdenum-containing antioxidant in addition to the phenolic and / or aminic antioxidants discussed above. When a combination of these three antioxidants is used, preferably the treat rate ratio of the phenolic to the amine to the molybdenum-containing components is (0-3):(0-3):(0-3).

[0094] The one or more antioxidants may be present in the range of from about 0 to about 20 weight percent, or from about 0.1 to about 10 weight percent, or from about 1 to about 5 weight percent of the lubricating oil composition.

[0095] Other antiwear agents: The lubricating oil compositions herein may also optionally contain one or more antiwear agents. Examples of suitable antiwear agents include, but are not limited to, metal thiophosphates; metal dialkyldithiophosphates; phosphate esters or salts thereof; phosphate ester(s); phosphites; phosphorus-containing carboxylic esters, ethers, or amides; sulfurized olefins; thiocarbamate-containing compounds, such as thiocarbamate esters, alkylene-linked thiocarbamates, and bis(S-alkyldithiocarbamyl) disulfides; and mixtures thereof. A suitable antiwear agent may be molybdenum dithiocarbamate. Phosphorus-containing antiwear agents are more fully described in EP 612839. The metal in the dialkyldithiophosphate salt may be an alkali metal, alkaline earth metal, aluminum, lead, tin, molybdenum, manganese, nickel, copper, titanium, or zinc. A useful antiwear agent may be zinc dialkyldithiophosphate.

[0096] Further examples of suitable antiwear agents include titanium compounds, tartrates, tartrimides, oil-soluble amine salts of phosphorus compounds, sulfurized olefins, phosphites (e.g., dibutyl phosphite), phosphonates, thiocarbamate-containing compounds such as thiocarbamate esters, thiocarbamate amides, thiocarbamic acid ethers, alkylene-linked thiocarbamates, and bis(S-alkyldithiocarbamyl) disulfides. The tartrates or tartrimides may contain alkyl-ester groups, but the total of carbon atoms on the alkyl group may be at least 8. The antiwear agent may, in one embodiment, include citrates.

[0097] The antiwear agent may be present in ranges including from about 0 to about 15 weight percent, or from about 0.01 to about 10 weight percent, or from about 0.05 to about 5 weight percent, or from about 0.1 to about 3 weight percent of the lubricating oil composition.

[0098] Boron-containing compounds: The lubricating oil compositions herein may optionally contain one or more boron-containing compounds. Examples of boron-containing compounds include borate esters, borated fatty amines, borated epoxides, borated detergents, and borated dispersants, such as borated succinimide dispersants, as disclosed in U.S. Pat. No. 5,883,057. The boron-containing compounds, when present, may be used in an amount sufficient to provide up to about 8% by weight, about 0.01 to about 7% by weight, about 0.05 to about 5% by weight, or about 0.1 to about 3% by weight of the lubricating oil composition.

[0099] Other detergents: The lubricating oil composition may optionally further comprise one or more neutral, low-based, or overbased detergents, and mixtures thereof. Suitable detergent substrates include phenates, sulfur-containing phenates, sulfonates, calixarates, salixarates, salicylates, carboxylic acids, phosphoric acids, mono- and / or di-thiophosphoric acids, alkylphenols, sulfur-linked alkylphenol compounds, or methylene-bridged phenols. Suitable detergents and their preparation methods are described in more detail in numerous patent publications, including U.S. Pat. No. 7,732,390 and references cited therein.

[0100] The detergent substrate may be salified with an alkali 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 may contain trace amounts of other metals, such as magnesium or calcium, in amounts such as 50 ppm or less, 40 ppm or less, 30 ppm or less, 20 ppm or less, or 10 ppm or less. Suitable detergents may include alkali or alkaline earth metal salts of petroleum sulfonic acids and long chain mono- or di-alkylaryl sulfonic acids, where the aryl groups are benzyl, tolyl, and xylyl. Examples of suitable detergents include, but are not limited to, calcium phenate, calcium sulfur-containing phenate, calcium sulfonate, calcium calixarate, calcium salixarate, calcium salicylate, calcium carboxylic acid, calcium phosphoric acid, calcium mono- and / or di-thiophosphoric acid, calcium alkyl phenol, calcium sulfur-bound alkyl phenol compound, calcium methylene bridged phenol, magnesium phenate, magnesium sulfur-containing phenate, magnesium sulfonate, magnesium calixarate, magnesium salixarate, magnesium salicylate, magnesium carboxylic acid, magnesium phosphoric acid, magnesium mono- and / or di-thiophosphoric acid, magnesium alkyl phenol, magnesium sulfur-bound alkyl phenol compound, magnesium methylene bridged phenol, sodium phenate, sodium sulfonate, sodium calixarate, sodium salixarate, sodium salicylate, sodium carboxylic acid, sodium phosphoric acid, sodium mono- and / or di-thiophosphoric acid, sodium alkyl phenol, sodium sulfur-bound alkyl phenol compound, or sodium methylene bridged phenol.

[0101] Overbased detergent additives are well known in the art and may be alkali or alkaline earth metal overbased detergent additives. Such detergent additives may be prepared by reacting a metal oxide or metal hydroxide with a substrate and carbon dioxide gas. The substrate is typically an acid, such as an aliphatic substituted sulfonic acid, an aliphatic substituted carboxylic acid, or an aliphatic substituted phenol.

[0102] The term "overbased" refers to metal salts, such as metal salts of sulfonates, carboxylates, and phenates, in which the amount of metal present exceeds the stoichiometric amount. Such salts may have a conversion level of more than 100% (i.e., such salts may contain more than 100% of the theoretical amount of metal required to convert the acid to its "standard" or "neutral" salt). The expression "metal ratio", often abbreviated as MR, is used to indicate the ratio of the total chemical equivalents of the metal in an overbased salt to the chemical equivalents of the metal in a neutral salt, according to known chemical reactivity and stoichiometry. In standard or neutral salts, the metal ratio (MR) is 1, whereas in overbased salts, the MR is greater than 1. They are generally referred to as overbased, hyperbased, or superbased salts, and may be salts of organic sulfur acids, carboxylic acids, or phenols.

[0103] The overbased detergent of the lubricating oil composition may have a Total Base Number (TBN) of about 200 mg KOH / g or greater, or, as a further example, about 250 mg KOH / g or greater, or about 350 mg KOH / g or greater, or about 375 mg KOH / g or greater, or about 400 mg KOH / g or greater, as measured by the method of ASTM D2896.

[0104] Examples of suitable overbased detergents include, but are not limited to, overbased calcium phenate, overbased calcium sulfur-containing phenate, overbased calcium sulfonate, overbased calcium calixarate, overbased calcium salixarate, overbased calcium salicylate, overbased calcium carboxylic acid, overbased calcium phosphate, overbased calcium mono- and / or di-thiophosphate, overbased calcium alkylphenol, overbased calcium sulfur-bound alkylphenol compound, overbased calcium methylene bridged phenol, overbased magnesium phenate, overbased magnesium sulfur-containing phenate, overbased magnesium sulfonate, overbased magnesium calixarate, overbased magnesium salixarate, overbased magnesium salicylate, overbased magnesium carboxylic acid, overbased magnesium phosphate, overbased magnesium mono- and / or di-thiophosphate, overbased magnesium alkylphenol, overbased magnesium sulfur-bound alkylphenol compound, or overbased magnesium methylene bridged phenol.

[0105] The overbased calcium phenate detergents have a total base number of at least about 150 mg KOH / g, at least about 225 mg KOH / g, at least about 225 to about 400 mg KOH / g, at least about 225 to about 350 mg KOH / g, or about 230 to about 350 mg KOH / g, all measured by the method of ASTM D 2896. When such detergent compositions are formed in an inert diluent, such as a process oil, usually a mineral oil, the total base number reflects the basicity of the entire composition, including the diluent and any other materials that may be included in the detergent composition (e.g., accelerators, etc.).

[0106] The overbased detergent may have a metal to substrate ratio of 1.1:1 or greater, or 2:1 or greater, or 4:1 or greater, or 5:1 or greater, or 7:1 or greater, or 10:1 or greater. In some embodiments, the detergent is effective in reducing or preventing rust in engines or other automotive components such as transmissions or gears. The detergent may be present in the lubricating composition from about 0 to about 10 wt%, or from about 0.1 to about 8 wt%, or from about 1 to about 4 wt%, or from greater than about 4 wt% to about 8 wt%.

[0107] Extreme Pressure Agents: The lubricating oil compositions herein may also optionally contain one or more extreme pressure agents. Extreme pressure (EP) agents that are soluble in oil include sulfur and chlorosulfur containing EP agents, chlorinated hydrocarbon EP agents, and phosphorus EP agents. Examples of such EP agents include chlorinated waxes; organic sulfides and polysulfides such as dibenzyl disulfide, bis(chlorobenzyl) disulfide, dibutyl tetrasulfide, sulfurized methyl ester of oleic acid, sulfurized alkylphenols, sulfurized dipentenes, sulfurized terpenes, and sulfurized Diels-Alder adducts; phosphorus sulfurized hydrocarbons such as the reaction products of phosphorus sulfide with turpentine or methyl oleate; dihydrocarbyl and trihydrocarbyl phosphites, for example, phosphate esters such as dibutyl phosphite, diheptyl phosphite, dicyclohexyl phosphite, pentyl phenyl phosphite; dipentyl phenyl phosphite, tridecyl phosphite, distearyl phosphite, and polypropylene substituted phenyl phosphites; metal thiocarbamates such as zinc dioctyldithiocarbamate and barium heptylphenol diacid; amine salts of alkyl and dialkyl phosphates, including, for example, the amine salt of the reaction product of a dialkyl dithiophosphoric acid with propylene oxide; and mixtures thereof.

[0108] Friction modifiers: The lubricating oil compositions herein may also optionally contain one or more friction modifiers. Suitable friction modifiers may include metal-containing and metal-free friction modifiers, but may include, but are not limited to, imidazolines, amides, amines, succinimides, alkoxylated amines, alkoxylated ether amines, amine oxides, amidoamines, nitriles, betaines, quaternary amines, imines, amine salts, aminoguanidines, alkanolamides, phosphonates, metal-containing compounds, glycerol esters, sulfurized fatty compounds and olefins, sunflower oil, other naturally occurring vegetable or animal oils, dicarboxylic acid esters, esters or partial esters of polyols with one or more aliphatic or aromatic carboxylic acids, and the like.

[0109] Suitable friction modifiers may contain hydrocarbyl groups selected from linear, branched, or aromatic hydrocarbyl groups, or mixtures thereof, and may be saturated or unsaturated. The hydrocarbyl groups may be composed of carbon and hydrogen or heteroatoms such as sulfur or oxygen. The hydrocarbyl groups may range from about 12 to about 25 carbon atoms. In some embodiments, the friction modifier may be a long chain fatty acid ester. In other embodiments, the long chain fatty acid ester may be a mono-ester, or a di-ester, or a (tri)glyceride. The friction modifier may be a long chain fatty amide, a long chain fatty ester, a long chain fatty epoxide derivative, or a long chain imidazoline.

[0110] Other suitable friction modifiers may include organic, ashless (metal-free), nitrogen-free mechanical friction modifiers. Such friction modifiers include esters formed by reacting carboxylic acids and anhydrides with alkanols, and may generally include polar end groups (e.g., carboxyl or hydroxyl) covalently bonded to an oleophilic hydrocarbon chain. An example of an organic ashless nitrogen-free friction modifier is generally known as glycerol monooleate (GMO), which may include mono-, di-, and tri-esters of oleic acid. Other suitable friction modifiers are described in U.S. Patent No. 6,723,685, the entirety of which is incorporated herein by reference.

[0111] Aminic friction modifiers may include amines or polyamines. Such compounds may have hydrocarbyl groups that are linear, either saturated or unsaturated, or a mixture thereof, and may contain from about 12 to about 25 carbon atoms. Further examples of suitable friction modifiers include alkoxylated amines and alkoxylated ether amines. Such compounds may have hydrocarbyl groups that are linear, either saturated or unsaturated, or a mixture thereof. They may contain from about 12 to about 25 carbon atoms. Examples include ethoxylated amines and ethoxylated ether amines.

[0112] The amines and amides may be used by themselves or in the form of adducts or reaction products with boron compounds such as boron oxides, boron halides, metaborates, boric acid or mono-, di-, or tri-alkyl borates. Other suitable friction modifiers are described in U.S. Patent No. 6,300,291, which is incorporated herein by reference in its entirety.

[0113] Friction modifiers may optionally be present in a range such as from about 0 to about 10 weight percent, or from about 0.01 to about 8 weight percent, or from about 0.1 to about 4 weight percent.

[0114] Molybdenum-containing components: The lubricating oil compositions herein may also optionally contain one or more molybdenum-containing compounds. The oil-soluble molybdenum compounds may have the functional properties of antiwear agents, antioxidants, friction modifiers, or mixtures thereof. The oil-soluble molybdenum compounds may include molybdenum dithiocarbamates, molybdenum dialkyldithiophosphates, molybdenum dithiophosphinates, amine salts of molybdenum compounds, molybdenum xanthates, molybdenum thioxanthates, molybdenum sulfides, molybdenum carboxylates, molybdenum alkoxides, trinuclear organomolybdenum compounds, and / or mixtures thereof. Molybdenum sulfides include molybdenum disulfide. The molybdenum disulfide may be in the form of a stable dispersion. In one embodiment, the oil-soluble molybdenum compounds may be selected from the group consisting of molybdenum dithiocarbamates, molybdenum dialkyldithiophosphates, amine salts of molybdenum compounds, and mixtures thereof. In one embodiment, the oil soluble molybdenum compound can be a molybdenum dithiocarbamate.

[0115] Suitable examples of molybdenum compounds that may be used include commercially available materials sold under trade names such as Molyvan® 822, Molyvan® A, Molyvan® 2000, Molyvan® 855, Molyvan® 1055, and Molyvan® 3000 manufactured by R.T. Vanderbilt Co., Ltd., and Adeka Sakura-Lube® S-165, S-200, S-300, S-310G, S-525, S-600, S-700, and S-710 available from Adeka Corporation, and mixtures thereof. Suitable molybdenum components are described in U.S. Pat. No. 5,650,381, U.S. Reissue Pat. Nos. 37,363 (E1), 38,929 (E1), and 40,595 (E1), the entireties of which are incorporated herein by reference.

[0116] Additionally, the molybdenum compound can be an acidic molybdenum compound, including molybdic acid, ammonium molybdate, sodium molybdate, potassium molybdate, and other alkali metal molybdates and other molybdenum salts, such as sodium hydrogen molybdate, MoOCl4, MoO2Br2, Mo2O3Cl6, molybdenum trioxide, or similar acidic molybdenum compounds. Alternatively, the composition can provide the molybdenum via molybdenum / sulfur complexes of basic nitrogen compounds, as described, for example, in U.S. Pat. Nos. 4,263,152, 4,285,822, 4,283,295, 4,272,387, 4,265,773, 4,261,843, 4,259,195, and 4,259,194, and WO 94 / 06897, the foregoing patents being incorporated herein by reference in their entireties.

[0117] Another class of suitable organo-molybdenum compounds is the trinuclear molybdenum compounds, e.g., those of the formula MoS k L n Q z and mixtures thereof, where S represents sulfur, L represents an independently selected ligand having an organic group having a sufficient number of carbon atoms to render the compound soluble or dispersible in oil, n is 1-4, k varies from 4-7, Q is selected from the group of neutral electron donor compounds, such as water, amines, alcohols, phosphines, and ethers, and z ranges from 0-5, including non-stoichiometric values. There may be at least 21 total carbon atoms in the organic groups of all the ligands, such as at least 25, at least 30, or at least 35 carbon atoms. Additional suitable molybdenum compounds are described in U.S. Pat. No. 6,723,685, which is incorporated herein by reference in its entirety.

[0118] The oil soluble molybdenum compound may be present in an amount sufficient to provide from about 0.5 to about 2000 ppm, from about 1 to about 700 ppm, from about 1 to about 550 ppm, from about 5 to about 300 ppm, or from about 20 to about 250 ppm of molybdenum.

[0119] Transition metal-containing compounds: In another embodiment, the oil-soluble compound may be a transition metal-containing compound or metalloid. Transition metals may include, but are not limited to, titanium, vanadium, copper, zinc, zirconium, molybdenum, tantalum, tungsten, etc. Suitable metalloids include, but are not limited to, boron, silicon, antimony, tellurium, etc.

[0120] In some embodiments, the oil-soluble transition metal-containing compound may function as an antiwear agent, a friction modifier, an antioxidant, an adhesion control additive, or two or more of these functions. In some embodiments, the oil-soluble transition metal-containing compound may be an oil-soluble titanium compound, such as titanium (IV) alkoxide. Among the titanium-containing compounds that may be used in or for the preparation of the oil-soluble material of the technology of the present disclosure, include various Ti (IV) compounds, such as titanium (IV) oxide; titanium (IV) sulfide; titanium (IV) nitrate; titanium (IV) alkoxides, such as titanium methoxide, titanium ethoxide, titanium propoxide, titanium isopropoxide, titanium butoxide, titanium 2-ethylhexoxide; and other titanium compounds or complexes, such as, but not limited to, titanium phenate; titanium carboxylates, such as titanium (IV) 2-ethyl-1,3-hexanedioate or titanium citrate or titanium oleate; and titanium (IV) (triethanolaminato) isopropoxide. Other forms of titanium encompassed by the disclosed technology include titanium phosphates, such as titanium dithiophosphates (e.g., dialkyl dithiophosphates) and titanium sulfonates (e.g., alkyl benzene sulfonates), or generally reaction products of titanium compounds with various acidic materials to form salts, such as oil-soluble salts. Thus, titanium compounds may be derived from organic acids, alcohols, and glycols, among others. Ti compounds may also exist in dimeric or oligomeric forms containing Ti-O-Ti structures. Such titanium materials are commercially available or can be readily prepared by suitable synthetic techniques that will be apparent to those skilled in the art. They may exist at room temperature as solids or liquids, depending on the particular compound. They may also be provided in solution form in a suitable inert solvent.

[0121] In one embodiment, titanium may be provided as a Ti-modified dispersant, such as a succinimide dispersant. Such materials may 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 may be used directly or may be reacted with any of several materials, such as (a) polyamine-based succinimide / amide dispersants having free condensable -NH functional groups; (b) components of polyamine-based succinimide / amide dispersants, i.e., alkenyl (or alkyl) succinic anhydrides and polyamines; (c) hydroxy-containing polyester dispersants prepared by reaction of substituted succinic anhydrides with polyols, amino alcohols, polyamines, or mixtures thereof. Alternatively, the titanate-succinate intermediate can be reacted with other agents such as alcohols, amino alcohols, ether alcohols, polyether alcohols or polyols, or fatty acids, and the product can be used directly to impart Ti to lubricants or can be further reacted with succinic dispersants as described above. As an example, one part (mol) of tetraisopropyl titanate can be reacted with about two parts (mol) of polyisobutene-substituted succinic anhydride at 140-150°C for 5-6 hours to provide a titanium modified dispersant or intermediate. The resulting material (30g) can be further reacted with a succinimide dispersant from a polyisobutene-substituted succinic anhydride and polyethylene polyamine mixture (127g + diluent oil) at 150°C for 1.5 hours to produce a titanium modified succinimide dispersant.

[0122] Another titanium-containing compound is titanium alkoxide and C6-C 25 It may be a reaction product with a carboxylic acid. The reaction product has the following formula:

[0123] [ka] wherein n is an integer selected from 2, 3, and 4, and R is a hydrocarbyl group containing from about 5 to about 24 carbon atoms, or the following formula:

[0124] [ka] (wherein m+n=4, n ranges from 1 to 3, R4 is an alkyl moiety having from 1 to 8 carbon atoms, R1 is selected from hydrocarbyl groups containing from about 6 to 25 carbon atoms, and R2 and R3 are the same or different and are selected from hydrocarbyl groups containing from 1 to 6 carbon atoms). Alternatively, the titanium compound may be represented by the following formula:

[0125] [ka] (wherein x ranges from 0 to 3; R1 is selected from hydrocarbyl groups containing about 6 to 25 carbon atoms; R2 and R3 are the same or different and are selected from hydrocarbyl groups containing about 1 to 6 carbon atoms; R4 is H, C6-C 25 The carboxylic acid moiety may be selected from the group consisting of

[0126] Suitable carboxylic acids may include, but are not limited to, caproic acid, caprylic acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachic acid, oleic acid, erucic acid, linoleic acid, linolenic acid, cyclohexanecarboxylic acid, phenylacetic acid, benzoic acid, neodecanoic acid, and the like.

[0127] In one embodiment, the oil-soluble titanium compound may be present in the lubricating oil composition in an amount to provide from about 0 to about 3000 ppm by weight of titanium, or from 25 to about 1500 ppm by weight of titanium, or from about 35 to about 500 ppm by weight of titanium, or from about 50 to about 300 ppm by weight of titanium.

[0128] 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, polyisobutene, hydrogenated styrene-isoprene polymers, styrene / maleic acid ester copolymers, hydrogenated styrene / butadiene copolymers, hydrogenated isoprene polymers, alpha-olefin maleic anhydride copolymers, polymethacrylates, polyacrylates, polyalkylstyrenes, hydrogenated alkenylaryl conjugated diene copolymers, or mixtures thereof. Viscosity index improvers may include star polymers, suitable examples of which are described in U.S. Patent Application Publication No. 2012 / 0101017(A1).

[0129] The lubricating oil compositions herein may also optionally contain one or more dispersant viscosity index improvers in addition to or instead of the viscosity index improver. Suitable viscosity index improvers may include functionalized polyolefins, such as ethylene-propylene copolymers functionalized with the reaction product of an acylating agent (such as maleic anhydride) with an amine; amine-functionalized polymethacrylates; or esterified maleic anhydride-styrene copolymers reacted with an amine.

[0130] The total amount of viscosity index improver and / or dispersant viscosity index improver can be from about 0 to about 20 weight percent, from about 0.1 to about 15 weight percent, from about 0.1 to about 12 weight percent, or from about 0.5 to about 10 weight percent of the lubricating oil composition.

[0131] Other optional additives: Other additives may be selected to perform one or more functions required in a lubricating fluid. Additionally, one or more of the aforementioned additives may be multifunctional, providing functions in addition to or other than those described herein.

[0132] The lubricating oil composition according to the present disclosure may optionally contain other performance additives. The other performance additives may be in addition to the specific additives of the present disclosure and / or may include one or more of metal deactivators, viscosity index improvers, detergents, ashless TBN boosters, friction modifiers, antiwear agents, corrosion inhibitors, rust inhibitors, dispersants, dispersant viscosity index improvers, extreme pressure agents, antioxidants, foam suppressants, demulsifiers, emulsifiers, pour point depressants, seal swell agents, and mixtures thereof. Typically, a fully formulated lubricating oil will contain one or more of these performance additives.

[0133] Suitable metal deactivators may include derivatives of benzotriazole (typically tolyltriazole), dimercaptothiadiazole derivatives, 1,2,4-triazole, benzimidazole, 2-alkyldithiobenzimidazole, or 2-alkyldithiobenzothiazole; foam suppressors including copolymers of ethyl acrylate 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.

[0134] Suitable suds suppressors include silicon-based compounds such as siloxanes.

[0135] Suitable pour point depressants may include polymethyl methacrylate or mixtures thereof. The pour point depressant may be present in an amount sufficient to provide from about 0 to about 1 wt. %, from about 0.01 to about 0.5 wt. %, or from about 0.02 to about 0.04 wt. %, based on the final weight of the lubricating oil composition.

[0136] A suitable rust inhibitor can be a single compound or a mixture of compounds that have the property of inhibiting corrosion of ferrous metal surfaces. Non-limiting examples of rust inhibitors useful herein include oil-soluble high molecular weight organic acids such as 2-ethylhexanoic acid, lauric acid, myristic acid, palmitic acid, oleic acid, linoleic acid, linolenic acid, behenic acid, and cerotic acid, as well as oil-soluble polycarboxylic acids including dimer and trimer acids such as those produced from tall oil fatty acids, oleic acid, and linoleic acid. Other suitable corrosion inhibitors include long chain alpha, omega-dicarboxylic acids in the molecular weight range of about 600 to about 3000, and alkenyl succinic acids in which the alkenyl group contains about 10 or more carbon atoms, such as tetrapropenyl succinic acid, tetradecenyl succinic acid, and hexadecenyl succinic acid. Another useful class of acidic corrosion inhibitors are the half esters of alkenyl succinic acids having about 8 to about 24 carbon atoms in the alkenyl group with alcohols such as polyglycols. The corresponding half amides of such alkenyl succinic acids are also useful.Useful rust inhibitors are high molecular weight organic acids.

[0137] When present, the rust inhibitor may be used in an amount sufficient to provide from about 0 to about 5 wt. %, from about 0.01 to about 3 wt. %, from about 0.1 to about 2 wt. %, based on the final weight of the lubricating oil composition.

[0138] Generally speaking, suitable lubricants containing detergent metals herein may contain additive components in the ranges listed in the table below.

[0139] [Table 2]

[0140] The percentages of each component above represent the weight percent of each component based on the weight of the final lubricant composition. The remainder of the lubricant composition consists of one or more base oils. The additives used in formulating the compositions described herein may be blended into the base oil individually or in various partial combinations. However, it may be preferred to blend all of the components simultaneously using an additive concentrate (i.e., additives plus a diluent such as a hydrocarbon solvent). Fully formulated lubricants conventionally contain an additive package, referred to herein as a dispersant / inhibitor package or DI package, that provides the characteristics required in the formulation.

[0141] definition For purposes of this disclosure, the chemical elements are identified according to the Periodic Table of the Elements, CAS version, Handbook of Chemistry and Physics, 75th Ed. Additionally, general principles of organic chemistry are described in "Organic Chemistry", Thomas Sorrell, University Science Books, Sausolito: 1999, and "March's Advanced Organic Chemistry", 5th Ed., Ed.: Smith, M. B. and March, J., John Wiley & Sons, New York: 2001, the entire contents of which are incorporated herein by reference.

[0142] As described herein, compounds may be optionally substituted with one or more substituents as illustrated generally above, or as illustrated by the specific classes, subclasses, and species of the present disclosure.

[0143] Unless otherwise clear from the context, the term "major amount" is understood to mean an amount of 50% by weight or more, for example, about 80 to about 98% by weight, based on the total weight of the composition. Also, as used herein, the term "minor amount" is understood to mean an amount of less than 50% by weight, based on the total weight of the composition.

[0144] As used herein, the term "hydrocarbyl group" or "hydrocarbyl" is used in its ordinary sense, well known to those skilled in the art. Specifically, it refers to a group having a carbon atom directly attached to the remainder of the molecule and having predominantly hydrocarbon character. Examples of hydrocarbyl groups include: (1) hydrocarbon substituents, i.e., aliphatic (e.g., alkyl or alkenyl), alicyclic (e.g., cycloalkyl, cycloalkenyl) and aromatic, aliphatic and alicyclic substituted aromatic substituents, as well as cyclic substituents in which a ring is completed through another portion of the molecule (e.g., two substituents taken together form an alicyclic radical); (2) substituted hydrocarbon substituents, i.e., substituents containing non-hydrocarbon groups (e.g., halo (especially chloro and fluoro), hydroxy, alkoxy, mercapto, alkylmercapto, nitro, nitroso, amino, alkylamino, and sulfoxy) that do not alter the predominantly hydrocarbon substituent in the context of this disclosure; (3) hetero substituents, i.e., substituents that, while having predominantly hydrocarbon character in the context of this disclosure, contain other than carbon in the ring or chain or are otherwise composed of carbon atoms. Heteroatoms include sulfur, oxygen, and nitrogen, and encompass such substituents as pyridyl, furyl, thienyl, and imidazolyl. Generally, no more than 2, or as a further example, only one non-hydrocarbon substituent will be present for every 10 carbon atoms in the hydrocarbyl group, and in some embodiments, there will be no non-hydrocarbon substituents in the hydrocarbyl group.

[0145] As used herein, the term "aliphatic" encompasses the terms alkyl, alkenyl, alkynyl, each of which is optionally substituted as described below.

[0146] As used herein, an "alkyl" group refers to a saturated aliphatic hydrocarbon group containing 1 to 12 (e.g., 1 to 8, 1 to 6, or 1 to 4) carbon atoms. The alkyl group can be straight or branched chain. Examples of alkyl groups include, but are not limited to, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, n-heptyl, or 2-ethylhexyl. An alkyl group can have one or more substituents, such as halo, phospho, alicyclic [e.g., cycloalkyl or cycloalkenyl], heteroalicyclic [e.g., heterocycloalkyl or heterocycloalkenyl], aryl, heteroaryl, alkoxy, aroyl, heteroaroyl, acyl [e.g., (aliphatic)carbonyl, (alicyclic)carbonyl, or (heteroalicyclic)carbonyl], nitro, cyano, amido [e.g., (cycloalkylalkyl)carbonylamino, arylcarbonylamino, aralkylcarbonylamino, (heterocycloalkyl)carbonylamino, (heterocycloalkylalkyl)carbonylamino, heteroarylcarbonylamino, heteroaralkylcarbonylamino,

[0046] The aryloxy group may be substituted (i.e., optionally substituted) with alkylaminocarbonyl, cycloalkylaminocarbonyl, heterocycloalkylaminocarbonyl, arylaminocarbonyl, or heteroarylaminocarbonyl], amino, [e.g., aliphatic amino, alicyclic amino, or heteroalicyclic amino], sulfonyl [e.g., aliphatic -SO2-], sulfinyl, sulfanyl, sulfoxy, urea, thiourea, sulfamoyl, sulfamido, oxo, carboxy, carbamoyl, alicyclicoxy, heterocycloaliphaticoxy, aryloxy, heteroaryloxy, aralkyloxy, heteroarylalkoxy, alkoxycarbonyl, alkylcarbonyloxy, or hydroxy.Without being limiting, some examples of substituted alkyl include carboxyalkyl (e.g., HOOC-alkyl, alkoxycarbonylalkyl, and alkylcarbonyloxyalkyl), cyanoalkyl, hydroxyalkyl, alkoxyalkyl, acylalkyl, aralkyl, (alkoxyaryl)alkyl, (sulfonylamino)alkyl (e.g., (alkyl-SO2-amino)alkyl), aminoalkyl, amidoalkyl, (alicyclic)alkyl, or haloalkyl.

[0147] As used herein, an "alkenyl" group refers to an aliphatic carbon group containing 2 to 8 (e.g., 2 to 12, 2 to 6, or 2 to 4) carbon atoms and at least one double bond. Like an alkyl group, an alkenyl group can be straight or branched chain. Examples of alkenyl groups include, but are not limited to, allyl, isoprenyl, 2-butenyl, and 2-hexenyl. An alkenyl group can have one or more substituents, such as halo, phospho, alicyclic [e.g., cycloalkyl or cycloalkenyl], heteroalicyclic [e.g., heterocycloalkyl or heterocycloalkenyl], aryl, heteroaryl, alkoxy, aroyl, heteroaroyl, acyl [e.g., (aliphatic)carbonyl, (alicyclic)carbonyl, or (heteroalicyclic)carbonyl], nitro, cyano, amido [e.g., (cycloalkylalkyl)carbonylamino, arylcarbonylamino, aralkylcarbonylamino, (heterocycloalkyl)carbonylamino, (heterocycloalkylalkyl)carbonylamino, heteroarylcarbonylamino, heteroaralkylcarbonylaminoalkylaminocarbonyl], or heteroarylcarbonylamino. nyl, cycloalkylaminocarbonyl, heterocycloalkylaminocarbonyl, arylaminocarbonyl, or heteroarylaminocarbonyl], amino, [e.g., aliphatic amino, alicyclic amino, heteroalicyclic amino, or aliphatic sulfonylamino], sulfonyl [e.g., alkyl-SO2-, alicyclic-SO2-, or aryl-SO2-], sulfinyl, sulfanyl, sulfoxy, urea, thiourea, sulfamoyl, sulfamido, oxo, carboxy, carbamoyl, alicyclicoxy, heteroalicyclicoxy, aryloxy, heteroaryloxy, aralkyloxy, heteroaralkoxy, alkoxycarbonyl, alkylcarbonyloxy, or hydroxy. Without limitation, some examples of substituted alkenyls include cyanoalkenyl, alkoxyalkenyl, acylalkenyl, hydroxyalkenyl, aralkenyl, (alkoxyaryl)alkenyl, (sulfonylamino)alkenyl (e.g., (alkyl-SO2-amino)alkenyl), aminoalkenyl, amidoalkenyl, (alicyclic)alkenyl, or haloalkenyl.

[0148] As used herein, an "alkynyl" group refers to an aliphatic carbon group containing 2 to 8 (e.g., 2 to 12, 2 to 6, or 2 to 4) carbon atoms and having at least one triple bond. Alkynyl groups can be straight or branched chain. Examples of alkynyl groups include, but are not limited to, propargyl and butynyl. Alkynyl groups can be substituted with one or more substituents, such as, for example, aroyl, heteroaroyl, alkoxy, cycloalkyloxy, heterocycloalkyloxy, aryloxy, heteroaryloxy, aralkyloxy, nitro, carboxy, cyano, halo, hydroxy, sulfo, mercapto, sulfanyl [e.g., aliphatic sulfanyl or cycloaliphatic sulfanyl], sulfinyl [e.g., aliphatic sulfinyl or cycloaliphatic finyl], sulfonyl [e.g., aliphatic -SO2-, aliphatic amino-SO2-, or cycloaliphatic -SO2-], amido [e.g., aminocarbonyl, alkylaminocarbonyl, alkylcarbonylamino, cycloalkylaminocarbonyl, heterocycloalkylaminocarbonyl, cycloalkylcarbonylamino, aryl and optionally substituted with aminocarbonyl, arylcarbonylamino, aralkylcarbonylamino, (heterocycloalkyl)carbonylamino, (cycloalkylalkyl)carbonylamino, heteroaralkylcarbonylamino, heteroarylcarbonylamino, or heteroarylaminocarbonyl], urea, thiourea, sulfamoyl, sulfamido, alkoxycarbonyl, alkylcarbonyloxy, alicyclic, heteroalicyclic, aryl, heteroaryl, acyl [e.g., (alicyclic)carbonyl or (heteroalicyclic)carbonyl], amino [e.g., aliphatic amino], sulfoxy, oxo, carboxy, carbamoyl, (alicyclic)oxy, (heteroalicyclic)oxy, or (heteroaryl)alkoxy.

[0149] As used herein, an "amino" group refers to an -NR X R Y In the formula, R X and R YEach of is independently hydrogen, alkyl, cycloalkyl, (cycloalkyl)alkyl, aryl, aralkyl, heterocycloalkyl, (heterocycloalkyl)alkyl, heteroaryl, carboxy, sulfanyl, sulfinyl, sulfonyl, (alkyl)carbonyl, (cycloalkyl)carbonyl, ((cycloalkyl)alkyl)carbonyl, arylcarbonyl, (aralkyl)carbonyl, (heterocycloalkyl)carbonyl, ((heterocycloalkyl)alkyl)carbonyl, (heteroaryl)carbonyl, or (heteroaralkyl)carbonyl, each of which is defined herein and optionally substituted. Examples of amino groups include alkylamino, dialkylamino, or arylamino. When the term "amino" is not a terminal group (e.g., alkylcarbonylamino), it is not limited to -NR X - Represented by R X is as defined above.

[0150] As used herein, a "cycloalkyl" group refers to a saturated carbocyclic monocyclic or bicyclic (fused or bridged) ring of 3 to 10 (e.g., 5 to 10) carbon atoms. Examples of cycloalkyl groups include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, adamantyl, norbornyl, cubyl, octahydroindenyl, decahydronaphthyl, bicyclo[3.2.1]octyl, bicyclo[2.2.2]octyl, bicyclo[3.3.1]nonyl, bicyclo[3.3.2.]decyl, bicyclo[2.2.2]octyl, adamantyl, or ((aminocarbonyl)cycloalkyl)cycloalkyl.

[0151] As used herein, a "heterocycloalkyl" group refers to a 3- to 10-membered mono- or bicyclic (fused or bridged) (e.g., 5- to 10-membered mono- or bicyclic) saturated ring structure in which one or more of the ring atoms is a heteroatom (e.g., N, O, S, or combinations thereof). Examples of heterocycloalkyl groups include piperidyl, piperazyl, tetrahydropyranyl, tetrahydrofuryl, 1,4-dioxolanyl, 1,4-dithianyl, 1,3-dioxolanyl, oxazolidyl, isoxazolidyl, morpholinyl, thiomorpholyl, octahydrobenzofuryl, octahydrochromenyl, octahydrothiochromenyl, octahydroindolyl, octahydropyrindinyl, decahydroquinolinyl, octahydrobenzo[b]thiophenyl, 2-oxa-bicyclo[2.2.2]octyl, 1-aza-bicyclo[2.2.2]octyl, 3-aza-bicyclo[3.2.1]octyl, and 2,6-dioxa-tricyclo[3.3.1.0]nonyl. Monocyclic heterocycloalkyl groups can be fused with a phenyl moiety to form structures such as tetrahydroisoquinoline, which would be classified as heteroaryls.

[0152] As used herein, a "heteroaryl" group refers to a monocyclic, bicyclic, or tricyclic ring system having 4 to 15 ring atoms, where one or more ring atoms are heteroatoms (e.g., N, O, S, or combinations thereof), and the monocyclic ring system is aromatic, or at least one of the rings in the bicyclic or tricyclic ring system is aromatic. Heteroaryl groups include benzo-fused ring systems having 2 to 3 rings. For example, benzo-fused groups include benzo fused to one or two 4-8 membered heterocyclic aliphatic moieties (e.g., indolisyl, indolyl, isoindolyl, 3H-indolyl, indolinyl, benzo[b]furyl, benzo[b]thiophenyl, quinolinyl, or isoquinolinyl). Some examples of heteroaryl are pyridyl, 1H-indazolyl, furyl, pyrrolyl, thienyl, thiazolyl, oxazolyl, imidazolyl, tetrazolyl, benzofuryl, isoquinolinyl, benzthiazolyl, xanthene, thioxanthene, phenothiazine, dihydroindole, benzo[1,3]dioxole, benzo[b]furyl, benzo[b]thiophenyl, indazolyl, benzimidazolyl, benzthiazolyl, puryl, cinnolyl, quinolyl, quinazolyl, cinnolyl, phthalazyl, quinazolyl, quinoxalyl, isoquinolyl, 4H-quinolidyl, benzo-1,2,5-thiadiazole, or 1,8-naphthyridyl.

[0153] Monocyclic heteroaryls include, but are not limited to, furyl, thiophenyl, 2H-pyrrolyl, pyrrolyl, oxazolyl, thazolyl, imidazolyl, pyrazolyl, isoxazolyl, isothiazolyl, 1,3,4-thiadiazolyl, 2H-pyranyl, 4-H-pyranyl, pyridyl, pyridazyl, pyrimidyl, pyrazolyl, pyrazyl, or 1,3,5-triazyl. Monocyclic heteroaryls are numbered according to standard chemical nomenclature.

[0154] Bicyclic heteroaryls include indolizyl, indolyl, isoindolyl, 3H-indolyl, indolinyl, benzo[b]furyl, benzo[b]thiophenyl, quinolinyl, isoquinolinyl, indolizinyl, isoindolyl, indolyl, benzo[b]furyl, bexo[b]thiophenyl, indazolyl, benzimidazyl, benzthiazolyl, purinyl, 4H-quinolizyl, quinolyl, isoquinolyl, cinnolyl, phthalazyl, quinazolyl, quinoxalyl, 1,8-naphthyridyl, or pteridyl. Bicyclic heteroaryls are numbered according to standard chemical nomenclature.

[0155] As used herein, the term "treat rate" refers to the weight percentage of a component in a finished lubricant or passenger car motor oil.

[0156] Weight average molecular weight (Mw) and number average molecular weight (Mn) may be determined using a gel permeation chromatography (GPC) instrument from Waters or similar instrumentation and Waters Empower Software or similar software. The GPC instrument may be provided with a Waters separation module and a Waters refractive index detector (or similar optional instrumentation). GPC operating conditions may include a guard column, four Agilent PLgel columns (length 300×7.5 mm, particle size 5μ, and pore size range 100-10000 Å), and a column temperature of about 40° C. Non-stabilized HPLC grade tetrahydrofuran (THF) may be used as the solvent at a flow rate of 1.0 mL / min. The GPC instrument may be calibrated with commercially available poly(methyl methacrylate) (PMMA) standards with narrow molecular weight distributions ranging from 960 to 1,568,000 g / mol. The calibration curve may be extrapolated for samples with masses less than 500 g / mol. Samples and PMMA standards are dissolved in THF and prepared at concentrations of 0.1-0.5% by weight and can be used without filtration. GPC measurements are also described in U.S. Pat. No. 5,266,223, which is incorporated herein by reference. The GPC method also provides molecular weight distribution information. See, for example, W.W. Yau, J.J. Kirkland and D.D. Ly, "Modern Size Exclusion Liquid Chromatography", John Wiley and Sons, New York, 1979, which is incorporated herein by reference. EXAMPLES

[0157] A better understanding of the present disclosure and its many advantages can be made clear with the following examples. The following examples are illustrative and are not intended to limit it in scope or spirit. Those skilled in the art will readily understand that variations of the components, methods, steps, and devices described in these examples can be used. Unless otherwise stated or clear from the context of the following examples and discussion throughout this disclosure, all percentages, ratios, and parts described in this disclosure are by weight. Herein, KV100 was measured according to ASTM D445.

[0158] Example 1 Additive packages of the present invention and comparative additive packages were prepared for lubricants containing the following dispersants, detergents, ZDDPs, and viscosity index improvers. Polyisobutylene succinimide dispersant A, derived from a highly reactive polyisobutylene having a number average molecular weight of about 2000 to about 2600 and having about 1.5% by weight of nitrogen. Polyisobutylene succinimide dispersion B derived from a highly reactive polyisobutylene having a number average molecular weight of about 1200 to about 1800 and having about 1.6% by weight of nitrogen, which has been post-treated with maleic anhydride and a boron source such that the dispersion has about 0.8% by weight of boron. ·An overbased magnesium sulfonate detergent with a TBN of 400 and a soap content of approximately 29%. ·An overbased calcium sulfonate detergent with a TBN of 300 and a soap content of about 26%. ·ZDDP-A is a zinc dialkyldithiophosphate, which contains alkyl groups derived from secondary alcohols. ·ZDDP-B Zinc dialkyldithiophosphates, containing alkyl groups derived from primary alcohols.

[0159] In addition to the components listed above, the comparative additive package and the additive package of the present invention in this example also contained other common additives suitable for passenger car motor oils and were the same for each additive package evaluated. The only difference in the additive packages in this example were the components listed above to derive the fluid relationships in Table 3 below.

[0160] [Table 3] NOTE: TBN was measured according to ASTM D2896, SASH was measured according to ASTM D874, and soap content was measured according to ASTM D3712.

[0161] Example 2 The inventive additive package of Example 1 and the comparative additive package were formulated into passenger car motor oil lubricating compositions having API Group II base oil and / or Group III base oil. The lubricants were then evaluated for average engine sludge merit according to the Sequence VH test of ASTM D8256 and average weighted piston deposits according to the General Motors Oxidization and Deposit (GMOD) test of GMW-17043. The test results for the lubricants, base oil blends, and fluids are shown below in Table 4 (GMOD) and Table 5 (Sequence VH) and in Figures 1-3.

[0162] [Table 4]

[0163] As shown in Table 4 and FIG. 1, when the comparative additive package was used in a 5W-30 lubricant with 100% API Group III oil, the 5W-30 lubricant had a lower level of piston deposits as evidenced by a higher WPD merit score (i.e., a higher WPD merit reflects a cleaner piston with fewer deposits according to GMW-17043). When the comparative additive package was used in a 5W-30 lubricant with a blend of API Group II and Group III base oils, piston deposits increased as evidenced by a lower WPD merit score. However, when the additive package of the present invention was used with a blend of API Group II and Group III base oils, surprisingly, piston cleanliness increased and the WPD merit score was comparable to the lubricant with 100% Group III base oil.

[0164] [Table 5]

[0165] The results in Table 5 above and shown in Figures 2 and 3 show that when the additive package of the present invention was used in a 5W-30 lubricant or a 0W-20 lubricant comprising a blend of API Group II and Group III base oils, the lubricants of the present invention had average engine sludge (AES) ratings that were comparable to, and in some cases surprisingly better than, lubricants having only the higher quality Group III base oils.

[0166] It should be noted that, as used in this specification and the appended claims, the singular forms "a," "an," and "the" include plural referents unless expressly and unambiguously limited to one referent. Thus, for example, reference to an "antioxidant" includes two or more different antioxidants. As used herein, the term "comprising" and grammatical variations thereof are intended to be open-ended such that the recitation of items in a list excludes other similar items that may be substituted for or added to the items in the list.

[0167] For purposes of this specification and the appended claims, unless otherwise indicated, all numbers expressing quantities, percentages or proportions, and other numerical values ​​used in the specification and claims should be understood in all instances to be modified by the term "about". Accordingly, unless indicated to the contrary, the numerical parameters set forth in the following specification and the appended claims are approximations that may vary depending on the desired properties sought to be obtained by the present disclosure. At the very least, and not as an approach to limiting the application of the doctrine of equivalents to the scope of the claims, each numerical parameter should at least be construed in light of the number of reported significant digits and by applying ordinary rounding techniques.

[0168] It is understood that each component, compound, substituent, or parameter disclosed herein should be construed as disclosed for use alone or in combination with one or more of any and all other components, compounds, substituents, or parameters disclosed herein.

[0169] It is further to be understood that each range disclosed herein should be construed as a disclosure of each specific value within the disclosed range having the same number of significant digits. Thus, for example, a range of 1 to 4 should be construed as an explicit disclosure of not only the values ​​1, 2, 3, and 4, but any range of such values.

[0170] It is further understood that each lower limit of each range disclosed herein should be interpreted as being disclosed in combination with each upper limit of each range and each specific value within each range disclosed herein for the same component, compound, substituent, or parameter. Thus, the present disclosure should be interpreted as a disclosure of all ranges derived by combining each lower limit of each range with each upper limit of each range or each specific value within each range, or by combining each upper limit of each range with each specific value within each range. That is, it is further understood that any range between the endpoint values ​​within the broad range is also contemplated herein. Thus, a range of 1 to 4 also means a range of 1 to 3, 1 to 2, 2 to 4, 2 to 3, etc.

[0171] Furthermore, a specific amount / value of a component, compound, substituent, or parameter disclosed in the description or examples should be construed as a disclosure of either a lower or upper limit of a range and therefore can be combined with any other lower or upper limit of a range or specific amount / value for the same component, compound, substituent, or parameter disclosed elsewhere in this application to form a range for that component, compound, substituent, or parameter.

[0172] While particular embodiments have been described, alternatives, modifications, variations, improvements, and substantial equivalents may occur that are not presently anticipated or that cannot be currently anticipated by the applicants or others skilled in the art. It is therefore intended that the appended claims as filed, and the appended claims as they may be amended, cover all such alternatives, modifications, variations, improvements, and substantial equivalents.

Claims

1. 1. A passenger car motor oil lubricating composition suitable for improving at least one of deposits, sludge, oxidation, and wear, comprising: a blend of base oils of lubricating viscosity comprising one or more API Group II base oils, and one or more API Group III base oils and / or one or more API Group IV base oils; an oil-soluble nitrogen-containing dispersant additive comprising: (i) at least one boronated oil-soluble nitrogen-containing dispersant additive; and (ii) at least one non-boronated oil-soluble nitrogen-containing dispersant additive, said oil-soluble nitrogen-containing dispersant additive providing an amount of dispersant boron (B), an amount of dispersant nitrogen (N), and a dispersant total base number (TBN) to said passenger car motor oil lubricating composition; (i) at least one calcium-containing cleaning additive; and (ii) at least one magnesium-containing cleaning additive; The passenger car motor oil lubricating composition has a dispersant formula B / (N ＊ 1. A passenger car motor oil lubricating composition, comprising: a ratio of said dispersant boron, said dispersant nitrogen, and said dispersant TBN, defined as: dispersant boron, said dispersant nitrogen, and said dispersant TBN, of less than 0.

25.

2. The dispersant formula B / (N ＊ 2. The passenger car motor oil lubricating composition of claim 1, wherein the total bulk weight (TBN) is less than 0.

2.

3. 2. The passenger car motor oil lubricating composition of claim 1, wherein the blend of base oils comprises at least about 25 wt.% of said one or more API Group II base oils, and / or the blend of base oils comprises at least about 50 wt.% of said one or more API Group II base oils, and / or the blend of base oils is from about 25 to about 80 wt.% of said one or more API Group II base oils and from about 20 to about 75 wt.% of said one or more API Group III base oils.

4. 2. The passenger car motor oil lubricating composition of claim 1, wherein said oil-soluble nitrogen-containing dispersant additive provides not more than about 250 ppm of said dispersant boron to said passenger car motor oil lubricating composition and / or said oil-soluble nitrogen-containing dispersant additive provides not more than about 200 ppm of said dispersant boron to said passenger car motor oil lubricating composition.

5. 5. The passenger car motor oil lubricating composition of claim 4, wherein said dispersant TBN of said oil-soluble nitrogen-containing dispersant additive is from about 1.0 to about 1.28 mg KOH / g, as measured in accordance with ASTM D2896.

6. 2. The passenger car motor oil lubricating composition of claim 1, wherein said at least one boronated oil-soluble nitrogen-containing dispersant additive provides up to 230 ppm of dispersant boron and said nitrogen-containing dispersant additive provides up to 700 ppm of dispersant nitrogen.

7. 3. The passenger car motor oil lubricating composition of claim 2, wherein said at least one boronated oil-soluble nitrogen-containing dispersant additive provides up to 200 ppm of dispersant boron and said nitrogen-containing dispersant additive provides up to 650 ppm of dispersant nitrogen.

8. 10. The passenger car motor oil lubricating composition of claim 1, wherein the metal-containing detergent additive provides an amount of calcium soaps and an amount of magnesium soaps to the passenger car motor oil lubricating composition, the passenger car motor oil lubricating composition having more calcium soaps than magnesium soaps.

9. 9. The passenger car motor oil lubricating composition of claim 8, wherein the metal-containing detergent additive has a weight ratio of the calcium soaps to the magnesium soaps of up to about 1.6:1, and / or the metal-containing detergent additive has a weight ratio of the calcium soaps to the magnesium soaps of up to about 1.4:1; and / or the metal-containing detergent additive is substantially free of detergent additives that provide phenate soaps.

10. 2. The passenger car motor oil lubricating composition of claim 1, wherein the passenger car motor oil lubricating composition has an average engine sludge (AES) of at least about 7.6 Merit as measured according to ASTM D8256, and / or the passenger car motor oil lubricating composition has an average weighted piston deposits of at least 5.3 Merit as measured according to GMW-17043.

11. 10. The passenger car motor oil lubricating composition of claim 1, further comprising a viscosity index improver having a shear stability index (SSI) of less than 50 as measured according to ASTM D6278.

12. 12. The passenger car motor oil lubricating composition of claim 11, wherein the viscosity index improver is a non-dispersant viscosity index improver selected from polyolefins, olefin copolymers, ethylene / propylene copolymers, polyisobutene, hydrogenated styrene-isoprene polymers, styrene / maleic ester copolymers, hydrogenated styrene / butadiene copolymers, hydrogenated isoprene polymers, alpha-olefin maleic anhydride copolymers, polymethacrylates, polyacrylates, polyalkylstyrenes, hydrogenated alkenyl aryl conjugated diene copolymers, and mixtures thereof.

13. 10. The passenger car motor oil lubricating composition of claim 1, wherein the lubricating composition has a sulfated ash (SASH) content of about 0.9 weight percent or less, as measured in accordance with ASTM D874.

14. 10. The passenger car motor oil lubricating composition of claim 1, wherein the lubricating composition has a sulfated ash (SASH) content of about 0.8 weight percent or less, as measured in accordance with ASTM D874.

15. 2. The passenger car motor oil lubricating composition of claim 1, further comprising one or more metal dihydrocarbyl dithiophosphate compounds, wherein the hydrocarbyl groups are derived from a mixture of secondary and primary alcohols, the ratio of the primary alcohol to the secondary alcohol being from about 0.3:1 to about 0.6:1, and / or the average number of carbon atoms in the hydrocarbyl groups per primary alcohol is about 0.6:1 or less.

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