Magnesium sulfonate detergent having improved compatibility with friction modifier

Abstract

To provide a process for preparing an overbased magnesium sulfonate detergent having improved compatibility with a friction modifier, and the overbased magnesium sulfonate detergent.SOLUTION: A process comprises: (a) preparing a mixture of a C14-C24 alkylarylsulfonic acid or a salt thereof, magnesium oxide or magnesium hydroxide, and one or more branched C8-C16 carboxylic acids; (b) carbonating the mixture to form an overbased magnesium sulfonate; and (c) treating the carbonated overbased magnesium sulfonate with about 6 to about 10 wt.% of a hydrocarbyl-substituted succinic acid or anhydride thereof at about 160°C to about 200°C. The hydrocarbyl substituent is derived from polyisobutylene having a number-average molecular weight of about 900 to about 1500 and more than 50 mol% of terminal double bonds, thereby forming the overbased magnesium sulfonate detergent.SELECTED DRAWING: None

Description

Technical Field

[0001] The present disclosure generally relates to lubricating oil compositions having improved compatibility with friction modifiers and magnesium sulfonate detergents therefor.

Background Art

[0002] Magnesium sulfonate is often used as a detergent in lubricating oil compositions for passenger cars and other vehicles. The detergent is often used in an overbased form, which is a compound having a stoichiometric excess of magnesium compared to the amount required to neutralize the sulfonic acid. However, conventional overbased magnesium sulfonate detergents tend to have compatibility issues with other additives commonly used in lubricants in some situations. For example, overbased magnesium sulfonate detergents can have compatibility issues with common friction modifiers, particularly glycerol monooleate, resulting in dropout, precipitation, and / or film formation in the oil composition. Thus, when a lubricating composition contains both an overbased magnesium sulfonate and a friction modifier such as glycerol monooleate, the loading rate of one or both of such components is often limited. Since it is often desired to increase the level of friction modifier to improve fuel efficiency, the compatibility issue of these two components tends to be a limiting factor in improving the performance of the lubricating composition.

Summary of the Invention

[0003] According to one embodiment, a process for preparing a magnesium overbased sulfonate detergent having improved compatibility with a friction modifier is described herein. In one aspect, the process comprises: (a) preparing a mixture of a C14-C24 alkylaryl sulfonic acid or a salt thereof, magnesium oxide or magnesium hydroxide, and one or more branched C8-C16 carboxylic acids; (b) carbonating the mixture to form a magnesium overbased sulfonate; and (c) treating the carbonated magnesium overbased sulfonate with about 6 to about 10 weight percent of a hydrocarbyl-substituted succinic acid or an anhydride thereof at about 160°C to about 200°C. In an aspect, the hydrocarbyl substituent of the hydrocarbyl-substituted succinic acid or an anhydride thereof is derived from polyisobutylene having a number average molecular weight of about 900 to about 1500 and having more than 50 mole percent terminal double bonds to form a magnesium overbased sulfonate detergent having improved compatibility with a friction modifier.

[0004] In another approach or embodiment, the process described in the previous paragraph may include other features, steps, or embodiments in any combination. These other features, steps, or embodiments may include one or more of the following: the overbased magnesium sulfonate before treatment has a total base number (TBN) of at least about 450 mg KOH / g, and the overbased magnesium sulfonate detergent after treatment has a total base number (TBN) of less than about 410 mg KOH / g; and / or the overbased magnesium sulfonate detergent contains at least about 60 weight percent of magnesium sulfonate as an active ingredient; and / or the overbased magnesium sulfonate detergent has up to about 35 weight percent of process oil; and / or the treatment step (c) is substantially free of dicarboxylic acid; and / or the dicarboxylic acid is one or more of phthalic acid, succinic acid, maleic acid, azelaic acid, suberic acid, sebacic acid, fumaric acid, adipic acid, malonic acid, or combinations thereof; and / or the overbased magnesium sulfonate is vacuum stripped at about 160°C to about 200°C before the treatment step (c); and / or the overbased magnesium sulfonate detergent has at least about 18 weeks of storage stability at about 55°C when combined with up to about 0.4 weight percent of glycerol monooleate.

[0005] In yet another approach or embodiment, a storage-stable overbased magnesium sulfonate detergent having improved compatibility with friction modifiers is described herein. In one aspect, the storage-stable overbased magnesium sulfonate detergent is made by a process comprising: a) preparing a mixture of a linear C14-C24 alkylaryl sulfonic acid or a salt thereof, magnesium oxide or magnesium hydroxide, and one or more branched C8-C16 carboxylic acids; b) carbonating the mixture to form an overbased magnesium sulfonate; and c) treating the carbonated overbased magnesium sulfonate with about 6 to about 10 weight percent of a hydrocarbyl-substituted succinic acid or its anhydride at about 160°C to about 200°C. In another aspect, the hydrocarbyl substituent of the hydrocarbyl-substituted succinic acid or its anhydride is derived from polyisobutylene having a number average molecular weight of about 900 to about 1500 and having more than 50 mole percent terminal double bonds to form the overbased magnesium sulfonate detergent, which has improved compatibility with friction modifiers.

[0006] In a further approach, the storage-stable overbased magnesium sulfonate detergent of the previous paragraph includes any combination of other features or embodiments. These other features, or embodiments, include one or more of the following: the overbased magnesium sulfonate prior to treatment has a total base number (TBN) of at least about 450 mg KOH / g, and the overbased magnesium sulfonate detergent after treatment has a total base number (TBN) of less than about 410 mg KOH / g; and / or the overbased magnesium sulfonate detergent includes at least about 60 weight percent magnesium sulfonate as an active ingredient; and / or the overbased magnesium sulfonate detergent has up to about 35 weight percent process oil; and / or the treatment step (c) is substantially free of dicarboxylic acid; and / or the dicarboxylic acid is one or more of phthalic acid, succinic acid, maleic acid, azelaic acid, suberic acid, sebacic acid, fumaric acid, adipic acid, malonic acid, or combinations thereof; and / or the overbased magnesium sulfonate is vacuum stripped at about 160 °C to about 200 °C prior to treatment step (c); and / or the overbased magnesium sulfonate detergent has a total base number (TBN) of about 350 to about 410 mg KOH / g and is storage stable at about 55 °C for at least about 18 weeks when combined with up to about 0.4 weight percent glycerol monooleate friction modifier.

[0007] In yet another approach or embodiment, an engine oil lubricating composition is described herein that includes a major amount of one or more lubricating viscosity base oils, any embodiment of the storage-stable overbased magnesium sulfonate detergent described herein (e.g., about 0.02 to about 5 weight percent or about 0.2 to about 2 weight percent), and up to about 0.4 weight percent glycerol monooleate friction modifier.

[0008] In yet another method or embodiment, a method for improving the storage stability of a magnesium overbased sulfonate detergent is described herein. In one aspect, the method comprises: (a) preparing a mixture of a linear C14-C24 alkylaryl sulfonic acid or a salt thereof, magnesium oxide or magnesium hydroxide, and one or more branched C8-C16 carboxylic acids, carbonating the mixture to form a magnesium overbased sulfonate, and treating the formed magnesium overbased sulfonate with about 6 to about 10 weight percent of a hydrocarbyl-substituted succinic anhydride at about 160°C to about 200°C, wherein the hydrocarbyl substituent is derived from a polyisobutylene having a number average molecular weight of about 900 to about 1500 and having more than 50 mole percent terminal double bonds, to form a magnesium overbased sulfonate detergent; and (b) combining about 0.02 to about 5 weight percent of the magnesium overbased sulfonate detergent with a glycerol monooleate friction modifier at up to about 0.4, wherein the combination of the magnesium overbased sulfonate detergent and the glycerol monooleate friction modifier has a storage stability of at least about 18 weeks at about 55°C.

[0009] In other embodiments, the method of the preceding paragraph may include other steps, features, or embodiments in any combination. These other steps, features, or embodiments include one or more of the following: The pre-treatment overbased magnesium sulfonate has a total base number (TBN) of at least about 450 mg KOH / g, and the post-treatment overbased magnesium sulfonate detergent has a total base number (TBN) of less than about 410 mg KOH / g; and / or the overbased magnesium sulfonate detergent contains at least about 60 weight percent of magnesium sulfonate as an active ingredient; and / or the overbased magnesium sulfonate detergent has up to about 35 weight percent process oil; and / or the treatment step (c) is substantially free of dicarboxylic acid; and / or the dicarboxylic acid is one or more of phthalic acid, succinic acid, maleic acid, azelaic acid, suberic acid, sebacic acid, fumaric acid, adipic acid, malonic acid, or combinations thereof; and / or the overbased magnesium sulfonate is vacuum stripped at about 160°C to about 200°C prior to treatment step (c); and / or the overbased magnesium sulfonate detergent has a total base number (TBN) of about 350 to about 410 mg KOH / g and is storage stable at about 55°C for at least about 18 weeks when combined with up to about 0.4 weight percent glycerol monooleate friction modifier.

[0010] In yet another approach or embodiment, the use of about 6 to about 10 weight percent of a hydrocarbyl-substituted succinic anhydride for the post-treatment of overbased magnesium sulfonate prepared via any of the methods or embodiments of this summary at about 160°C to about 200°C, wherein the hydrocarbyl substituent is derived from polyisobutylene having a number average molecular weight of about 900 to about 1500 and having more than 50 mole percent terminal double bonds, forms an overbased magnesium sulfonate detergent, and the combination of the post-treated overbased magnesium sulfonate detergent (e.g., about 0.02 to about 5 weight percent) with a glycerol monooleate friction modifier (up to about 0.4 weight percent) is storage stable at about 55°C for at least about 18 weeks. The use may include any embodiment of this summary.

[0011] Additional details and advantages of the present disclosure are in part described in the following description and may be learned by the practice of the present disclosure. The details and advantages of the present disclosure may be realized and attained by means of the elements and combinations particularly pointed out in the appended claims. It is to be understood that both the foregoing general description and the following detailed description are exemplary and explanatory only and are not restrictive of the claimed disclosure.

Mode for Carrying Out the Invention

[0012] The present disclosure relates to an improved overbased magnesium sulfonate detergent, a method for preparing an improved overbased magnesium sulfonate detergent, and a method for improving the storage stability of an overbased magnesium sulfonate detergent. In one aspect, the methods and detergents herein produce an improved overbased magnesium sulfonate detergent having improved storage stability and / or compatibility with additives in lubricating oil compositions, particularly compatibility with friction modifiers such as glycerol monooleate conventionally used in automotive lubricating oil compositions.

[0013] In one embodiment, a process for preparing an improved overbased magnesium sulfonate detergent having improved compatibility with a friction modifier (such as glycerol monooleate) is described herein. In one aspect, the process comprises: (a) preparing a reaction mixture of a C14-C24 alkylaryl sulfonic acid or a salt thereof, a magnesium compound, and one or more branched C8-C16 carboxylic acids; (b) carbonating the reaction mixture to form an overbased magnesium sulfonate (the carbonation is either mixed with the reaction mixture or carried out after the reaction mixture is prepared); (c) then treating the carbonated overbased magnesium sulfonate with about 6 to about 10 weight percent of a hydrocarbyl-substituted succinic acid or its anhydride at about 160°C to about 200°C (in other approaches, about 6 to about 8 weight percent or about 8 to about 10 weight percent), wherein the hydrocarbyl substituent has a number average molecular weight of about 900 to about 1500 g / mol (in other approaches, about 900 to about 1200 g / mol) and is derived from polyisobutylene having more than 50 mole percent terminal double bonds. Such a process forms an improved overbased magnesium sulfonate detergent. In another aspect, the improved overbased magnesium sulfonate detergent formed by such a process has improved compatibility with a friction modifier such as glycerol monooleate and / or improved storage stability, as shown in the examples herein.

[0014] Conventional (e.g., not the post-treatment described herein) overbased detergents are well-known in the art and can be overbased detergents of alkali metals or alkaline earth metals. Such detergents can be prepared, for example, by reacting a metal oxide or metal hydroxide with a substrate and an overbased acid. The substrate is typically an acid and, in the case of a sulfonate detergent, a substituted sulfonic acid (e.g., an alkylaryl sulfonic acid or sulfonate). The term "overbased" relates to the metal salts formed, such as metal salts in the form of sulfonates, where the amount of metal present exceeds the stoichiometric amount. Such salts can have a conversion level greater than 100% (i.e., such salts can contain more than 100% of the theoretical amount of metal required to convert the acid substrate to its normal salt, or "neutral salt"). In many cases, the expression "metal ratio", abbreviated as MR, is used to indicate the ratio of the total chemical equivalent of the metal in the overbased salt to the chemical equivalent of the metal in the neutral salt, according to known chemical reactivity and stoichiometry. In the normal or neutral salt, the metal ratio is 1, but in the overbased salt, the MR is greater than 1. Such detergents are generally referred to as overbased, highly basic, or superbasic salts and, in the case of sulfonate detergents, can be salts of organic sulfonic acids. As used herein, an overbased magnesium sulfonate detergent can have a TBN of greater than 170 mg KOH / gram, greater than or equal to about 250 mg KOH / gram, greater than or equal to about 300 mg KOH / gram, greater than or equal to about 350 mg KOH / gram, greater than or equal to about 375 mg KOH / gram, greater than or equal to about 400 mg KOH / gram, or from about 400 to about 410 mg KOH / gram, as measured by the method of ASTM D-2896. In other embodiments, the overbased magnesium sulfonate detergents herein have a TBN of from about 175 to about 450 mg KOH / gram (or any other range therewith).

[0015] In one method or embodiment, the improved overbased magnesium sulfonate detergent herein is prepared by post-treating a conventionally formed overbased magnesium sulfonate detergent with an effective amount of a selected hydrocarbyl-substituted succinic acid or its anhydride under conditions effective to improve the stability of the overbased magnesium sulfonate detergent. As further contemplated below, the hydrocarbyl substituent of the succinic acid or its anhydride post-treatment compound preferably is derived from polyisobutylene having a number average molecular weight of about 900 to about 1500 g / mol and more than 50 mole percent terminal double bonds (in other methods, about 900 to about 1200 g / mol).

[0016] The starting, conventionally formed overbased magnesium sulfonate can be prepared by methods known in the art using either a one-step or two-step process. In an exemplary two-step process, a sulfonic acid or sulfonate (and preferably an alkylaryl sulfonic acid or sulfonate) is first neutralized with a magnesium compound in a first step to produce neutral magnesium sulfonate, and then overbased magnesium sulfonate is formed through a second overbasing step using additional magnesium and an overbasing acid as needed. Such a two-step process can also include water, an optional accelerator, a base oil, and a hydrocarbon solvent as needed. In most cases, a one-step process is generally preferred. In an exemplary one-step process, a sulfonic acid or sulfonate (preferably an alkylaryl sulfonic acid or sulfonate) is combined with a molar excess of a magnesium compound, water, an optional accelerator, a base oil, and a hydrocarbon solvent. An overbasing acid is then mixed with this reaction mixture to form overbased magnesium hydroxide in a single-step process.

[0017] In one approach, the alkylaryl sulfonic acid or sulfonate as the starting material can be derived from sulfonating alkyltoluene or alkylbenzene such as linear or branched alkyltoluene or benzene using various known sulfonating agents such as sulfuric acid, sulfur trioxide, chlorosulfonic acid, or sulfamic acid. The alkylaryl sulfonic acid or alkylaryl sulfonate can be natural or synthetic, and synthetic alkylaryl sulfonic acid and / or alkylaryl sulfonate are preferred. The alkyl substituent in such an alkylaryl moiety can have 14 or more carbon atoms, preferably a linear or branched alkyl substituent of C14 - C24. In one approach, the alkyl substituent is typically a polyolefin formed from olefins having 2 - 5 carbon atoms, including ethylene, propylene, butylene, and / or pentylene monomers. In one approach, the alkyl substitution is an olefin such as a normal alpha olefin having about 14 - about 24 carbon atoms. More preferably, the olefin is a normal alpha olefin having about 20 - about 24 carbon atoms. In another approach, the alkyl substituent is a branched alkyltoluene or benzene and can be prepared by alkylating toluene with a branched-chain olefin. The branched-chain olefin can be prepared by isomerization of a normal alpha olefin having at least 14 carbon atoms (preferably 14 - 24 carbon atoms). The normal alpha olefin can be isomerized before, during, or after the alkylation step, but is preferably isomerized before the alkylation step. Methods for isomerizing olefins are known in the art. Preferably, the branched-chain olefin is derived from the isomerization of a normal alpha olefin having about 14 - about 24 carbon atoms. More preferably, the branched-chain olefin is derived from the isomerization of a normal alpha olefin having about 20 - about 24 carbon atoms. The branched-chain olefin can also be derived from oligomers of propylene or butene containing at least 9 carbon atoms, preferably about 9 - 40 carbon atoms, more preferably about 9 - 24 carbon atoms, and most preferably about 10 - 18 carbon atoms.

[0018] In an embodiment, the magnesium compound is present in a molar excess over the amount stoichiometrically required to provide basicity to the overbased magnesium sulfonate and react with the sulfonic acid. As noted above, the magnesium compound often reacts in the presence of a hydrocarbon solvent and / or a low molecular weight alcohol. In one approach, the magnesium compound is magnesium oxide (MgO), magnesium hydroxide (Mg(OH)₂), or magnesium alkoxide (Mg(OR)₂), where the alkoxide is derived from an alcohol having, for example, from 1 to 6 carbon atoms. Preferably, the magnesium compound is magnesium oxide, or a mixture of magnesium oxide and magnesium hydroxide.

[0019] In some approaches, the process for forming the conventional overbased magnesium sulfonate herein may also include a hydrocarbon solvent. Suitable hydrocarbon solvents can be n-pentane, n-hexane, cyclohexane, n-heptane, n-octane, isooctane, n-decane, benzene, toluene, xylene, or mixtures thereof. Preferably, the hydrocarbon solvent is an aromatic solvent, either xylene, benzene, toluene, or a mixture thereof, and most preferably, when used, the solvent is xylene.

[0020] In an approach, the process for forming the conventional overbased magnesium sulfonate herein may further include an optional low molecular weight alcohol. When used, the low molecular weight alcohol must have a sufficiently low boiling point so that it can be readily distilled off after the reaction occurs. Typically, the low molecular weight alcohol has from about 1 to about 13 carbon atoms and a molecular weight of about 200 or less. In one embodiment, the low molecular weight alcohol is a low molecular weight monohydric alcohol. In a more preferred embodiment, the low molecular weight monohydric alcohol is C1-C 13It may be selected from the group consisting of alcohols and glycol monoethers and monoesters. Preferably, the low molecular weight alcohol is a monohydric alcohol selected from the group consisting of methanol, ethanol, propanol, isooctanol, cyclohexanol, cyclopentanol, isobutyl alcohol, benzyl alcohol, beta-phenylethyl alcohol, 2-ethylhexanol, dodecanol, tridecanol, 2-methylcyclohexanol, the monomethyl ether of ethylene glycol, the monobutyl ether of ethylene glycol, sec-pentyl alcohol, and tert-butyl alcohol. The most preferred low molecular weight monohydric alcohol is methanol (which can be added as an accelerator).

[0021] Processes for forming conventional overbased magnesium sulfonates can include an accelerator or a co-accelerator. The accelerator tends to improve acid-base contact and promote the neutralization and subsequent overbasing reaction. When used, the accelerator or co-accelerator is preferably one or more monocarboxylic acids. Suitable monocarboxylic acids have from 1 to 24 carbon atoms, preferably branched 8 to 16 carbon atoms, and most preferably a branched chain of 8 to 16 carbons. The monocarboxylic acid can be aliphatic or aromatic, saturated or unsaturated, and suitable monocarboxylic acids include formic acid, acetic acid, stearic acid, benzoic acid, salicylic acid, neodecanoic acid, or mixtures thereof. Preferably, the accelerator or co-accelerator is a branched C8-C16 carboxylic acid, and most preferably, the accelerator or co-accelerator is neodecanoic acid.

[0022] In the methods or embodiments of this specification, the process for forming the conventional overbased magnesium sulfonate detergent of this specification substantially does not contain, and preferably does not contain, any accelerator or co-accelerator derived from or based on a hydrocarbyl-substituted succinic acid, its anhydride, or its derivatives. For example, the processes of this specification substantially do not contain, and preferably do not contain, any accelerator or co-accelerator of a dodecenyl succinic acid or its anhydride, an octadecenyl succinic acid or its anhydride, and / or a polyisobutylene succinic acid or its anhydride-based accelerator. As used herein, "substantially does not contain" means that the reaction mixture for forming the conventional overbased magnesium sulfonate contains less than about 1 wt%, preferably less than about 0.5 wt%, more preferably less than about 0.1 wt% of a hydrocarbyl-substituted succinic acid, its anhydride, or a derivative-based accelerator or co-accelerator. Also, as used herein, "does not contain" means that the reaction mixture for forming the conventional overbased magnesium sulfonate does not contain a detectable amount of a hydrocarbyl-substituted succinic acid, its anhydride, or a derivative-based accelerator or co-accelerator. As will be discussed below, certain hydrocarbyl-substituted succinic acids or their anhydrides are used in the post-treatment, but such an additional post-treatment is different from the accelerators or co-accelerators previously used during overbasing.

[0023] In the method, the overbased acid used to form the conventional overbased magnesium sulfonate is any acid capable of providing a magnesium oil-soluble sulfonate having a stoichiometric excess of magnesium relative to the alkylaryl sulfonic acid or its salt. The most common overbased acid is carbon dioxide, although other overbased acids can include sulfur dioxide and / or sulfur trioxide. The acid itself can be part of the overbasing process or, alternatively, an overbased acid source such as ethylene carbonate can be used to introduce the overbased acid. The most preferred acid is carbon dioxide, and the one-step or two-step process using the overbased acid is typically referred to as carbonation of such components, regardless of the type of overbased acid used.

[0024] An exemplary reaction scheme for forming a conventional overbased magnesium sulfonate as a starting material is provided by Reaction Scheme I below, where R1 is hydrogen or a C1-C4 hydrocarbyl group (preferably a methyl group), and R2 is a linear or branched C14-C24 hydrocarbyl group. The conventional overbased magnesium sulfonate as a starting material has a total base number (TBN) of greater than 170 mg KOH / gram as measured by the method of ASTM D-2896, or as a further example, a TBN of about 250 mg KOH / gram or more, about 300 mg KOH / gram or more, or about 350 mg KOH / gram or more, or about 375 mg KOH / gram or more, or about 400 mg KOH / gram or more, or about 400 - about 450 mg KOH / gram or more.

[0025]

Chemical formula

[0026] This conventionally formed overbased magnesium sulfonate from Reaction Scheme I can also be subjected to many optional post-processing steps (which are different from the post-treatment steps described further below). Suitable post-processing includes one or more of vacuum stripping, distillation, sparging, filtration, degassing, evaporation, wiped film evaporation, centrifugation, dilution, liquid-liquid extraction, film separation, chromatography, absorption, supercritical extraction, and / or combinations thereof, and all post-processing is generally carried out at a temperature of about 160°C to about 200°C, either individually and / or in combination. Any of such optional post-processing steps is carried out before the post-treatment steps described below using a selected hydrocarbyl-substituted succinic acid or its anhydride.

[0027] As shown in the examples, such conventionally formed basic magnesium sulfonate has a tendency to be incompatible with friction modifiers commonly used in lubricating oil compositions, particularly glycerol monooleate. Such conventional basic magnesium sulfonate has a limited storage stability of about 7 to 10 weeks or less at about 55 °C before forming dropout, precipitate, and / or film when combined with glycerol monooleate in a lubricating oil composition. Without being bound by theory, the inorganic magnesium core of conventional basic magnesium sulfonate can interact with various parts of the friction modifier, particularly the part of glycerol monooleate, which is considered to cause instability of the composition and its detergent.

[0028] Post-treatment

[0029] To improve the storage stability of conventionally formed basic magnesium sulfonate detergents, conventional basic magnesium sulfonate detergents are post-treated with a selected amount of a post-treatment reactant containing a hydrocarbyl-substituted succinic acid or its anhydride, preferably a hydrocarbyl-substituted succinic acid or its anhydride having a hydrocarbyl substituent derived from polyisobutylene having a number average molecular weight of about 900 to about 1500 g / mol (in other methods, about 900 to about 1200 g / mol, about 900 to about 1100 g / mol, or about 950 to about 1000 g / mol) and having more than 50 mole percent terminal double bonds, under selected conditions.

[0030] In an embodiment, the post-treatment is carried out at a temperature of about 160 °C to about 200 °C (in other methods, 170 °C to about 185 °C, in a further method, 175 °C to about 185 °C, most preferably about 180 °C), and about 6 to about 10 weight percent of a hydrocarbyl-substituted succinic acid or its anhydride (in other methods, about 6 to about 8 weight percent or about 8 to about 10 weight percent). The post-treatment is for about 15 minutes to about 60 minutes, after which the mixture is cooled to about 70 to about 80 °C. The post-treatment mixture typically comprises about 60 to about 70 weight percent of overbased magnesium sulfonate (active basis), about 25 to about 35 weight percent of process oil, and an effective amount of a selected hydrocarbyl-substituted succinic acid or its anhydride. Thus, in an embodiment herein, the overbased magnesium sulfonate detergent produced, formed and improved by the process herein is a detergent or detergent composition comprising about 60 to about 70 weight percent of overbased magnesium sulfonate (active basis), about 25 to about 35 weight percent of process oil, and about 6 to about 10 weight percent (or about 6 to about 8 weight percent or about 8 to about 10 weight percent) of a selected hydrocarbyl-substituted succinic acid or its anhydride.

[0031] Before post-treatment, the TBN of the overbased magnesium sulfonate detergent is often about 400 mg KOH / gram or more, and in some cases, about 450 mg KOH / gram or more (preferably greater than 410 to about 470, or about 420 to about 460). After post-treatment, the TBN of the improved overbased magnesium sulfonate detergent is usually about 375 to about 410 mg KOH / gram (preferably about 400 to about 410 mg KOH / gram) or other TBN values described herein for overbased detergents. After post-treatment, the KV100 of the post-treated overbased magnesium detergent containing the detergent, process oil, and hydrocarbyl-substituted succinic acid or its anhydride is about 100 to about 200 cSt (ASTM D425), about 125 to about 175 cSt, or about 140 to about 160 cSt. As shown in the following examples, such an improved overbased magnesium sulfonate detergent has storage stability of at least about 18 weeks, at least about 20 weeks, at least about 24 weeks, or more at about 55 °C when combined with up to about 0.4 weight percent glycerol monooleate.

[0032] In some embodiments, the post-treatment step is substantially free of, and preferably does not contain, dicarboxylic acid. For example, the post-treatment step of the processes herein that use a selected dicarboxylic acid preferably is substantially free of, or does not contain, a dicarboxylic acid that includes one or more of phthalic acid, succinic acid, maleic acid, azelaic acid, suberic acid, sebacic acid, fumaric acid, adipic acid, malonic acid, or combinations thereof. As used herein, "substantially free of" in the context of dicarboxylic acid in the post-treatment means that the post-treatment contains less than about 1 weight percent, preferably less than about 0.5 weight percent, more preferably less than about 0.1 weight percent of dicarboxylic acid. Also, as used herein, "does not contain" in the context of dicarboxylic acid in the post-treatment means that there is no detectable amount of any dicarboxylic acid.

[0033] Post-treatment agent: The post-treatment agent is a selected hydrocarbyl-substituted succinic acid or its anhydride. The selected hydrocarbyl-substituted succinic acid or its anhydride can be prepared as known in the art by reacting an olefinically unsaturated hydrocarbon of the described molecular weight with maleic acid or maleic anhydride (or those considered below) to form the hydrocarbyl-substituted succinic acid or its anhydride. A reaction temperature of about 100 °C to about 250 °C can be used. This reaction is often promoted by the addition of chlorine.

[0034] Examples of selected hydrocarbyl substituents can include, but are not limited to, olefins such as cracked wax olefins, linear alpha-olefins, branched-chain alpha-olefins, polymers and copolymers of lower olefins. The olefin can be selected from ethylene, propylene, butylene such as isobutylene, 1-octene, 1-hexene, 1-decene. Some useful polymers and / or copolymers of lower olefins include, but are not limited to, polypropylene, polybutene, polyisobutene, ethylene-propylene copolymer, ethylene-isobutylene copolymer, propylene-isobutylene copolymer, ethylene-1-decene copolymer, etc. Hydrocarbyl substituents have also been made from olefin terpolymers. Useful products are ethylene-C3~ 12 alpha-olefin-C5~ 12 non-conjugated diene terpolymers, for example, can be made from ethylene-propylene-1,4-hexadiene terpolymer, ethylene-propylene-1,5-cyclooctadiene terpolymer, ethylene-propylene norbornene terpolymer, etc.

[0035] The number average molecular weight of the selected hydrocarbyl substituent for the post-treatment reactant of this specification is about 900 to about 1500 g / mol when determined by gel permeation chromatography (GPC) using polystyrene as the calibration standard described in this specification, about 900 to about 1200 g / mol by other methods, about 950 to about 1100 g / mol by other methods, or limited to about 950 to about 1000 g / mol. As shown in the following examples, lower and higher molecular weights of the hydrocarbyl substituent unexpectedly reduce the stability when the resulting overbased magnesium sulfonate (even when post-treated) is combined with a friction modifier.

[0036] In some methods for forming the polycarboxylic acid or its anhydride of this specification, carboxylic acid reactants other than maleic acid or maleic anhydride can also be used. Suitable reactants also include, but are not limited to, fumaric acid, malic acid, tartaric acid, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride, mesaconic acid, ethyl maleic anhydride, dimethyl maleic anhydride, ethyl maleic acid, dimethyl maleic acid, hexyl maleic acid, etc., including the corresponding acid halides and lower aliphatic esters.

[0037] In some embodiments, the selected hydrocarbyl-substituted succinic anhydride or hydrocarbyl-substituted succinic acid can be prepared, for example, by the thermal reaction of a polyolefin and maleic anhydride as described in U.S. Pat. Nos. 3,361,673 and 3,676,089, the disclosures of which are incorporated herein by reference. Alternatively, substituted succinic anhydrides can be prepared, for example, by the reaction of a chlorinated polyolefin and maleic anhydride as described in U.S. Pat. No. 3,172,892, the disclosure of which is also incorporated herein by reference. Further considerations of hydrocarbyl-substituted succinic anhydrides can be found, for example, in U.S. Pat. Nos. 4,234,435, 5,620,486, and 5,393,309, the disclosures of which are incorporated herein by reference.

[0038] In some processes, the molar ratio of maleic anhydride (or other acylating agent) to olefinically unsaturated hydrocarbon can vary widely. For example, this can vary from about 5:1 to about 1:5, in other processes from about 3:1 to about 1:3, and in still other processes, maleic anhydride can be used in stoichiometric excess to complete the reaction. If desired, unreacted maleic anhydride can be removed by vacuum distillation.

[0039] In a preferred embodiment, the hydrocarbyl substituent used to form the post-treatment reactant herein is derived from polyisobutylene (PIB), most preferably polyisobutylene having 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 referred to as highly reactive PIB ("HR-PIB"). HR-PIB having a number average molecular weight in the range of about 900 to about 1500 is most suitable for use in embodiments of the present disclosure when determined by GPC. 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%. Such HR-PIB can be commercially available or synthesized by the polymerization of isobutene in the presence of a non-chlorinated catalyst such as boron trifluoride as described in U.S. Patent Nos. 4,152,499 and / or 5,739,355, both of which are incorporated herein by reference.

[0040] Lubricating oil composition

[0041] The improved overbased magnesium sulfonate detergent herein can be combined with a major amount of a base oil blend or a base oil blend of lubricating viscosity (such as described below) in combination with one or more additional optional additives to produce a lubricating oil composition. In an approach, the lubricating oil composition can include a base oil of about 50 weight percent or more, about 60 weight percent or more, about 70 weight percent or more, or about 80 weight percent or more to about 95 weight percent or less, about 90 weight percent or less, about 85 weight percent or less of the base oil further considered below.

[0042] In an approach, the lubricating oil composition herein can include from about 0.02 to about 5 weight percent, in other approaches from about 0.2 to about 3 weight percent, and in still other approaches from about 0.2 to about 2 weight percent of the improved overbased magnesium sulfonate detergent in the base oil or base oil blend. As shown in the examples below, the lubricating oil composition can also include up to about 0.4 weight percent of a friction modifier, particularly glycerol monooleate, and can maintain storage stability. Such combinations of additives (e.g., the improved overbased magnesium sulfonate detergent and glycerol monooleate) are storage stable (e.g., no sediment, dropout, and / or film formation) at about 55 °C for at least about 18 weeks. As used herein, storage stability means that there is no sediment or film present at the bottom of a 20 - 20 gram sample in a clear glass vial when viewed in the presence of a backlight.

[0043] The lubricants, component combinations, dispersant inhibitor packages, and / or individual components herein can be suitable for use in various types of lubricants such as automotive lubricants and / or greases, internal combustion engine oils, hybrid engine oils, hybrid engine oils, electric engine lubricants, drive train lubricants, transmission lubricating oils, gear oils, hydraulic lubricating oils, tractor hydraulic fluids, metalworking fluids, turbine engine lubricants, stationary engine lubricants, tractor lubricants, motorcycle lubricants, power steering fluids, clutch fluids, axle fluids, wet brake fluids, etc.

[0044] Suitable engine types may include, but are not limited to, heavy-duty diesel, passenger vehicle, light-duty diesel, medium-speed diesel, or marine engines. The internal combustion engine may be a diesel fuel engine, gasoline fuel engine, natural gas fuel engine, biofuel engine, diesel / biofuel blend-fuel engine, gasoline / biofuel blend-fuel engine, alcohol fuel engine, gasoline / alcohol fuel blend engine, compressed natural gas (CNG) fuel engine, or a mixture thereof. The diesel engine may be a compression ignition engine. The gasoline engine may be a spark ignition engine. The internal combustion engine may also be used in combination with electric or battery power. An engine configured in such a manner is generally known as a hybrid engine. The internal combustion engine may be a two-stroke, four-stroke, or rotary engine. Suitable internal combustion engines include marine diesel engines (such as inland vessels), aircraft piston engines, low-load diesel engines, as well as engines for motorcycles, automobiles, locomotives, and trucks. The engine may be connected to a turbocharger.

[0045] The lubricating oil composition for an internal combustion engine may be suitable for any engine lubricating oil, regardless of the sulfur, phosphorus, or sulfuric acid ash (ASTM D-874) content. The sulfur content of the engine oil lubricant may be about 1 wt% or less, or about 0.8 wt% or less, or about 0.5 wt% or less, or about 0.3 wt% or less, or about 0.2 wt% or less. In one embodiment, the sulfur content may be in the range of about 0.001 wt% to about 0.5 wt%, or about 0.01 wt% to about 0.3 wt%. The phosphorus content may be about 0.2 wt% or less, or about 0.1 wt% or less, or about 0.085 wt% or less, or about 0.08 wt% or less, or even about 0.06 wt% or less, about 0.055 wt% or less, or about 0.05 wt% or less. In one embodiment, the phosphorus content may be about 50 ppm to about 1000 ppm, or about 325 ppm to about 850 ppm. The total sulfuric acid ash content may be about 2 wt% or less, or about 1.5 wt% or less, or about 1.1 wt% or less, or about 1 wt% or less, or about 0.8 wt% or less, or about 0.5 wt% or less. In one embodiment, the sulfuric acid ash content may be about 0.05 wt% to about 0.9 wt%, or about 0.1 wt% or about 0.2 wt% to about 0.45 wt%. In another embodiment, the sulfur content may be about 0.4 wt% or less, the phosphorus content may be about 0.08 wt% or less, and the sulfuric acid ash may be about 1 wt% or less. In yet another embodiment, the sulfur content may be about 0.3 wt% or less, the phosphorus content may be about 0.05 wt% or less, and the sulfuric acid ash may be about 0.8 wt% or less.

[0046] Furthermore, the lubricants of the present specification meet one or more industry specification requirements such as ILSAC GF-3, GF-4, GF-5, GF-6, PC-11, CF, CF-4, CH-4, CK-4, FA-4, CJ-4, CI-4 Plus, CI-4, API SG, SJ, SL, SM, SN, SN PLUS, ACEA A1 / B1, A2 / B2, A3 / B3, A3 / B4, A5 / B5, C1, C2, C3, C4, C5, E4 / E6 / E7 / E9, Euro 5 / 6, JASO DL-1, Low SAPS, Mid SAPS, or Dexos1 (trademark), Dexos2 (trademark), MB-Approval 229.1, 229.3, 229.5, 229.51 / 229.31, 229.52, 229.6, 229.71, 226.5, 226.51, 228.0 / .1, 228.2 / .3, 228.31, 228.5, 228.51, 228.61, VW 501.01, 502.00, 503.00 / 503.01, 504.00, 505.00, 505.01, 506.00 / 506.01, 507.00, 508.00, 509.00, 508.88, 509.99, BMW Longlife-01, Longlife-01 FE, Longlife-04, Longlife-12 FE, Longlife-14 FE+, Longlife-17 FE+, Porsche A40, C30, Peugeot Citroen Automobiles B71 2290, B71 2294, B71 2295, B71 2296, B71 2297, B71 2300, B71 2302, B71 2312, B71 2007, B71 2008, Renault RN0700, RN0710, RN0720, Ford WSS-M2C153-H, WSS-M2C930-A, WSS-M2C945-A, WSS-M2C913A, WSS-M2C913-B, WSS-M2C913-C, WSS-M2C913-D, WSS-M2C948-B, WSS-M2C948-A, GM 6094-M, Chrysler MS-6395, Fiat 9.55535 G1, G2, M2, N1, N2, Z2, S1, S2, S3, S4, T2, DS1, DSX, GH2, GS1, GSX, CR1, Jaguar Land Rover STJLR.03.5003, STJLR.03.5004, STJLR.03.It may also be suitable to meet the specifications of original equipment manufacturers such as 5005, STJLR.03.5006, STJLR.03.5007, STJLR.51.5122, or the specifications of past or future PCMOs or HDDs not described in this specification. In some embodiments for passenger car motor oil (PCMO) applications, the amount of phosphorus in the final fluid is 1000 ppm or less, or 900 ppm or less, or 800 ppm or less.

[0047] Base oil or base oil blend: The base oil used in the lubricating oil composition herein may be an oil of lubricating viscosity and is selected from any of the base oils in Groups I - V as specified in the American Petroleum Institute (API) Base Oil Interchangeability Guidelines. The five base oil groups are generally shown in Table 1 below.

[0048]

Table 1

[0049] Groups I, II, and III are mineral oil process stocks. Group IV base oils contain true synthetic molecular species produced by the polymerization of olefinically unsaturated hydrocarbons. Many Group V base oils are also true synthetic products and may include diesters, polyol esters, polyalkylene glycols, alkylated aromatics, polyphosphate esters, polyvinyl ethers, and / or polyphenyl ethers, etc., or may be natural oils such as vegetable oils. It should be noted that Group III base oils are derived from mineral oils, but due to the rigorous treatment these fluids undergo, their physical properties become very similar to those of some true synthetic oils such as PAO. 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.

[0050] The base oil blend used in the disclosed lubricating oil composition can be mineral oil, animal oil, vegetable oil, synthetic oil, synthetic oil blend, or mixtures thereof. Suitable oils can be derived from hydrocracked, hydrogenated, hydrofinished, unrefined oil, refined oil, and re-refined oil, and mixtures thereof.

[0051] Unrefined oil is derived from natural, mineral, or synthetic sources without or with little further refining treatment. Refined oil is similar to unrefined oil except that it has been treated in one or more refining processes that can bring about improvement in one or more properties. Examples of suitable refining techniques are solvent extraction, secondary distillation, acid or base extraction, filtration, osmosis, etc. Oils refined to a quality suitable for consumption may or may not be useful. Edible oil may sometimes be called white oil. In some embodiments, the lubricating oil composition does not contain edible oil or white oil.

[0052] Re-refined oil is also known as recycled oil or reprocessed oil. These oils are obtained in the same or similar processes as refined oil. Often, these oils are additionally treated by techniques aimed at removing used additives and oil decomposition products.

[0053] Mineral oil can include oil obtained by drilling, or from plants and animals, or any mixture thereof. For example, such oils can include castor oil, lard oil, olive oil, peanut oil, corn oil, soybean oil, and linseed oil, and mineral lubricating oils such as liquid petroleum and paraffinic, naphthenic, or mixed paraffinic-naphthenic type solvent-treated or acid-treated mineral-based lubricating oils, but are not limited thereto. Such oils can be partially or fully hydrogenated if desired. Oils derived from coal or shale can also be useful.

[0054] Useful synthetic lubricating oils include hydrocarbon oils such as polymerized, oligomerized, or interpolymerized olefins (e.g., polybutylene, polypropylene, propylene isobutylene copolymer); poly(1-hexene), poly(1-octene), trimers or oligomers of 1-decene such as poly(1-decene) (such materials are often referred to as α-olefins), and mixtures thereof; alkyl-benzenes (e.g., dodecylbenzene, tetradecylbenzene, dinonylbenzene, di-(2-ethylhexyl)-benzene); polyphenyls (e.g., biphenyl, terphenyl, alkylated polyphenyls); diphenylalkanes, alkylated diphenylalkanes, alkylated diphenyl ethers and alkylated diphenyl sulfides, and derivatives, analogs and homologs thereof, or mixtures thereof. Polyalphaolefins are typically hydrogenated materials.

[0055] Other synthetic lubricating oils include polyol esters, diesters, liquid esters of phosphorus-containing acids (e.g., tricresyl phosphate, trioctyl phosphate, and diethyl ester of decanephosphonic acid), or polymerized tetrahydrofuran. Synthetic oils may be produced by the Fischer-Tropsch reaction and may typically be hydrogenated isomerized Fischer-Tropsch hydrocarbons or waxes. In one embodiment, the oil may be prepared by a Fischer-Tropsch gas-liquid synthesis procedure, as well as other gas-liquid oils.

[0056] The major amount of base oil contained in the lubricating composition can 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, provided that the major amount of base oil is other than that resulting from the provision of additive components or viscosity index improvers in the composition. In another embodiment, the major amount of base oil contained in the lubricating composition can be selected from the group consisting of Group II, Group III, Group IV, Group V, and combinations of two or more of the foregoing, provided that the major amount of base oil is other than that resulting from the provision of additive components or viscosity index improvers in the composition.

[0057] The amount of oil having a lubricating viscosity that is present can be the difference remaining after subtracting the total amount of performance additives including viscosity index improvers and / or pour point depressants and / or other top treatment additives from 100% by weight. For example, the oil having a lubricating viscosity that can be present in the final fluid can be 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.

[0058] Optional additives:

[0059] The lubricating oil compositions herein may also include any of a number of optional additives, optionally combined with overbased and sulfurized alkylphenate products, to meet performance criteria. Those optional additives are described in the following paragraphs.

[0060] Dispersants: The lubricating oil compositions may optionally include one or more dispersants or mixtures thereof. Dispersants are often known as ashless dispersants because they do not contain metals that form ash before being mixed into the lubricating oil composition and do not normally contribute to ash when added to the lubricant. Ashless dispersants are characterized by having a polar group bonded to a relatively high molecular weight hydrocarbon chain. Typical ashless dispersants include N-substituted long chain alkenyl succinimides. Examples of N-substituted long chain alkenyl succinimides include polyisobutylene succinimides where the number average molecular weight of the polyisobutylene substituent ranges from about 350 to about 50,000, or to about 5,000, or to about 3,000 as measured by GPC. Succinimide dispersants and their preparation are disclosed, for example, in U.S. Patent Nos. 7,897,696 or 4,234,435. The alkenyl substituent can 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(ethyleneamine)).

[0061] Preferred amines are selected from polyamines and hydroxyamines. Examples of polyamines that can be used include higher homologues such as diethylene triamine (DETA), triethylene tetramine (TETA), tetraethylene pentamine (TEPA), and pentaethylamine hexamine (PEHA), but are not limited thereto.

[0062] Suitable heavy polyamines include small amounts of lower polyamine oligomers such as TEPA and PEHA (pentaethylenehexamine), but mainly contain polyalkylene-polyamine mixtures containing six or more nitrogen atoms, two or more primary amines per molecule, and oligomers with a wider range of branching than conventional polyamine mixtures. The heavy polyamine preferably contains polyamine oligomers containing seven or more nitrogens per molecule and having two or more primary amines per molecule. The heavy polyamine contains more than 28% by weight (e.g., more than 32% by weight) of total nitrogen and 120 to 160 grams of equivalent of primary amine groups per equivalent.

[0063] In some approaches, suitable polyamines are generally known as PAM and contain mixtures of ethylene amines in which TEPA and pentaethylenehexamine (PEHA) are the main part and usually less than about 80%.

[0064] Typically, PAM has 8.7 to 8.9 milliequivalents of primary amine per gram (115 to 112 grams of equivalent per equivalent of primary amine) and a total nitrogen content of about 33 to 34% by weight. A heavier cut of PAM oligomers that contains substantially no TEPA and only a very small amount of PEHA but mainly contains more than six nitrogens and oligomers with a wider range of branching can produce a dispersant with improved dispersibility.

[0065] In an embodiment, the present disclosure further comprises at least one polyisobutylene succinimide dispersant derived from polyisobutylene having a number average molecular weight in the range of about 350 to about 50,000, or up to about 5,000, or up to about 3,000 when determined by GPC. The polyisobutylene succinimide can be used alone or in combination with other dispersants.

[0066] In some embodiments, when polyisobutylene is included, the polyisobutylene can have a terminal double bond content of more than 50 mol%, more than 60 mol%, more than 70 mol%, more than 80 mol%, or more 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 when 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%.

[0067] HR-PIB having a number average molecular weight in the range of about 900 to about 3000 when determined by GPC can be suitable. Such HR-PIB can be commercially available or can be synthesized by the 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 the HR-PIB is used in the above-mentioned thermal ene reaction, the HR-PIB can result in a higher conversion rate during the reaction and a lower amount of precipitate formation due to the increased reactivity. A suitable method is described in U.S. Patent No. 7,897,696.

[0068] In one embodiment, the present disclosure further comprises at least one dispersant derived from polyisobutylene succinic anhydride ("PIBSA"). PIBSA may have an average of about 1.0 to about 2.0 succinic acid moieties per polymer.

[0069] The active ingredient percentage of alkenyl or alkyl succinic anhydride can be determined using chromatographic techniques. This method is described in columns 5 and 6 of U.S. Patent No. 5,334,321.

[0070] The percent conversion of the polyolefin is calculated from the active ingredient percentage using the equations in columns 5 and 6 of U.S. Patent No. 5,334,321.

[0071] Unless otherwise stated, all percentages are weight percentages and all molecular weights are number average molecular weights determined by gel permeation chromatography (GPC) using commercially available polystyrene standards (having a number average molecular weight of 180 to about 18,000 as a calibration standard).

[0072] In one embodiment, the dispersant may be derived from polyalphaolefin (PAO) succinic anhydride. In one embodiment, the dispersant can be derived from an olefin maleic anhydride copolymer. As an example, the dispersant may be described as poly-PIBSA. In embodiments, the dispersant may be derived from an anhydride grafted onto an ethylene-propylene copolymer.

[0073] Suitable classes of nitrogen-containing dispersants can be derived from olefin copolymers (OCPs), and more specifically, ethylene-propylene dispersants that can be grafted with maleic anhydride. A more complete list of nitrogen-containing compounds that can react with functionalized OCPs is described in U.S. Patent Nos. 7,485,603, 7,786,057, 7,253,231, 6,107,257, and 5,075,383, and / or are commercially available.

[0074] One class of suitable dispersants can also be Mannich bases. Mannich bases are materials formed by the condensation of higher molecular weight alkyl-substituted phenols, polyalkylene polyamines, and aldehydes such as formaldehyde. Mannich bases are described in more detail in U.S. Patent No. 3,634,515.

[0075] Suitable classes of dispersants can also be high molecular weight esters or semi-ester amides. Suitable dispersants can also be post-treated by reaction with any of a variety of agents by conventional methods. These 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. U.S. Patent Nos. 7,645,726, 7,214,649, and 8,048,831 are hereby incorporated by reference in their entirety.

[0076] In addition to the post-treatment with carbonate and boric acid, the compounds can all be post-treated or further post-treated by various post-treatments designed to improve or impart different properties. Such post-treatments include those summarized in columns 27-29 of U.S. Patent No. 5,241,003, which is incorporated herein by reference. Such treatments include treatments with the following: inorganic phosphoric acid or anhydrides (e.g., U.S. Patent Nos. 3,403,102 and 4,648,980); organic phosphorus compounds (e.g., U.S. Patent No. 3,502,677); phosphorus pentasulfide; boron compounds as already described above (e.g., U.S. Patent Nos. 3,178,663 and 4,652,387); carboxylic acids, polycarboxylic acids, anhydrides, and / or acid halides (e.g., U.S. Patent Nos. 3,708,522 and 4,948,386); epoxides, polyepoxides, or thioepoxides (e.g., U.S. Patent Nos. 3,859,318 and 5,026,495); aldehydes or ketones (e.g., U.S. Patent No. 3,458,530); carbon disulfide (e.g., U.S. Patent No. 3,256,185); glycidol (e.g., U.S. Patent No. 4,617,137); urea, thiourea, or guanidine (e.g., U.S. Patent Nos. 3,312,619, 3,865,813, and British Patent No. 1,065,595); organic sulfonic acids (e.g., U.S. Patent No. 3,189,544 and British Patent No. 2,140,811); alkenyl cyanides (e.g., U.S. Patent Nos. 3,278,550 and 3,366,569); diketene (e.g., U.S. Patent No. 3,546,243); diisocyanates (e.g., U.S. Patent No. 3,573,205); alkanesultones (e.g., U.S. Patent No. 3,749,695); 1,3-dicarbonyl compounds (e.g., U.S. Patent No. 4,579,675); sulfates of alkoxylated alcohols or phenols (e.g., U.S. Patent No. 3,954,639); cyclic lactones (e.g., U.S. Patent 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. Patent Nos. 4,612,132, 4,647,390, 4,648,886, 4,670,170); nitrogen-containing carboxylic acids (e.g., U.S. Patent No. 4,971,598 and British Patent No. 2,140,811); hydroxy-protected dichlorocarbonyloxy compounds (e.g., U.S. Patent No. 4,614,522); lactams, thiolactams, thiolactones, or dithiolactones (e.g., U.S. Patent Nos. 4,614,603 and 4,666,460); cyclic carbonates or thiocarbonates, linear monocarbonates or polycarbonates, or chloroformates (e.g., U.S. Patent Nos. 4,612,132, 4,647,390, 4,646,860, and 4,670,170); nitrogen-containing carboxylic acids (e.g., U.S. Patent No. 4,971,598 and British Patent No. 2,440,811); hydroxy-protected dichlorocarbonyloxy compounds (e.g., U.S. Patent No. 4,614,522); lactams, thiolactams, thiolactones, or dithiolactones (e.g., U.S. Patent Nos. 4,614,603 and 4,666,460); cyclic carbamates, cyclic thiocarbamates, or cyclic dithiocarbamates (e.g., U.S. Patent Nos. 4,663,062 and 4,666,459); hydroxy aliphatic carboxylic acids (e.g., U.S. Patent Nos. 4,482,464, 4,521,318, 4,713,189); oxidizing agents (e.g., U.S. Patent No. 4,379,064); combinations of phosphorus pentasulfide and polyalkylene polyamines (e.g., U.S. Patent No. 3,185,647); combinations of carboxylic acids or aldehydes or ketones and sulfur or sulfur chloride (e.g., U.S. Patent Nos. 3,390,086, 3,470,098); combinations of hydrazine and carbon disulfide (e.g., U.S. Patent No. 3,519,564); combinations of aldehydes and phenols (e.g., U.S. Patent Nos. 3,649,229, 5,030,249, 5,039,307); combinations of aldehydes and O-diesters of dithiophosphoric acid (e.g., U.S. Patent No. 3,865,740);Combinations of hydroxyaliphatic carboxylic acids and boric acids (e.g., U.S. Patent No. 4,554,086); combinations of hydroxyaliphatic carboxylic acids, followed by formaldehyde and phenol (e.g., U.S. Patent No. 4,636,322); combinations of hydroxyaliphatic carboxylic acids and, followed by aliphatic dicarboxylic acids (e.g., U.S. Patent No. 4,663,064); combinations of formaldehyde and phenol, and, followed by glycolic acid (e.g., U.S. Patent No. 4,699,724); combinations of hydroxyaliphatic carboxylic acids or oxalic acid and, followed by diisocyanates (e.g., U.S. Patent No. 4,713,191); combinations of inorganic acids or anhydrides of phosphorus or their partial or total sulfur analogs and boron compounds (e.g., U.S. Patent No. 4,857,214); combinations of organic dibasic acids, followed by unsaturated fatty acids, and, followed by nitrosoaromatic amines, optionally followed by boron compounds, and, followed by glycolating agents (e.g., U.S. Patent No. 4,973,412); combinations of aldehydes and triazoles (e.g., U.S. Patent No. 4,963,278); combinations of aldehydes and triazoles, followed by boron compounds (e.g., U.S. Patent No. 4,981,492); combinations of cyclic lactones and boron compounds (e.g., U.S. Patent Nos. 4,963,275 and 4,971,711). Here, the patents mentioned above are incorporated herein in their entirety.;

[0077] The TBN of a suitable dispersant can be about 10 to about 65 mg KOH / g dispersant on an oil-free basis, comparable to about 5 to about 30 TBN when measured on a dispersant sample containing about 50% diluted oil. TBN is measured by the method of ASTM D2896.;

[0078] In still other embodiments, the optional dispersant additive can be a hydrocarbyl-substituted succinamide dispersant or a succinimide dispersant. In some approaches, the hydrocarbyl-substituted succinamide dispersant or succinimide dispersant can be derived from a hydrocarbyl-substituted acylating agent reacted with a polyalkylene polyamine, where the hydrocarbyl substituent of the succinamide dispersant or succinimide dispersant is a linear or branched hydrocarbyl group having a number average molecular weight of from about 250 to about 5,000 as measured by GPC using polystyrene as a calibration standard.

[0079] In some approaches, the polyalkylene polyamine used to form the dispersant has the following formula:

[0080] [Chemical formula] (wherein each R and R' is independently a divalent C1-C6 alkylene linker, each R1 and R2 is independently hydrogen, a C1-C6 alkyl group, or together with the nitrogen atom to which they are attached, forms a 5- or 6-membered ring optionally fused with one or more aromatic or non-aromatic rings, and n is an integer from 0 to 8). In other approaches, the polyalkylene polyamine is selected from the group consisting of mixtures of polyethylene polyamines having an average of 5 to 7 nitrogen atoms, triethylenetetramine, tetraethylenepentamine, and combinations thereof.

[0081] When present, the dispersant can be used in an amount sufficient to provide up to about 20 wt% based on the final weight of the lubricating oil composition. Another amount of dispersant that can be used is from about 0.1 wt% to about 15 wt%, or from about 0.1 wt% to about 10 wt%, from about 0.1 to 8 wt%, or from about 1 wt% to about 10 wt%, or from about 1 wt% to about 8 wt%, or from about 1 wt% to about 6 wt% based on the final weight of the lubricating oil composition. In some embodiments, the lubricating oil composition utilizes a mixed dispersant system. A mixture of a single type or two or more types of dispersants in any desired ratio can be used.

[0082] Antioxidant: The lubricating oil composition 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-naphthylamine, alkylated phenyl-alpha-naphthylamine, hindered non-aromatic amines, phenols, hindered phenols, oil-soluble molybdenum compounds, polymeric antioxidants, or mixtures thereof. The antioxidant compounds can be used alone or in combination.

[0083] The hindered phenol antioxidant may contain a secondary butyl group and / or a tertiary butyl group as a steric hindrance group. The phenol group may be further substituted with a hydrocarbyl group and / or a crosslinking group bonded to a second aromatic group. Examples of suitable hindered phenol antioxidants include 2,6-di-tert-butylphenol, 4-methyl-2,6-di-tert-butylphenol, 4-ethyl-2,6-di-tert-butylphenol, 4-propyl-2,6-di-tert-butylphenol or 4-butyl-2,6-di-tert-butylphenol, or 4-dodecyl-2,6-di-tert-butylphenol. In one embodiment, the hindered phenol antioxidant can be an ester and can include, for example, Irganox™ L-135 available from BASF or an adduct derived from 2,6-di-tert-butylphenol and an alkyl acrylate, where the alkyl group can 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 can be an ester and can include Ethanox™ 4716 available from Albemarle Corporation.

[0084] Useful antioxidants can include diarylamines and high molecular weight phenols. In embodiments, the lubricating oil composition can contain a mixture of a diarylamine and a high molecular weight phenol, and each antioxidant can be present in an amount sufficient to provide up to about 5 wt% based on the final weight of the lubricating oil composition. In embodiments, the antioxidant can be a mixture of about 0.3 to about 1.5 wt% diarylamine and about 0.4 to about 2.5 wt% high molecular weight phenol based on the final weight of the lubricating oil composition.

[0085] Examples of suitable olefins that can be sulfided 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, and their dimers, trimers, and tetramers are particularly useful olefins. Alternatively, the olefin can be a Diels - Alder adduct of a diene such as 1,3 - butadiene and an unsaturated ester such as butyl acrylate.

[0086] Another class of sulfurized olefins includes sulfurized fatty acids and their esters. Fatty acids are often obtained from vegetable or animal oils and typically contain 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, fatty acids are obtained from lard oil, tall oil, peanut oil, soybean oil, cottonseed oil, sunflower seed oil, or mixtures thereof. Fatty acids and / or esters can be mixed with olefins such as α - olefins.

[0087] In another alternative embodiment, the antioxidant composition also contains a molybdenum-containing antioxidant in addition to the phenolic and / or amine antioxidants discussed above. When a combination of these three antioxidants is used, preferably, the ratio of phenol to amine to molybdenum-containing is (0 to 2):(0 to 2):(0 to 1).

[0088] One or more antioxidants may be present in the range of about 0 wt% to about 20 wt%, or about 0.1 wt% to about 10 wt%, or about 1 wt% to about 5 wt% of the lubricating oil composition.

[0089] Antiwear agent: The lubricating oil composition 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 esters; phosphites; phosphorus-containing carboxylic acid esters, ethers, or amides; sulfurized olefins; thiocarbamate-containing compounds such as thiocarbamate esters, alkylene-bonded thiocarbamates, and bis(S-alkyldithiocarbamyl) disulfides; and mixtures thereof, but are not limited thereto. A suitable antiwear agent can be molybdenum dithiocarbamate. Phosphorus-containing antiwear agents are fully described by European Patent No. 612839. The metal in the dialkyldithiophosphate salt can be an alkali metal, an alkaline earth metal, aluminum, lead, tin, molybdenum, manganese, nickel, copper, titanium, or zinc. A useful antiwear agent can be zinc dialkyldithiophosphate.

[0090] 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-bonded thiocarbamates, and bis(S-alkyl dithiocarbamyl) disulfide. Tartrates or tartrimides may contain alkyl-ester groups, but the total number of carbon atoms on the alkyl group can be at least 8. The antiwear agent may, in one embodiment, include citrate.

[0091] The antiwear agent may be present in an amount ranging from about 0 wt% to about 15 wt%, or about 0.01 wt% to about 10 wt%, or about 0.05 wt% to about 5 wt%, or about 0.1 wt% to about 3 wt% of the lubricating oil composition.

[0092] 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, boric acid fatty amines, boric acid epoxides, boronated detergents, and boronated dispersants such as boronated succinimide dispersants as disclosed in U.S. Patent No. 5,883,057. The boron-containing compound, if present, may be used in an amount sufficient to provide up to about 8 wt%, about 0.01 wt% to about 7 wt%, about 0.05 wt% to about 5 wt%, or about 0.1 wt% to about 3 wt% of the lubricating oil composition.

[0093] Additional detergents: The lubricating oil composition may optionally further contain one or more neutral detergents, low-base detergents, 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-bonded alkylphenol compounds, or methylene-bridged phenols. Suitable detergents and methods for their preparation are described in detail in numerous patent publications, including U.S. Patent No. 7,732,390 and the references cited therein.

[0094] The detergent matrix can be salted with an alkali metal or alkaline earth metal such as calcium, magnesium, potassium, sodium, lithium, barium, or a mixture thereof, but is not limited thereto. 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 an amount of 50 ppm or less, 40 ppm or less, 30 ppm or less, 20 ppm or less, or 10 ppm or less. Suitable detergents may include alkali metal salts or alkaline earth metal salts of petroleum sulfonic acids and long-chain mono- or di-alkylaryl sulfonic acids whose aryl groups are benzyl, tolyl, and xylyl. Examples of suitable detergents include calcium phenolate, sulfur-containing calcium phenolate, calcium sulfonate, calcium carlexarate, calcium salexarate, calcium salicylate, calcium carboxylate, calcium phosphate, mono- and / or di-thiophosphate calcium, calcium alkylphenol, calcium sulfur-bonded alkylphenol compound, calcium methylene-bridged phenol, magnesium phenolate, sulfur-containing magnesium phenolate, magnesium sulfonate, magnesium carlexarate, magnesium salexarate, magnesium salicylate, magnesium carboxylate, magnesium phosphate, mono- and / or di-thiophosphate magnesium, magnesium alkylphenol, magnesium sulfur-bonded alkylphenol compound, magnesium methylene-bridged phenol, sodium phenolate, sulfur-containing sodium phenolate, sodium sulfonate, sodium carlexarate, sodium salexarate, sodium salicylate, sodium carboxylate, sodium phosphate, mono- and / or di-thiophosphate sodium, sodium alkylphenol, sodium sulfur-bonded alkylphenol compound, or sodium methylene-bridged phenol, but are not limited thereto.

[0095] Overbased detergent additives are well known in the art and can be alkali or alkaline earth metal overbased detergent additives. Such detergent additives can be prepared by reacting a metal oxide or metal hydroxide with a 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.

[0096] The term "overbased" relates to metal salts such as metal salts of sulfonic acids, carboxylic acids, and phenols where the amount of metal present exceeds the stoichiometric amount. Such salts can have a conversion level greater than 100% (i.e., such salts can contain more than 100% of the theoretical amount of metal required to convert the acid to its "standard salt", "neutral salt"). In many cases, the expression "metal ratio", abbreviated as MR, is used to indicate the ratio of the total chemical equivalents of metal in the overbased salt to the chemical equivalents of metal in the neutral salt according to known chemical reactivity and stoichiometry. In the standard or neutral salt, the metal ratio is 1, but in the overbased salt, the MR is greater than 1. They are generally referred to as overbased, highly basic, or superbasic salts and can be salts of organic sulfuric acids, carboxylic acids, or phenols.

[0097] The overbased detergent of the lubricating oil composition can have a total base number (TBN) of about 200 mg KOH / gram or more, or as a further example, about 250 mg KOH / gram or more, or about 350 mg KOH / gram or more, or about 375 mg KOH / gram or more, or about 400 mg KOH / gram or more. The TBN is measured by the method of ASTM D-2896.

[0098] 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 carboxylate, overbased calcium phosphate, overbased calcium mono- and / or di-thiophosphate, overbased calcium alkylphenol, overbased calcium sulfur-bonded 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 carboxylate, overbased magnesium phosphate, overbased magnesium mono- and / or di-thiophosphate, overbased magnesium alkylphenol, overbased magnesium sulfur-bonded alkylphenol compound, or overbased magnesium methylene-bridged phenol.

[0099] Overbased calcium phenate detergents, when measured by the method of ASTM D-2896, all have a total base number of at least about 150 mg KOH / g, at least about 225 mg KOH / g, at least about 225 mg KOH / g to about 400 mg KOH / g, at least about 225 mg KOH / g to about 350 mg KOH / g, or about 230 mg KOH / g to about 350 mg KOH / g. When such a detergent composition is formed in an inert diluent, such as a process oil, usually a mineral oil, the total base number reflects the basicity of the overall composition including the diluent and any other materials (e.g., accelerators, etc.) that may be included in the detergent composition.

[0100] Overbased detergents can 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 for reducing or preventing rust within an engine or other automotive components such as a transmission or gears. The detergent can be present in the lubricating composition at from about 0 wt% to about 10 wt%, or from about 0.1 wt% to about 8 wt%, or from about 1 wt% to about 4 wt%, or greater than about 4 wt% to about 8 wt%.

[0101] Extreme Pressure Agents: The lubricating oil compositions herein may also optionally contain one or more extreme pressure agents. Extreme Pressure (EP) agents 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 dibenzyldisulfide, bis(chlorobenzyl)disulfide, dibutyltetrasulfide, methyl ester of sulfurized oleic acid, sulfurized alkylphenol, sulfurized dicyclopentadiene, sulfurized terpene, and sulfurized Diels-Alder adducts; phosphorus-sulfurized hydrocarbons such as reaction products of phosphorus sulfide with terpentine or methyl oleate; phosphoric acid esters such as dihydrocarbyl and trihydrocarbyl phosphites, e.g., dibutyl phosphite, diheptyl phosphite, dicyclohexyl phosphite, pentylphenyl phosphite; dipentylphenyl phosphite, tridecyl phosphite, distearyl phosphite, and polypropylene-substituted phenyl phosphite; metal thiocarbamates such as zinc dioctyldithiocarbamate and barium heptylphenol diacid; amine salts of alkyl and dialkyl phosphoric acids, including, for example, amine salts of reaction products of dialkyldithiophosphoric acid with propylene oxide; and mixtures thereof.

[0102] Friction modifier: The lubricating oil composition herein may also optionally contain one or more friction modifiers. Suitable friction modifiers can include those containing metals and those not containing metals, such as imidazoline, amide, amine, succinimide, alkoxylated amine, alkoxylated ether amine, amine oxide, amide amine, nitrile, betaine, quaternary amine, imine, amine salt, aminoguanidine, alkanolamide, phosphonate, metal-containing compounds, glycerol ester, sulfurized fatty compounds and olefins, sunflower oil, other naturally occurring vegetable or animal oils, dicarboxylic acid esters, esters or partial esters of polyols and one or more aliphatic or aromatic carboxylic acids, etc., but are not limited thereto.

[0103] Suitable friction modifiers can contain a hydrocarbyl group selected from a straight-chain, branched-chain, or aromatic hydrocarbyl group, or a mixture thereof, and can be saturated or unsaturated. The hydrocarbyl group can be composed of carbon and hydrogen or heteroatoms such as sulfur or oxygen. The hydrocarbyl group can range from about 12 to about 25 carbon atoms. In some embodiments, the friction modifier can be a long-chain fatty acid ester. In another embodiment, the long-chain fatty acid ester can be a mono-ester, or a di-ester, or a (tri)glyceride. The friction modifier can be a long-chain fatty amide, a long-chain fatty ester, a long-chain fatty epoxide derivative, or a long-chain imidazoline.

[0104] Other suitable friction modifiers can include organic, ashless (metal-free), nitrogen-free organic friction modifiers. Such friction modifiers include esters formed by reacting carboxylic acids and anhydrides with alkanols and can generally include polar end groups (such as carboxyl or hydroxyl) covalently bonded to lipophilic hydrocarbon chains. Examples of organic ashless nitrogen-free friction modifiers are generally known as glycerol monooleate (GMO), which can contain mono-, di-, and tri-esters of oleic acid. Other suitable friction modifiers are described in U.S. Patent No. 6,723,685, which is hereby incorporated by reference in its entirety.

[0105] Aminic friction modifiers can include amines or polyamines. Such compounds can have hydrocarbyl groups that are linear, either saturated or unsaturated, or mixtures thereof, and can contain from about 12 to about 25 carbon atoms. Further examples of suitable friction modifiers include alkoxylated amines and alkoxylated ether amines. Such compounds can have hydrocarbyl groups that are linear, either saturated or unsaturated, or mixtures thereof. These can contain from about 12 to about 25 carbon atoms. Examples include ethoxylated amines and ethoxylated ether amines.

[0106] Amines and amides can be used as such or in the form of adducts or reaction products with boron compounds such as boron oxide, boron halides, metaborates, boric acid, or mono-, di-, or tri-alkyl borates. Other suitable friction modifiers are described in U.S. Patent No. 6,300,291, which is hereby incorporated by reference in its entirety.

[0107] The friction modifier can optionally be present in a range such as from about 0 wt% to about 10 wt%, or from about 0.01 wt% to about 8 wt%, or from about 0.1 wt% to about 4 wt%.

[0108] Molybdenum-containing component: The lubricating oil composition herein may also optionally contain one or more molybdenum-containing compounds. The oil-soluble molybdenum compounds may have the functional performance of antiwear agents, antioxidants, friction modifiers, or mixtures thereof. The oil-soluble molybdenum compounds may include molybdenum dithiocarbamate, molybdenum dialkyldithiophosphate, molybdenum dithiophosphinate, amine salts of molybdenum compounds, molybdenum xanthate, molybdenum thioxanthate, molybdenum sulfide, molybdenum carboxylate, molybdenum alkoxide, trinuclear organic molybdenum compounds, and / or mixtures thereof. Examples of molybdenum sulfide include molybdenum disulfide. Molybdenum disulfide may be in the form of a stable dispersion. In one embodiment, the oil-soluble molybdenum compound may be selected from the group consisting of molybdenum dithiocarbamate, molybdenum dialkyldithiophosphate, amine salts of molybdenum compounds, and mixtures thereof. In one embodiment, the oil-soluble molybdenum compound may be molybdenum dithiocarbamate.

[0109] Suitable examples of molybdenum compounds that can be used include commercially available materials sold under trade names such as Molyvan 822 (trademark), Molyvan (trademark) A, Molyvan 2000 (trademark), and Molyvan 855 (trademark) of R.T. Vanderbilt Co., Ltd., and Sakura-Lube (trademark) 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. Patent No. 5,650,381, U.S. Reissue Patent Nos. 37,363 (E1), 38,929 (E1), and 40,595 (E1), the entire contents of which are incorporated herein by reference.

[0110] Additionally, the molybdenum compound can be an acidic molybdenum compound. Those included are molybdic acid, ammonium molybdate, sodium molybdate, potassium molybdate, and other alkali metal molybdates, as well as other molybdenum salts, such as sodium hydrogen molybdate, MoOCl4, MoO2Br2, Mo2O3Cl6, molybdenum trioxide, or similar acidic molybdenum compounds. Alternatively, the composition can provide molybdenum by a molybdenum / sulfur complex of a basic nitrogen compound, as described, for example, in U.S. Patent Nos. 4,263,152, 4,285,822, 4,283,295, 4,272,387, 4,265,773, 4,261,843, 4,259,195, and 4,259,194, and International Publication No. 94 / 06897, the foregoing patent documents being incorporated herein by reference in their entirety.

[0111] Another class of suitable organic molybdenum compounds are trinuclear molybdenum compounds such as compounds of the formula Mo3SkLnQz and mixtures thereof, wherein S represents sulfur, L represents independently selected ligands having a sufficient number of carbon atoms such that the compound is soluble or dispersible in oil, n is from 1 to 4, k varies from 4 to 7, Q is selected from the group of neutral electron donating compounds such as water, amines, alcohols, phosphines, and ethers, z ranges from 0 to 5, including non-stoichiometric values. Among the organic groups of all ligands, there can be at least 21 total carbon atoms, such as at least 25, at least 30, or at least 35 carbon atoms. Additional suitable molybdenum compounds are described in U.S. Patent No. 6,723,685, which is incorporated herein by reference in its entirety.

[0112] The oil-soluble molybdenum compound can be present in an amount sufficient to provide from about 0.5 ppm to about 2000 ppm, from about 1 ppm to about 700 ppm, from about 1 ppm to about 550 ppm, from about 5 ppm to about 300 ppm, or from about 20 ppm to about 250 ppm of molybdenum.

[0113] Transition metal-containing compound: In another embodiment, the oil-soluble compound may be a transition metal-containing compound or a 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.

[0114] In an embodiment, the oil-soluble transition metal-containing compound may function as an antiwear agent, a friction modifier, an antioxidant, an adhesion control additive, or one or more of these functions. In an embodiment, 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 can be used or can be used for the preparation of the oil-soluble material in the technology of the present disclosure, there are various Ti(IV) compounds such as titanium(IV) oxide; titanium(IV) sulfide; titanium(IV) nitrate; titanium(IV) alkoxides, such as titanium methoxide, titanium ethoxide, titanium propoxide, titanium isopropoxide, titanium butoxide, titanium 2-ethylhexoxide; and other titanium compounds or complexes, such as titanium phenate; titanium carboxylates, such as titanium(IV) 2-ethyl-1,3-hexanedioate or titanium citrate or titanium oleate; and titanium(IV)(triethanolaminato) isopropoxide, but are not limited to these. Other forms of titanium included in the disclosed technology include titanium phosphates such as titanium dithiophosphate (e.g., dialkyldithiophosphate) and titanium sulfonate (e.g., alkylbenzene sulfonate), or generally reaction products of titanium compounds forming salts such as oil-soluble salts with various acid materials. Therefore, titanium compounds can be derived, inter alia, from organic acids, alcohols, and glycols. Ti compounds may also exist in dimer or oligomer form containing a Ti-O-Ti structure. Such titanium materials are commercially available or can be easily prepared by suitable synthetic techniques known to those skilled in the art. These may exist as solids or liquids at room temperature depending on the specific compound. These may also be provided in solution form in a suitable inert solvent.

[0115] In one embodiment, titanium can be supplied as a Ti-modified dispersant such as a succinimide dispersant. Such materials can be prepared by forming a titanium mixed anhydride between a titanium alkoxide and a hydrocarbyl-substituted succinic anhydride such as alkenyl- (or alkyl) succinic anhydride. The resulting titanate-succinate intermediate can be used directly or reacted with any of several materials such as (a) a polyamine-based succinimide / amide dispersant having a free condensable -NH functional group; (b) components of a polyamine-based succinimide / amide dispersant, namely, alkenyl (or alkyl) succinic anhydride and polyamine; (c) a hydroxy-containing polyester dispersant prepared by reaction of a substituted succinic anhydride with a polyol, amino alcohol, polyamine, or mixtures thereof. Alternatively, the titanate-succinate intermediate can be reacted with other agents such as alcohols, amino alcohols, ether alcohols, polyether alcohols or polyols, or fatty acids, but the product can be used directly to impart Ti to the lubricating oil or further reacted with a succinic acid dispersant as described above. By way of example, 1 part (mole) of tetraisopropyl titanate can be reacted with about 2 parts (mole) of polyisobutene-substituted succinic anhydride at 140-150 °C for 5-6 hours to provide a titanium-modified dispersant or intermediate. The resulting material (30 g) can be further reacted at 150 °C for 1.5 hours with a succinimide dispersant from a polyisobutene-substituted succinic anhydride and polyethylene polyamine mixture (127 grams + diluent oil) to produce a titanium-modified succinimide dispersant.

[0116] Another titanium-containing compound can be the reaction product of a titanium alkoxide and a C6-C 25 carboxylic acid. The reaction product has the following formula:

[0117]

Chemical formula

[0118] [Chemical formula] (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), or the titanium compound is of the following formula:

[0119] [Chemical formula] (wherein x ranges from 0 to 3, R1 is selected from hydrocarbyl groups containing from about 6 to 25 carbon atoms, R2 and R3 are the same or different and are selected from hydrocarbyl groups containing from about 1 to 6 carbon atoms, and R4 is selected from the group consisting of H, C6 - C 25 any of the carboxylic acid moieties).

[0120] Suitable carboxylic acids can include, but are not limited to, caproic acid, caprylic acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, oleic acid, erucic acid, linoleic acid, linolenic acid, cyclohexanecarboxylic acid, phenylacetic acid, benzoic acid, neodecanoic acid, etc.

[0121] In embodiments, the oil - soluble titanium compound can be present in the lubricating oil composition in an amount to provide from about 0 to about 3000 weight ppm of titanium, or from 25 to about 1500 weight ppm of titanium, or from about 35 weight ppm to about 500 weight ppm of titanium, or from about 50 ppm to about 300 ppm.

[0122] 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. The viscosity index improver may include star polymers, and suitable examples are described in U.S. Patent Application Publication No. 20120101017(A1).

[0123] The lubricating oil composition herein may optionally contain one or more dispersant viscosity index improvers in addition to, or in place of, the viscosity index improver. Suitable viscosity index improvers may include functionalized polyolefins, such as ethylene-propylene copolymers functionalized with the reaction product of an acylating agent (such as maleic anhydride) and an amine, polymethacrylates functionalized with an amine, or esterified maleic anhydride-styrene copolymers reacted with an amine.

[0124] The total amount of the viscosity index improver and / or dispersant viscosity index improver may be about 0 wt% to about 20 wt%, about 0.1 wt% to about 15 wt%, about 0.1 wt% to about 12 wt%, or about 0.5 wt% to about 10 wt% of the lubricating oil composition.

[0125] Other Optional Additives: Other additives may be selected to perform one or more functions required for the lubricating fluid. Further, one or more of the aforementioned additives may be multifunctional and may provide additional functions in addition to, or other functions than, the functions described herein.

[0126] The lubricating oil composition according to the present disclosure may optionally contain other performance additives. The other performance additives may be additional to the specific additives of the present disclosure and / or may include one or more of a metal deactivator, a viscosity index improver, a detergent, an ashless TBN booster, a friction modifier, an antiwear agent, a corrosion inhibitor, a rust inhibitor, a dispersant, a dispersant viscosity index improver, an extreme pressure agent, an antioxidant, an antifoaming agent, a demulsifier, an emulsifier, a pour point depressant, a seal swell agent, and mixtures thereof. Typically, a fully formulated lubricating oil will contain one or more of these performance additives.

[0127] Suitable metal deactivators include derivatives of benzotriazole (typically tolyltriazole), dimercaptothiadiazole derivatives, 1,2,4-triazole, benzimidazole, 2-alkyldithiobenzimidazole, or 2-alkyldithiobenzothiazole; antifoaming agents including copolymers of ethyl acrylate and 2-ethylhexyl acrylate and optionally vinyl acetate; demulsifiers including trialkyl phosphate, polyethylene glycol, polyethylene oxide, polypropylene oxide, and (ethylene oxide - propylene oxide) polymers; and pour point depressants including esters of maleic anhydride - styrene, polymethacrylate, polyacrylate, or polyacrylamide may be mentioned.

[0128] Suitable antifoaming agents include silicon-based compounds such as siloxane.

[0129] Suitable pour point depressants may include polymethyl methacrylate or mixtures thereof. The pour point depressant may be present in an amount sufficient to provide from about 0 wt% to about 1 wt%, from about 0.01 wt% to about 0.5 wt%, or from about 0.02 wt% to about 0.04 wt% based on the final weight of the lubricating oil composition.

[0130] Suitable rust inhibitors can be a single compound or a mixture of compounds having the property of suppressing corrosion of the iron metal surface. 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 serotic acid, and oil-soluble polycarboxylic acids including dimeric and trimeric acids such as those produced from tall oil fatty acid, 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 such as tetrapropenyl succinic acid, tetradecenyl succinic acid, and hexadecenyl succinic acid, wherein the alkenyl group contains about 10 or more carbon atoms. Another useful type of acidic corrosion inhibitor is a semi-ester of an alkenyl succinic acid having about 8 to about 24 carbon atoms in the alkenyl group and an alcohol such as polyglycol. The corresponding semi-amides of such alkenyl succinic acids are also useful. Useful rust inhibitors are high molecular weight organic acids.

[0131] When present, the rust inhibitor can be used in an amount sufficient to provide from about 0 wt% to about 5 wt%, from about 0.01 wt% to about 3 wt%, from about 0.1 wt% to about 2 wt% based on the final weight of the lubricating oil composition.

[0132] Generally speaking, suitable lubricating oils containing neutral to overbased alkylphenate sulfide products herein may contain additive components within the ranges listed in the following table.

[0133]

Table 2

[0134] The percentages of the above components represent the weight percentages of the respective components based on the weight of the final lubricating oil composition. The remainder of the lubricating oil composition consists of one or more base oils. The additives used when formulating the compositions described herein can be blended into the base oil individually or in various partial combinations. However, it may be preferred to use an additive concentrate (i.e., an additive plus a diluent such as a hydrocarbon solvent) to blend all of the components simultaneously. A fully formulated lubricating oil conventionally contains a dispersant / inhibitor package or DI package and an additive package, as referred to herein, that supplies the properties required in the formulation.

[0135] The following definitions are provided to clarify the meaning of specific terms used herein.

[0136] The terms "oil composition", "lubricating composition", "lubricating oil composition", "lubricating oil", "lubricating oil composition", "lubricating composition", "fully formulated lubricating oil composition", and "lubricant" are synonymous and considered to be fully interchangeable terms, and refer to a finished lubricating product comprising a major amount of base oil and a minor amount of additive composition.

[0137] As used herein, the terms "additive package", "additive concentrate", and "additive composition" are considered to be synonymous and fully interchangeable terms that refer to a portion of the lubricating oil composition excluding the major amount of base oil stock mixture.

[0138] The term "overbased" relates to metal salts such as sulfonates, carboxylates, salicylates, and / or phenates where the amount of metal present exceeds the stoichiometric amount. Such salts can have a conversion level greater than 100% (i.e., such salts can contain more than 100% of the theoretical amount of metal required to convert the acid to its "standard salt", "neutral salt"). Often, the expression "metal ratio", abbreviated as MR, is used to indicate the ratio of the total chemical equivalent of the metal in the overbased salt to the chemical equivalent of the metal in the neutral salt, according to known chemical reactivity and stoichiometry. In the standard or neutral salt, the metal ratio is 1, but in the overbased salt the MR is greater than 1. These are generally referred to as overbased, highly basic, or superbasic salts and may be salts of organic sulfuric acids, carboxylic acids, salicylates, sulfonates, and / or phenols.

[0139] The term "alkaline earth metal" relates to calcium, barium, magnesium, and strontium, and the term "alkali metal" refers to lithium, sodium, potassium, rubidium, and cesium.

[0140] As used herein, the terms "hydrocarbyl" or "hydrocarbyl substituent" or "hydrocarbyl group" are used in their ordinary meaning well known to those skilled in the art. Specifically, it refers to a group having a carbon atom directly bonded to the remainder of the molecule and having predominantly hydrocarbon character. Each hydrocarbyl group is independently selected from hydrocarbon substituents, and the substituted hydrocarbon substituents contain one or more of halo group, hydroxyl group, alkoxy group, mercapto group, nitro group, nitroso group, amino group, pyridyl group, furyl group, imidazolyl group, oxygen, and nitrogen, and two or less non-hydrocarbon substituents are present per ten carbon atoms in the hydrocarbyl group.

[0141] As used herein, the terms "hydrocarbylene substituent" or "hydrocarbylene group" are used in their ordinary meaning well known to those skilled in the art. Specifically, it refers to a group that is directly bonded to the remainder of the molecule by carbon atoms at two locations in the molecule and mainly has the characteristics of hydrocarbons. Each hydrocarbylene group is independently selected from divalent hydrocarbon substituents, and the substituted divalent hydrocarbon substituents are halo groups, alkyl groups, aryl groups, alkylaryl groups, arylalkyl groups, hydroxyl groups, alkoxy groups, mercapto groups, nitro groups, nitroso groups, amino groups, pyridyl groups, furyl groups, imidazolyl groups, oxygen, and nitrogen, and two or less non-hydrocarbon substituents are present per 10 carbon atoms in the hydrocarbylene group.

[0142] As used herein, the term "weight percent" means the percentage that the stated component represents relative to the total weight of the composition, unless otherwise expressly stated.

[0143] As used herein, the terms "soluble", "oil-soluble", or "dispersible" may indicate that a compound or additive is soluble, soluble, miscible, or suspendable in any proportion in oil, but not necessarily so. However, the foregoing terms mean that they are soluble, suspendable, soluble, or stably dispersible in oil to such an extent that they can exert their intended effects, for example, in an environment where oil is used. Further, if desired, incorporating other additives may also make it possible to incorporate higher levels of specific additives.

[0144] As used herein, the term "TBN" is used to indicate the total base number (Total Base Number) in mg KOH / g when measured by the method of ASTM D2896.

[0145] As used herein, the term "lime" refers to calcium hydroxide, calcium oxide, and similar compounds, also known as slaked lime or hydrated lime, for example.

[0146] As used herein, the term "alkyl" refers to a straight-chain, branched, cyclic, and / or substituted saturated chain moiety of from about 1 to about 100 carbon atoms. As used herein, the term "alkenyl" refers to a linear, branched, cyclic, and / or substituted unsaturated chain moiety of from about 3 to about 10 carbon atoms. As used herein, the term "aryl" refers to monocyclic and polycyclic aromatic compounds that may contain alkyl, alkenyl, alkylaryl, amino, hydroxyl, alkoxy, halo substituents, and / or heteroatoms including, but not limited to, nitrogen, oxygen, and sulfur.

[0147] The molecular weight of any embodiment herein can be determined using gel permeation chromatography (GPC) equipment obtained from Waters or similar equipment, and data processed with Waters Empower Software or similar software. The GPC equipment can be provided with a Waters separation module and a Waters refractive index detector (or any similar optional equipment). The GPC operating conditions can include a guard column, four Agilent PLgel columns (length 300×7.5 mm, particle size 5 μm, and pore diameter in the range of 100 - 10,000 Å), and a column temperature of about 40°C. Unstabilized HPLC grade tetrahydrofuran (THF) can be used as the solvent at a flow rate of 1.0 mL / min. The GPC equipment can be calibrated with commercially available polystyrene (PS) standards having a narrow molecular weight distribution in the range of 500 - 380,000 g / mol. The calibration curve can be extrapolated for samples having a mass of less than 500 g / mol. The samples and PS standards can be dissolved in THF, prepared at a concentration of 0.1 - 0.5 wt%, and used without filtration. The GPC measurement is also described in U.S. Patent No. 5,266,223, which is incorporated herein by reference. The GPC method additionally provides molecular weight distribution information. See also, for example, W.W. Yau, J.J. Kirkland and D.D. Bly, “Modern Size Exclusion Liquid Chromatography”, John Wiley and Sons, New York, 1979, which is incorporated herein by reference.

Example

[0148] The following examples illustrate exemplary embodiments of the present disclosure. In these examples as well as elsewhere in this application, all ratios, parts, and percentages are by weight unless otherwise indicated. It is intended that these examples be presented for illustrative purposes only and not be intended to limit the scope of the invention disclosed herein.

[0149] Example 1

[0150] Using xylene, methanol as an accelerator, molar excess magnesium oxide, carbon dioxide as an overbased acid, and neodecanoic acid, a comparative (e.g., conventional) overbased magnesium sulfonate detergent was prepared by overbasing C14 - C24 alkylbenzene sulfonic acid at a temperature of about 50 to about 70 °C. The mixture was vacuum stripped at about 180 °C to form a comparative overbased magnesium sulfonate detergent having a TBN of about 450 mg KOH / gram, about 9.5 to about 10.5 weight percent magnesium, and a KV100 viscosity of about 9 to about 10 cSt. Unreacted solids were removed by filtration and / or centrifugation. This conventional or comparative detergent was not further post - treated after vacuum stripping.

[0151] Example 2

[0152] Next, the conventional overbased magnesium sulfonate detergent of Example 1 was further post - treated with polyisobutylene succinic anhydride (PIBSA) at about 180 °C. Here, different polyisobutenes having a number average molecular weight of about 550 g / mol, about 850 g / mol, about 950 g / mol, about 1000 g / mol, or about 2400 g / mol were used. The polyisobutylene in each case was considered to be HR - PIB having at least about 50 mol% terminal double bonds. The comparative overbased magnesium sulfonate detergent of Example 1 was post - treated to prepare a post - treated overbased magnesium sulfonate detergent by treating it at 180 °C for about 15 minutes to about 60 minutes using each of the post - treatment reactants in Table 2 below.

[0153]

Table 3

[0154] The storage stability of a lubricating oil composition containing magnesium overbased sulfonate and 0.4 weight percent glycerol monooleate was evaluated at about 55°C. For this study, the control (C) contained in the same GF-6 lubricant the comparative or conventional magnesium overbased sulfonate of Example 1, followed by the post-treated magnesium overbased sulfonate detergents 1-8 from Example 2 (Table 2).

[0155] To test for storage stability, more than 20 grams to about 25 grams of each lubricant were added to clear glass vials. Each vial was stored at about 55°C and evaluated for stability once a week for up to 28 weeks (after about 168 hours). As shown in Table 3 below, passing stability is indicated by "P" and failing stability is indicated by "F". Passing means that the lubricant contained no sediment, dropout, and film formation. A failing sample means that any sediment (solid particles) or film was present at the bottom of the vial when visually inspected at the appropriate time (weeks) using a backlight.

[0156]

Table 4

[0157] As shown by the stability chart of Example 3, control sample C of conventional overbased magnesium sulfonate and glycerol monooleate (i.e., untreated) failed stability after only 4 weeks. As shown by comparative sample 8, post-treatment with PIBSA of molecular weight 550 improved stability, but it was only added for 1 week. Post-treatment with PIBSA of higher molecular weights of 850 or even 2400 improved stability, but only up to a maximum of 17 weeks (i.e., comparative samples 1-2 and 7). Samples 4, 5, and 6 of the present invention post-treated with about 8 - about 10 weight percent of PIBSA of about 950 - about 1000 g / mol had unexpectedly improved storage stability up to at least 18 weeks (sample 4 of the present invention using about 8 percent of about 950 Mn PIBSA), up to 27 weeks (sample 5 of the present invention using about 10 percent of about 950 Mn PIBSA), and up to 26 weeks (sample 6 of the present invention using about 10 percent of about 1000 Mn PIBSA).

[0158] 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 specifically limited to one referent. Thus, for example, reference to "an antioxidant" includes two or more different antioxidants. As used herein, the term "comprising" and its grammatical variations are intended to be non-limiting such that the listing of items in a list does not exclude other similar items where the listing of items in the list may be replaced or additional to the items in the list.

[0159] For the purposes of this specification and the appended claims, unless otherwise indicated, all numbers expressing amounts, percentages, or proportions, and other numerical values used in this specification and the claims are to be understood as being modified in all instances by the term "about." Accordingly, unless otherwise indicated, the numerical parameters set forth in the following specification and attached claims are approximations that may vary depending upon the desired properties sought to be obtained by the present disclosure. At the very least, and not as an attempt to limit the application of the doctrine of equivalents to the scope of the claims, each numerical parameter should be construed in light of the number of reported significant digits and in reference to ordinary rounding techniques.

[0160] It should be understood that each component, compound, substituent, or parameter disclosed herein is disclosed for use alone or in combination with one or more of any other components, compounds, substituents, or parameters disclosed herein.

[0161] It should be further understood that each range disclosed herein is to be interpreted as disclosing each and every specific value within the range having the same number of significant digits. Thus, for example, a range of 1 to 4 is to be interpreted as disclosing not only the values 1, 2, 3, and 4, but also any range of such values.

[0162] It should be further understood that each lower limit of each range disclosed herein is to be construed as disclosed in combination with each upper limit of each range and each specific value within each range for the same component, compound, substituent, or parameter disclosed herein. Accordingly, the present disclosure should be construed as a disclosure of all ranges derived by combining each lower limit of each range with each upper limit of each range, or with 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 should be further understood that any range between the endpoint values within a broad range is also contemplated herein. Accordingly, the range of 1 to 4 also means ranges such as 1 to 3, 1 to 2, 2 to 4, 2 to 3, etc.

[0163] Furthermore, the specific amounts / values of components, compounds, substituents, or parameters disclosed in the detailed description or examples should be construed as a disclosure of either the lower or upper limit of a range, and thus can form a range for the same component, compound, substituent, or parameter in combination with any other lower or upper limit or specific amount / value within the range for the same component, compound, substituent, or parameter disclosed elsewhere in the present application.

[0164] Although specific embodiments have been described, alternatives, modifications, variations, improvements, and substantial equivalents that are not presently contemplated or that cannot presently be contemplated by the applicants or other persons of ordinary skill in the art may arise. Accordingly, the filed and potentially amended appended claims are intended to embrace all such alternatives, modifications, variations, improvements, and substantial equivalents.

Claims

Claim 1 A process for preparing a magnesium overbased sulfonate detergent having improved compatibility with a friction modifier, comprising: (a) preparing a mixture of a C14-C24 alkylaryl sulfonic acid or its salt, magnesium oxide or magnesium hydroxide, and one or more branched C8-C16 carboxylic acids; (b) carbonating the mixture to form a magnesium overbased sulfonate; (c) treating the carbonated magnesium overbased sulfonate with about 6 to about 10 weight percent of a hydrocarbyl-substituted succinic acid or its anhydride at about 160°C to about 200°C, wherein the hydrocarbyl substituent is derived from a polyisobutylene having a number average molecular weight of about 900 to about 1500 and having more than 50 mole percent terminal double bonds, to form the magnesium overbased sulfonate detergent; The process, wherein the magnesium overbased sulfonate detergent has improved compatibility with a friction modifier. Claim 2 The process of claim 1, wherein the magnesium overbased sulfonate before the treatment has a total base number (TBN) of at least about 450 mg KOH / g, the magnesium overbased sulfonate detergent after the treatment has a total base number (TBN) of less than about 410 mg KOH / g, and / or the treatment step (c) is substantially free of a dicarboxylic acid, and the dicarboxylic acid is one or more of phthalic acid, succinic acid, maleic acid, azelaic acid, suberic acid, sebacic acid, fumaric acid, adipic acid, malonic acid, or combinations thereof. Claim 3 The process of claim 2, wherein the magnesium overbased sulfonate detergent contains at least about 60 weight percent of magnesium sulfonate as an active ingredient, and / or the magnesium overbased sulfonate detergent has up to about 35 weight percent of process oil. Claim 4 The process of claim 1, wherein the magnesium overbased sulfonate is vacuum stripped at about 160°C to about 200°C prior to the treatment step (c), and / or the magnesium overbased sulfonate detergent has a storage stability of at least about 18 weeks at about 55°C when combined with up to about 0.4 weight percent of glycerol monooleate. Claim 5 A storage-stable overbased magnesium sulfonate detergent having improved compatibility with a friction modifier, (a) preparing a mixture of a linear C14-C24 alkylaryl sulfonic acid or a salt thereof, magnesium oxide or magnesium hydroxide, and one or more branched C8-C16 carboxylic acids; (b) carbonating the mixture to form overbased magnesium sulfonate; (c) treating the carbonated overbased magnesium sulfonate with about 6 to about 10 weight percent of a hydrocarbyl-substituted succinic acid or its anhydride at about 160 °C to about 200 °C, wherein the hydrocarbyl substituent is derived from polyisobutylene having a number average molecular weight of about 900 to about 1500 and having more than 50 mole percent terminal double bonds, to form the overbased magnesium sulfonate detergent; and The overbased magnesium sulfonate detergent having improved compatibility with a friction modifier, a storage-stable overbased magnesium sulfonate detergent.

6. The overbased magnesium sulfonate before the treatment has a total base number (TBN) of at least about 450 mg KOH / g, the overbased magnesium sulfonate detergent after the treatment has a total base number (TBN) of less than about 410 mg KOH / g, and / or the treatment step (c) is substantially free of dicarboxylic acids, wherein the dicarboxylic acids are one or more of phthalic acid, succinic acid, maleic acid, azelaic acid, suberic acid, sebacic acid, fumaric acid, adipic acid, malonic acid, or combinations thereof. The storage-stable overbased magnesium sulfonate detergent according to claim 5.

7. The overbased magnesium sulfonate detergent contains at least about 60 weight percent of magnesium sulfonate as an active ingredient, and / or the overbased magnesium sulfonate detergent has about 35 weight percent or less of process oil. The storage-stable overbased magnesium sulfonate detergent according to claim 5.

9. The magnesium overbased sulfonate is vacuum stripped at about 160 °C to about 200 °C prior to said treatment step (c), and / or the magnesium overbased sulfonate detergent has a total base number (TBN) of about 350 to about 410 mg KOH / g and is at least about 18 weeks storage stable at about 55 °C when combined with a maximum of about 0.4 weight percent glycerol monooleate friction modifier. The storage stable magnesium overbased sulfonate detergent according to claim 5.

10. An engine oil lubricating composition comprising a major amount of one or more lubricating viscosity base oils, the storage stable magnesium overbased sulfonate detergent according to claim 5, and a maximum of about 0.4 weight percent glycerol monooleate friction modifier.

11. A method for improving the storage stability of a magnesium overbased sulfonate detergent, comprising: (a) preparing a mixture of a linear C14-C24 alkylaryl sulfonic acid or a salt thereof, magnesium oxide or magnesium hydroxide, and one or more branched C8-C16 carboxylic acids; carbonating said mixture to form a magnesium overbased sulfonate; treating the formed magnesium overbased sulfonate with about 6 to about 10 weight percent of a hydrocarbyl-substituted succinic anhydride at about 160 °C to about 200 °C, wherein the hydrocarbyl substituent is derived from a polyisobutylene having a number average molecular weight of about 900 to about 1500 and having more than 50 mole percent terminal double bonds, to form the magnesium overbased sulfonate detergent; (b) combining about 0.02 to about 5 weight percent of said magnesium overbased sulfonate detergent with a maximum of about 0.4 glycerol monooleate friction modifier; wherein the combination of the magnesium overbased sulfonate detergent and the glycerol monooleate friction modifier is at least about 18 weeks storage stable at about 55 °C. A method for improving the storage stability of a magnesium overbased sulfonate detergent.

12. The method according to claim 11, wherein the magnesium overbased sulfonate before the treatment has a total base number (TBN) of at least about 450 mg KOH / g and the magnesium overbased sulfonate detergent after the treatment has a total base number (TBN) of less than about 410 mg KOH / g.

13. The method according to claim 11, wherein the overbased magnesium sulfonate detergent contains at least about 60 weight percent of magnesium sulfonate as an active ingredient and / or the overbased magnesium sulfonate detergent has up to about 35 weight percent of process oil.

14. The method according to claim 11, wherein the treatment step (c) is substantially free of dicarboxylic acid, and the dicarboxylic acid is one or more of phthalic acid, succinic acid, maleic acid, azelaic acid, suberic acid, sebacic acid, fumaric acid, adipic acid, malonic acid, or combinations thereof.

15. The method according to claim 11, wherein the overbased magnesium sulfonate is vacuum stripped at about 160 °C to about 200 °C prior to the treatment step (c) and / or the overbased magnesium sulfonate detergent has a total base number (TBN) of about 350 to about 410 mg KOH / g and has at least about 18 weeks of storage stability at about 55 °C when combined with up to about 0.4 weight percent of a glycerol monooleate friction modifier.

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