Lubricating composition for improved fuel economy

Abstract

To provide a passenger vehicle engine lubricating oil composition, and a method for improving fuel economy in a passenger vehicle engine by using the lubricating oil composition.SOLUTION: There is provided a method for improving fuel economy, comprising: lubricating an engine crankcase of a passenger vehicle engine with a lubricating oil composition; and achieving a positive increase in fuel economy as measured by fuel economy. The lubricating oil composition includes: (i) a calcium-containing hydrocarbyl-substituted sulfonate compound providing about 900 ppm or more of calcium to the lubricating oil composition, in which the lubricating oil composition lacks a sulfur-free detergent; (ii) an oil-soluble molybdenum compound providing from about 500 to about 1200 ppm of molybdenum to the lubricating oil composition; (iii) an ash-contributing additive in an amount to provide a total measured sulfated ash content of about 0.8 wt.% or less; (iv) a total base number (TBN) of the lubricating oil composition of about 6.0 mg KOH / g or more; and (v) a high temperature, high shear viscosity of about 1.7 to about 2.9 cSt at 150°C.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present disclosure relates to lubricating compositions, particularly lubricating compositions that exhibit improved fuel economy. [Background technology]

[0002] Automotive manufacturers continue to push for improved efficiency, fluid life, and fuel economy, thereby placing ever-increasing demands on engines, lubricants, and their components. Today's engines are often becoming smaller, lighter, and more efficient with technologies designed to improve fuel economy, performance, and power output. These requirements also mean that the performance of engine oils must evolve to meet the higher demands of such modern engines and the corresponding performance standards associated with their unique uses and applications. Due to such stringent demands on engine oils, lubricant manufacturers often tailor lubricants and their additives to meet specific performance requirements for industry and / or manufacturer applications.

[0003] Typically, industry standards and / or automotive manufacturers require certain performance characteristics, and therefore, a lubricant designed for one use or application may not meet all requirements for a different use or application. For example, there is often a trade-off in engine oil performance between fuel economy and other performance requirements. Fuel economy can be evaluated, for example, through the ratings established by the Japanese Automotive Standards Organization (JASO) in the JASO M366 Combustion Engine Fuel Economy Test and / or the JASO M365 Motoring Engine Fuel Economy Test. Previously, it was generally understood that the use of additives based on salicylate chemicals tended to result in lubricants with lower friction coefficients and / or improved surfactant functionality compared to other detergent chemicals, which were expected to provide benefits in terms of fuel economy and detergency. However, advances in lubricant formulations and component interactions have created shortcomings of traditional salicylate additive chemicals in the context of achieving improved fuel efficiency in ultra-low viscosity engine oil compositions. Summary of the Invention

[0004] The present disclosure relates to engine lubricating oil compositions and methods of lubricating the engine crankcase of a passenger vehicle engine with the lubricating oil compositions to achieve a positive increase in fuel economy as measured according to one or both of JASO M 366 and / or JASO M 365. In one approach or embodiment, provided herein is a method of improving fuel economy in a passenger vehicle engine using the lubricating oil compositions. In an aspect of this approach or embodiment, a method herein comprises lubricating an engine crankcase of a passenger vehicle engine with a lubricating oil composition and achieving a positive increase in fuel economy as measured according to one or both of JASO M366 and / or JASO M365, the lubricating oil composition comprising: (i) at least one calcium-containing hydrocarbyl-substituted sulfonate compound providing about 900 ppm or more of calcium to the lubricating oil composition, wherein the lubricating oil composition is essentially devoid of sulfur-free detergents; (ii) at least one oil-soluble molybdenum compound providing about 500 to about 1200 ppm of molybdenum to the lubricating oil composition; (iii) an ash-containing additive in an amount to provide a total measured sulfated ash of about 0.8 weight percent or less, as measured according to ASTM D874; and (iv) a total base number of the lubricating oil composition of at least about 6.0 mg KOH / gram, as measured according to ASTM D2896. number, TBN); and (v) a high temperature, high shear viscosity of about 1.7 to about 2.9 cSt when measured at 150° C. according to ASTM D4683.

[0005] In other approaches or embodiments, the method described in the preceding paragraph may include one or more other features, steps, or embodiments in any combination. These other features, steps, or embodiments include one or more of the following: the lubricating oil composition has a positive fuel economy increase of greater than 1.1% as measured in accordance with JASO M366; and / or the lubricating oil composition has a positive fuel economy increase of greater than 1.5% (Japan WLTC mode) as measured in accordance with JASO M365; and / or the calcium-containing hydrocarbyl-substituted sulfonate compound provides up to about 1500 ppm of calcium; and / or the calcium-containing hydrocarbyl-substituted sulfonate compound provides at least about 175 mg of calcium as measured in accordance with ASTM D2896. and / or the calcium-containing hydrocarbyl-substituted sulfonate compound comprises a hydrocarbyl portion thereof having a number average molecular weight of from about 80 to 300 g / mole; and / or the hydrocarbyl portion of the calcium-containing hydrocarbyl-substituted sulfonate component comprises a linear or branched C6 to C30 hydrocarbyl group; and / or the sulfur-free detergent comprises a metal-containing salicylate detergent; and / or the lubricating oil composition has a calcium to molybdenum weight ratio of from about 1:1 to about 2:1; and / or the oil-soluble molybdenum compound is selected from the group consisting of molybdenum dithiocarbamate, molybdenum dialkyldithiophosphate, molybdenum sulfide, molybdenum disulfide, molybdenum dithiophosphinate, amine salts of molybdenum compounds, and / or the lubricating oil composition has a weight ratio of calcium to molybdenum of from about 1:1 to about 2:1; and / or the lubricating oil composition is essentially devoid of metal salts of phenates, calixarates, salixarates, salicylates, carboxylic acids, or combinations thereof; and / or the lubricating oil composition is substantially free of organic friction modifiers; and / or the lubricating oil composition has a KV100 of about 8 cSt or less (or about 7.8 cSt or less, or about 7.4 cSt or less, or about 7.0 cSt or less).

[0006] In yet another approach or embodiment, described herein are passenger car engine lubricating oil compositions having components and relationships of such components configured such that the composition achieves a positive fuel economy improvement in accordance with JASO M366 and / or JASO M365. In an aspect of this approach or embodiment, a composition includes at least one calcium-containing hydrocarbyl-substituted sulfonate compound providing about 900 ppm or more of calcium to a lubricating oil composition, wherein the lubricating oil composition is essentially devoid of sulfur-free detergents; at least one oil-soluble molybdenum-containing compound providing about 500 to about 1200 ppm of molybdenum to the lubricating oil composition; an ash-contributing additive in an amount to provide a total measured sulfated ash of about 0.8 weight percent or less, as measured in accordance with ASTM D874; a total base number (TBN) of the lubricating oil composition of at least about 6.0 mg KOH / gram, as measured in accordance with ASTM D2896; and a high temperature, high shear viscosity of about 1.7 to about 2.9 cSt, as measured at 150°C in accordance with ASTM D4683, wherein the lubricating oil composition has a calcium to molybdenum weight ratio of about 1:1 to about 2:1.

[0007] In yet another approach or embodiment, the lubricating composition described in the preceding paragraph includes other features or embodiments in any combination. These other features or embodiments include one or more of the following (and / or may include any feature or embodiment of the lubricating oil composition described above with respect to the method): the lubricating oil composition has a positive fuel economy increase of greater than 1.1% as measured in accordance with JASO M366; and / or the lubricating oil composition has a positive fuel economy increase of greater than 1.5% (Japan WLTC mode) as measured in accordance with JASO M365; and / or the calcium-containing hydrocarbyl-substituted sulfonate compound provides up to about 1500 ppm of calcium; and / or the calcium-containing hydrocarbyl-substituted sulfonate compound has a number average molecular weight of about 80 to 300 g / mol and includes a hydrocarbyl moiety derived from a C14 to C30 olefin.

[0008] In yet another approach or embodiment, the disclosure provides for the use of any of the embodiments of the lubricating oil compositions described in this Summary to achieve a positive fuel economy increase of greater than 1.1% when measured in accordance with JASO M366, and / or a positive fuel economy increase of greater than 1.5% (Japan WLTC mode) when measured in accordance with JASO M365, when the lubricating oil composition lubricates the crankcase of a passenger car engine. DETAILED DESCRIPTION OF THE INVENTION

[0009] The present disclosure relates to passenger car engine lubricating oil compositions and methods of lubricating the crankcase of a passenger car engine (preferably a spark-ignition or gasoline-fueled engine) with selected calcium sulfonate-based compounds in combination with one or more oil-soluble molybdenum compounds in ultra-low viscosity engine oils (e.g., lubricating oil compositions having a high-temperature, high-shear viscosity of about 2.9 cSt or less and / or a KV100 viscosity of about 8 cSt or less at 150°C) to achieve improved fuel economy. The Japan Automotive Society (JASO) publishes standards and test procedures for evaluating the fuel economy of automotive gasoline engine lubricants. As described in the Background Art, the JASO M365 standard evaluates fuel economy improvement in a motoring engine test compared to a reference oil, and the JASO M366 standard evaluates fuel economy improvement in a combustion engine test compared to a reference oil. Additives utilizing salicylate chemicals have previously been expected to offer the most powerful options for achieving improved fuel economy in such tests. However, it has been unexpectedly discovered that lubricant compositions comprising at least one calcium-containing hydrocarbyl-substituted sulfonate compound in combination with one or more oil-soluble molybdenum compounds achieve better fuel economy improvements in one or both of the M365 and / or M366 tests compared to compositions utilizing conventional salicylate chemistries.

[0010] In one embodiment, the passenger car engine lubricant composition used in the methods and methods herein has a composition and certain component relationships effective to achieve a positive fuel economy increase as measured in accordance with one or both of JASO M365 and / or M366, specifically, a fuel economy improvement of greater than 1.4 percent (or 1.5 percent in the Japan WLTC cycle) as measured in accordance with JASO M365, and / or a fuel economy improvement of greater than 1.1 percent (FEI adjusted) as measured in accordance with M366. In some approaches, the passenger car engine lubricating oil compositions of the methods and processes herein also have a composition effective to provide a high temperature high shear (HTHS) viscosity at 150°C of from about 1.7 to about 2.9 cSt, as measured in accordance with ASTM D4683 (in other approaches, from about 2.3 to about 2.8 cSt, or from about 2.4 to about 2.8 cSt), and / or an ultra-low KV100 viscosity of 8 cSt or less, as measured in accordance with ASTM D445 (in other approaches, from about 7.8 cSt or less, from about 7.6 cSt or less, or from about 7.4 cSt or less).

[0011] In one approach or embodiment, the lubricating oil compositions of the methods and methods described herein have a selected composition utilizing one or more sulfonate-based compounds to provide a method of improving fuel economy when combined with a selected oil-soluble molybdenum compound. In one aspect, the present disclosure provides a method of improving fuel economy in a passenger car engine (preferably a spark-ignition engine or a gasoline engine) using a lubricating oil composition, the method comprising lubricating an engine crankcase of the passenger car engine with the lubricating oil composition and achieving a positive increase in fuel economy as measured in accordance with one or both of JASO M366 and / or JASO M365. In one approach, the lubricating oil composition comprises: (i) at least one calcium-containing hydrocarbyl-substituted sulfonate compound providing the lubricating oil composition with about 900 ppm or more of calcium, wherein the lubricating oil composition is essentially devoid of sulfur-free detergent additives (e.g., less than about 100 ppm of sulfur-free detergent additives, preferably less than about 50 ppm of sulfur-free detergent additives, more preferably less than about 20 ppm of sulfur-free detergent additives, and more preferably no functional amount of sulfur-free detergent additives); (ii) at least one oil-soluble molybdenum compound providing the lubricating oil composition with about 500 to about 1200 ppm of molybdenum; (iii) an ash-contributing additive in an amount to provide a total measured sulfated ash of about 0.8 weight percent or less, as measured in accordance with ASTM D874; (iv) a total base number (TBN) of the lubricating oil composition of at least about 6.0 mg KOH / gram, as measured in accordance with ASTM D2896; and (v) an ash-contributing additive in an amount to provide a total measured sulfated ash of about 0.8 weight percent or less, as measured in accordance with ASTM D2896. and a high temperature, high shear viscosity of about 1.7 to about 2.9 cSt as measured at 150°C in accordance with D4683. As shown in the examples herein, such methods of using the lubricating oil compositions herein result in a positive fuel economy increase of greater than 1.1% (FEI adjusted) as measured in accordance with JASO M366, and / or a positive fuel economy increase of greater than 1.4% as measured in accordance with JASO M365 (or at least about 1.5% as measured in the Japan WLTC cycle).Methods and compositions including additives that use conventional salicylate-based compounds have not been able to achieve such performance in the M366 and / or M365 tests. As discussed further below, sulfur-free detergent additives generally include metal-containing salicylate-based compounds, and the methods and lubricants herein are essentially devoid of such chemicals (e.g., less than about 100 ppm of metal-containing salicylate-based compounds, preferably less than about 50 ppm of metal-containing salicylate-based compounds, more preferably less than about 20 ppm of metal-containing salicylate-based compounds, and more preferably no functional amount of metal-containing salicylate-based compounds).

[0012] As discussed further below, embodiments of the methods and engine lubricating oil compositions herein achieve such performance through the use of specific sulfonate-based chemistries, an essential lack of salicylate chemistries (in some approaches, essentially lacking other metallated detergent compounds, such as magnesium, sodium, etc.), and in other embodiments, the selection of one or more specific additives that, when combined with selected oil-soluble molybdenum compounds, provide amounts of calcium and molybdenum to fluids having ultra-low viscosities. In some exemplary approaches, the lubricating oil compositions of the methods and methods herein have an additive package that contributes about 900 ppm or more calcium (preferably, about 900 to about 1500 ppm calcium) provided by the selected sulfonate-based compounds and 500 to about 1200 ppm molybdenum (preferably, about 500 to about 1000 ppm molybdenum) from one or more selected oil-soluble molybdenum compounds. In some approaches, the methods and compositions herein also have a calcium to molybdenum weight ratio of about 1:1 to about 2:1 (preferably about 1.2 to about 1.9). Further details regarding lubricant components and additive packages are provided below and illustrated in the Examples herein.

[0013] Hydrocarbyl-substituted sulfonate compounds The methods and passenger car engine lubricating oil compositions of the present invention include the use of selected compounds based on sulfonate chemistry, specifically one or more calcium-containing hydrocarbyl-substituted sulfonate compounds configured to improve fuel economy when, for example, such sulfonate compounds are combined with one or more oil-soluble molybdenum compounds.

[0014] In one approach or embodiment, suitable calcium-containing hydrocarbyl-substituted sulfonate compounds include those having linear or branched hydrocarbyl substituents, specifically linear or branched C6 to C30 hydrocarbyl groups, and in some approaches, hydrocarbyl substituents derived from blends of C14 to C26 olefins, having a number average molecular weight of about 80 to about 300 g / mol (in other approaches, about 100 to about 300 g / mol, about 200 to about 300 g / mol, or about 225 to about 300 g / mol). Preferably, the calcium-containing hydrocarbyl-substituted sulfonate compounds are used in the methods and compositions herein in an amount to provide the lubricant with at least about 900 ppm of calcium, more preferably from about 900 ppm to about 1500 ppm of calcium. In another approach, the calcium-containing hydrocarbyl-substituted sulfonate compounds are considered to be overbased, and in this context, have a total base number (TBN) of at least about 175 mg KOH / gram, or in another approach, from about 175 mg KOH / gram to about 500 mg KOH / gram (or in yet another approach, from about 200 to about 450 mg KOH / gram, from about 250 to about 425 mg KOH / gram, or from about 300 to about 425 mg KOH / gram), as measured in accordance with ASTM D2896. In another approach, the sulfonate compounds herein may have a calcium to sulfonate ratio of about 1.1:1 or less, about 2:1 or less, about 4:1 or less, about 5:1 or less, about 7:1 or less, about 10:1 or less, about 12:1 or less, about 15:1 or less, or about 20:1 or less.

[0015] In one approach, suitable calcium-containing hydrocarbyl-substituted sulfonate compounds herein may have about 0.5 to about 4 weight percent sulfur (in other approaches, a sulfur content of about 1 to about 2 weight percent, or about 1.2 to about 2 weight percent sulfur). To this end, the calcium-containing hydrocarbyl-substituted sulfonate compounds may also provide about 1 weight percent to about 15 weight percent total sulfur in the finished lubricant (or in other approaches, about 5 to 10 weight percent total sulfur in the finished lubricant).

[0016] In yet another approach, the TBN values ​​set forth above for the sulfonate compounds herein reflect the TBN values ​​of the finished sulfonate compounds diluted in base oil. In other embodiments, the TBN values ​​for the sulfonate compounds herein may reflect the neat or undiluted version of the sulfonate component. In such a context, for example, a calcium sulfonate compound, as an undiluted additive, may have a TBN of about 300 to about 450 mg KOH / g, or in another approach, about 380 to about 420 mg KOH / g, as measured in accordance with ASTM D2896.

[0017] In embodiments, suitable sulfonate compounds are provided in the form of alkali or alkali metal salts of hydrocarbyl sulfonates. More specifically, sulfonate compounds can include linear or branched alkali or alkaline earth metal salts (preferably calcium) of petroleum sulfonic acids and long-chain mono- or di-alkylaryl sulfonic acids in which the aryl groups are benzyl, tolyl, and xylyl, with alkyl or hydrocarbyl substituents as mentioned above (see, for example, U.S. Pat. No. 7,732,390 and the references cited therein, which are incorporated herein by reference). In one approach, sulfonate compounds can be prepared by reacting a metal oxide or metal hydroxide with a suitable sulfonate base and carbon dioxide gas. The base is typically an acid, such as an aliphatic-substituted sulfonic acid.

[0018] In other embodiments or approaches, the compositions and additive packages herein also essentially lack (e.g., have little or no) other metallate salts, such as phenates, calixarates, salixarates, salicylates, carboxylic acids, sulfurized derivatives thereof, or combinations thereof. As used herein, essentially lacking means that the compositions herein have less than about 100 ppm of phenates, calixarates, salixarates, salicylates, carboxylic acids, sulfurized derivatives thereof, or combinations thereof; preferably, less than about 50 ppm of phenates, calixarates, salixarates, salicylates, carboxylic acids, sulfurized derivatives thereof, or combinations thereof; more preferably, less than about 20 ppm of phenates, calixarates, salixarates, salicylates, carboxylic acids, sulfurized derivatives thereof, or combinations thereof; and most preferably, no functional amounts of phenates, calixarates, salixarates, salicylates, carboxylic acids, sulfurized derivatives thereof, or combinations thereof.

[0019] In some approaches or embodiments, the lubricant compositions of the methods and processes herein may contain from about 0.1 to about 5 weight percent of the calcium-containing hydrocarbyl-substituted sulfonate compound, in other approaches from about 0.15 to about 3 weight percent, and in yet other approaches from about 0.15 to 2.6 weight percent of the calcium-containing hydrocarbyl-substituted sulfonate compound, so long as the calcium-containing hydrocarbyl-substituted sulfonate compound satisfies the calcium content, TBN, SASH, and other relationships described herein.

[0020] Oil-soluble molybdenum compounds In some approaches, the engine lubricating oil composition of the present invention includes one or more oil-soluble molybdenum-containing compounds. The oil-soluble molybdenum compounds may be any of molybdenum dithiocarbamates, molybdenum dialkyldithiophosphates, molybdenum sulfides, molybdenum disulfides, molybdenum dithiophosphinates, amine salts of molybdenum compounds, organomolybdenum nitrogen complexes, molybdenum xanthates, molybdenum thioxanthates, molybdenum sulfides, molybdenum carboxylates, molybdenum alkoxides, trinuclear organomolybdenum compounds, and / or mixtures thereof. The molybdenum-containing compounds may be sulfur-containing or sulfur-free compounds. The molybdenum disulfide may be in the form of a stable dispersion.

[0021] In one embodiment, the oil-soluble molybdenum compound may be selected from the group consisting of molybdenum dithiocarbamates, molybdenum dialkyldithiophosphates, sulfur-free organo-molybdenum complexes of organic amides, organo-molybdenum nitrogen complexes, and mixtures thereof. In one embodiment, the oil-soluble molybdenum compound may be molybdenum dithiocarbamates. In yet a further embodiment, the oil-soluble molybdenum compound may be a molybdenum dialkyldithiocarbamate compound and / or an organo-molybdenum nitrogen complex, providing the total amount of molybdenum in the lubricating compositions herein. Exemplary sulfur-free organo-molybdenum complexes of organic amides are disclosed in U.S. Patent No. 5,137,647.

[0022] In one approach or embodiment, suitable molybdenum dithiocarbamates may be represented by the formula:

[0023] [ka] In the formula, R 5 , R 6 , R 7 , and R 8 are each independently a hydrogen atom, C1 to C 20 Alkyl groups, C6-C 20a cycloalkyl, aryl, alkylaryl, or aralkyl group, or optionally a C3-C containing ester, ether, alcohol, or carboxyl group; 20 R is a hydrocarbyl group, and X1, X2, Y1 and Y2 are each independently a sulfur atom or an oxygen atom. 5 , R 6 , R 7 , and R 8 Examples of suitable groups for each of R include 2-ethylhexyl, nonylphenyl, methyl, ethyl, n-propyl, iso-propyl, n-butyl, t-butyl, n-hexyl, n-octyl, nonyl, decyl, dodecyl, tridecyl, lauryl, oleyl, linoleyl, cyclohexyl, and phenylmethyl. 5 , R 6 , R 7 , and R 8 are C6 to C 18 Alkyl groups (preferably, independently, C6 to C8 alkyl groups and / or C 10 ~C 14 alkyl group), and in another approach, R 5 and R 6 one of which is a linear or branched C6-C8 alkyl chain, and R 5 and R 6 The other of the two is linear or branched C 10 ~C 14 alkyl chains, together R 7 and R 8 one of which is linear or branched C6-C8, and R 7 and R 8 The other of the two is linear or branched C 10 ~C 14 X1 and X2 may be the same, and Y1 and Y2 may be the same. X1 and X2 may both contain a sulfur atom, and Y1 and Y2 may both contain an oxygen atom. Further examples of molybdenum dithiocarbamates include C6-C 18Included are dialkyl or diaryl dithiocarbamates or alkyl-aryl dithiocarbamates such as dibutyl-, diamyl-di-(2-ethylhexyl)-, dilauryl-, dioleyl-, and dicyclohexyl-dithiocarbamate.

[0024] Suitable examples of molybdenum compounds that can be used include commercially available materials sold under trade names such as Molyvan® 822, Molyvan® A, Molyvan® 2000, Molyvan® 807 and Molyvan® 855 manufactured by RT Vanderbilt Co., Ltd., Sakura-Lube™ S-165, S-200, S-300, S-310G, S-525, S-600, S-700, and S-710 available from Adeka Corporation, and mixtures thereof. Suitable molybdenum components are described in U.S. Pat. No. 5,650,381, U.S. Reissue Pat. No. 37,363 (E1), U.S. Reissue Pat. No. 38,929 (E1), and U.S. Reissue Pat. No. 40,595 (E1), the entire contents of which are incorporated herein by reference.

[0025] In one embodiment, when included in the formulation, the molybdenum compound may be present in the engine lubricating oil compositions of the methods and processes herein in an amount providing from about 500 to about 1200 ppm molybdenum, or in another approach, from about 500 to 1000 ppm molybdenum. As noted above, the compositions of the methods and processes herein may have a weight ratio of calcium to molybdenum from the at least one calcium-containing hydrocarbyl-substituted sulfonate compound of from about 1:1 to about 2:1, or in another approach, from about 1.2 to about 1.9.

[0026] Base oil or base oil blend: The base oil used in the lubricating compositions and methods herein can be an oil of lubricating viscosity and can be selected from any of API Groups I-V as specified in the American Petroleum Institute (API) Base Oil Interchangeability Guidelines. Preferably, the one or more base oils have a combined base oil viscosity (BOV) of about 5.4 cSt or less at 100°C. In some approaches, the one or more base oils of lubricating viscosity are selected from API Group II base oils, API Group III base oils, API Group IV base oils, or mixtures thereof. In yet other approaches, the one or more base oils of lubricating viscosity are gas-to-liquid (GTL) derived base oils, preferably GTL base oils having a viscosity of about 4 to about 8 cSt at 100°C. In some approaches or embodiments, the combined base oil viscosity (BOV) of the base oil blends herein at 100° C. may be about 5.4 cSt or less, about 5.2 cSt or less, about 5.1 cSt or less, about 5.0 cSt or less, about 4.8 cSt or less, about 4.5 cSt or less, or about 4.2 cSt or less. In other approaches, the combined base oil viscosity of the base oil blends herein is at least about 3 cSt, at least about 3.2 cSt, at least about 3.4 cSt, at least about 3.6 cSt, or at least about 3.8 cSt. The five base oil groups are generally set forth in Table 1 below.

[0027] [Table 1]

[0028] Group I, Group II, and Group III are mineral oil processing 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, but may also be natural oils such as vegetable oils. Group III base oils are derived from mineral oils, but it should be noted that the rigorous processing these fluids undergo makes their physical properties very similar to some true synthetics, such as PAOs. Therefore, oils derived from Group III base oils may be referred to in industry as synthetic fluids. Group II+ may include high viscosity index Group II.

[0029] The base oil blends used in the disclosed lubricating oil compositions can be mineral, animal, vegetable, synthetic, synthetic oil blends, or mixtures thereof. Suitable oils can be derived from hydrocracked, hydrogenated, hydrofinished, unrefined, refined, and rerefined oils, and mixtures thereof.

[0030] Unrefined oils are derived from natural, mineral, or synthetic sources with little or no further purification processing. Refined oils are similar to unrefined oils except that they have been treated with one or more purification steps, which may result in the improvement of one or more properties. Examples of suitable purification techniques include solvent extraction, secondary distillation, acid or base extraction, filtration, percolation, etc. Oils refined to edible quality may or may not be useful. Edible oils may also be called white oils. In some embodiments, the lubricating oil composition does not include edible oils or white oils.

[0031] Re-refined oils are also known as reclaimed or reprocessed oils. These oils are obtained similarly to refined oils using the same or similar processes. Often, these oils are additionally processed by techniques directed to the removal of spent additives and oil breakdown products.

[0032] Mineral oils may include oils obtained by drilling, from plants and animals, or any mixture thereof. For example, such oils may include, but are not limited to, castor oil, lard oil, olive oil, peanut oil, corn oil, soybean oil, and linseed oil, as well as mineral lubricating oils, such as liquid petroleum oils and solvent- or acid-treated mineral lubricating oils of the paraffinic, naphthenic, or mixed paraffinic-naphthenic types. Such oils may be partially or fully hydrogenated if desired. Oils derived from coal or shale may also be useful.

[0033] Useful synthetic lubricating oils may include hydrocarbon oils such as polymerized, oligomerized, or interpolymerized olefins (e.g., polybutylene, polypropylene, propylene-isobutylene copolymers); poly(1-hexene), poly(1-octene), trimers or oligomers of 1-decene, such as poly(1-decene) (such materials are often referred to as α-olefins), and mixtures thereof; alkyl-benzenes (e.g., dodecylbenzene, tetradecylbenzene, dinonylbenzene, di-(2-ethylhexyl)-benzene); polyphenyls (e.g., biphenyl, terphenyl, alkylated polyphenyls); diphenylalkanes, alkylated diphenylalkanes, alkylated diphenyl ethers, and alkylated diphenyl sulfides, as well as derivatives, analogs, and homologs thereof, or mixtures thereof. Polyalphaolefins are typically hydrogenated materials.

[0034] Other synthetic lubricating oils include polyol esters, diesters, liquid esters of phosphorus-containing acids (e.g., tricresyl phosphate, trioctyl phosphate, and diethyl ester of decane phosphonic acid), or polymeric tetrahydrofurans. Synthetic oils may be produced by the Fischer-Tropsch reaction and are typically hydroisomerized Fischer-Tropsch hydrocarbons or waxes. In one embodiment, the oils may be prepared by the Fischer-Tropsch gas-to-liquid synthesis procedure, as well as other gas-to-liquid oils.

[0035] A major amount of base oil included in the lubricating composition may be selected from the group consisting of Group I, Group II, Group III, Group IV, Group V, and combinations of two or more of the foregoing, but the major amount of base oil is other than the base oil resulting from the provision of additive components or viscosity index improvers in the composition. In another embodiment, a major amount of base oil included in the lubricating composition may be selected from the group consisting of Group II, Group III, Group IV, Group V, and combinations of two or more of the foregoing, but the major amount of base oil is other than the base oil resulting from the provision of additive components or viscosity index improvers in the composition.

[0036] The amount of oil of lubricating viscosity present can be the difference remaining after subtracting the sum of the amounts of performance additives, including viscosity index improvers and / or pour point depressants and / or other top treat additives, from 100% by weight. For example, the oil of lubricating viscosity may be present in the final fluid in a major amount, such as greater than about 50%, greater than about 60%, greater than about 70%, greater than about 80%, greater than about 85%, or greater than about 90% by weight.

[0037] In some approaches or embodiments, the base oil system herein comprises one or more of Group I through Group V base oils and may have a KV100 of from about 2 to about 20 cSt, from about 2 to about 10 cSt in other approaches, from about 2.5 to about 6 cSt, from about 2.5 to about 3.5 cSt in still other approaches, and from about 2.5 to about 4.5 cSt in other approaches.

[0038] As used herein, the terms "oil composition," "lubricating composition," "lubricating oil composition," "lubricating oil," "lubricant composition," "fully formulated lubricant composition," "lubricant," and "lubricating and cooling fluid" are considered synonymous and fully interchangeable terms that refer to a finished lubricating product that includes a major amount of a base oil component and minor amounts of detergents and other optional components.

[0039] Engine lubricating oil composition The method and fully formulated passenger car engine oil composition of the present invention comprises the above-described selected base oil blend, at least one calcium-containing hydrocarbyl-substituted sulfonate compound, and an oil-soluble molybdenum compound in a composition configured to achieve one or more of the following: (a) a total measured sulfated ash of about 0.8 weight percent or less, as measured in accordance with ASTM D874 (wherein the calcium sulfated ash is about 80 to about 100% of the total sulfated ash content); (b) a total base number (TBN) of the lubricating oil composition of at least about 6.0 mg KOH / gram (or about 6 to about 10 mg KOH / g), as measured in accordance with ASTM D2896; (c) a total base number (TBN) of the lubricating oil composition of at least about 6.0 mg KOH / gram (or about 6 to about 10 mg KOH / g), as measured in accordance with ASTM D2896; and / or (d) a high temperature, high shear viscosity of about 1.7 to about 2.9 cSt (alternatively, about 2.3 to about 2.6 cSt) when measured at 150°C in accordance with D4683, and / or an ultra-low KV100 viscosity of about 8 cSt or less (preferably about 7.8 cSt or less, or about 7.6 cSt or less, or about 7.4 cSt or less). Such methods and compositions are effective such that the lubricating oil composition, when used to lubricate the crankcase of a passenger car engine, has a positive fuel economy increase of greater than 1.1% (FEI adjusted) when measured in accordance with JASO M366 (preferably about 1.1% to about 1.5%) and / or the lubricating oil composition has a positive fuel economy increase of greater than 1.4% when measured in accordance with JASO M365 (preferably about 1.5% to about 1.8%) in the Japan WLTC cycle.

[0040] In other approaches or embodiments, the passenger car engine oil compositions of the methods and processes herein also comprise a weight ratio of calcium from the at least one calcium-containing hydrocarbyl-substituted sulfonate compound to molybdenum from the oil-soluble molybdenum compound of from about 1:1 to about 2.5:1, or in other approaches, from 1.2:1 to about 2:1, or from about 1.2:1 to about 1.9:1, or from about 1.5:1 to about 1.8:1. The passenger car engine oil compositions of the methods and processes herein may also include embodiments having a total sulfur content of at least about 2000 ppm, or, in another approach, an amount of from about 2000 to about 3000 ppm total sulfur (and, in yet another approach, from about 2100 to about 2800 ppm total sulfur, or from about 2200 to about 2600 ppm total sulfur), and may further have a weight ratio of total sulfur to total calcium from the at least one calcium-containing hydrocarbyl-substituted sulfonate compound of at least about 1.5:1 or greater, or at least about 1.8:1 or greater (and, in another approach, from about 1.8:1 to about 2.6:1, or from about 1.9:1 to about 2.5:1).

[0041] As described above, the lubricating compositions of the methods and methods herein are substantially free of sulfur-free detergent additives, preferably detergent additives other than those provided by calcium-containing hydrocarbyl-substituted sulfonate compounds. To this end, the lubricating compositions of the methods and methods herein are essentially devoid of such salicylate chemicals (e.g., containing less than about 100 ppm of metal-containing salicylate-based compounds, preferably less than about 50 ppm of metal-containing salicylate-based compounds, more preferably less than about 20 ppm of metal-containing salicylate-based compounds, and more preferably free of functional amounts of metal-containing salicylate-based compounds). The lubricating compositions of the methods and methods herein are also preferably substantially free of magnesium and / or sodium (e.g., less than about 500 ppm of magnesium and / or sodium), preferably less than about 200 ppm of magnesium and / or sodium, more preferably less than about 100 ppm of magnesium and / or sodium, or less than about 50 ppm of magnesium and / or sodium, and more preferably free of functional amounts of magnesium and / or sodium metals).

[0042] Optional Additives: The lubricating oil compositions of the methods and processes herein may also contain, in combination with the at least one calcium-containing hydrocarbyl-substituted sulfonate compound and the oil-soluble molybdenum compound, several optional additives as needed to meet performance criteria, which optional additives are described in the following paragraphs.

[0043] Dispersants: The lubricating oil composition may optionally contain one or more other dispersants or mixtures thereof. Dispersants are often known as ashless dispersants because they do not contain ash-forming metals prior to incorporation into the lubricating oil composition and do not typically contribute ash when added to the lubricant. Ashless dispersants are characterized by polar groups attached to a relatively high molecular weight hydrocarbon chain. Typical ashless dispersants include N-substituted long-chain alkenyl succinimides. Examples of N-substituted long-chain alkenyl succinimides include polyisobutylene succinimides in which the number average molecular weight of the polyisobutylene substituent ranges from about 350 to about 50,000, or from about 5,000, or from about 3,000, as measured by GPC. Succinimide dispersants and their preparation are disclosed, for example, in U.S. Pat. No. 7,897,696 or U.S. Pat. No. 4,234,435. The alkenyl substituent may be prepared from polymerizable monomers containing from about 2 to about 16, or from about 2 to about 8, or from about 2 to about 6 carbon atoms. Succinimide dispersants are typically imides formed from polyamines, typically poly(ethyleneamines).

[0044] Preferred amines are selected from polyamines and hydroxylamines. Examples of polyamines that can be used include, but are not limited to, diethylene triamine (DETA), triethylene tetramine (TETA), tetraethylene pentamine (TEPA), and higher homologs such as pentaethylamine hexamine (PEHA).

[0045] Suitable heavy polyamines are mixtures of polyalkylene-polyamines containing small amounts of lower polyamine oligomers such as TEPA and PEHA (pentaethylenehexamine), but primarily oligomers with six or more nitrogen atoms, two or more primary amines per molecule, and more extensive branching than conventional polyamine mixtures. Heavy polyamines preferably include polyamine oligomers containing seven or more nitrogen atoms per molecule and two or more primary amines per molecule. Heavy polyamines contain greater than 28% by weight (e.g., greater than 32% by weight) total nitrogen and an equivalent weight of 120 to 160 grams of primary amine groups per equivalent.

[0046] In some approaches, suitable polyamines are commonly known as PAMs and contain a mixture of ethyleneamines, with TEPA and pentaethylenehexamine (PEHA) being the majority of the polyamine, usually less than about 80%.

[0047] Typically, PAM has 8.7-8.9 milliequivalents of primary amine per gram (115-112 gram equivalents per equivalent of primary amine) and a total nitrogen content of about 33-34% by weight. Heavier cuts of PAM oligomers, which are substantially free of TEPA and contain only small amounts of PEHA, but contain primarily oligomers with more than six nitrogen atoms and more extensive branching, can produce dispersants with improved dispersancy.

[0048] In embodiments, the present disclosure further includes at least one polyisobutylene succinimide dispersant derived from polyisobutylene having a number average molecular weight, as determined by GPC, ranging from about 350 to about 50,000, or from about 5,000, or from about 3,000. The polyisobutylene succinimide may be used alone or in combination with other dispersants.

[0049] In some embodiments, polyisobutylene, if present, may have a terminal double bond content of greater than 50 mol%, greater than 60 mol%, greater than 70 mol%, greater than 80 mol%, or greater than 90 mol%. Such PIB is also referred to as highly reactive PIB ("HR-PIB"). HR-PIB having a number average molecular weight in the range of about 800 to about 5000 as determined by GPC is suitable for use in embodiments of the present disclosure. Conventional PIB typically has a terminal double bond content of less than 50 mol%, less than 40 mol%, less than 30 mol%, less than 20 mol%, or less than 10 mol%.

[0050] HR-PIB having a number average molecular weight in the range of about 900 to about 3000, as determined by GPC, may be suitable. Such HR-PIB is commercially available or can be synthesized by polymerization of isobutene in the presence of a non-chlorinated catalyst, such as boron trifluoride, as described in U.S. Patent No. 4,152,499 to Boerzel et al. and U.S. Patent No. 5,739,355 to Gateau et al. When HR-PIB is used in the thermal ene reaction, it can result in higher conversion rates and less precipitate formation during the reaction due to increased reactivity. A suitable method is described in U.S. Patent No. 7,897,696.

[0051] In one embodiment, the present disclosure further comprises at least one dispersant derived from polyisobutylene succinic anhydride ("PIBSA"), which may have an average of about 1.0 to about 2.0 succinic moieties per polymer.

[0052] The percent active ingredient of the alkenyl or alkyl succinic anhydride can be determined using chromatographic techniques, which are described in columns 5 and 6 of U.S. Patent No. 5,334,321.

[0053] The percent polyolefin conversion is calculated from the % active ingredient using the formula in columns 5 and 6 of US Pat. No. 5,334,321.

[0054] Unless otherwise stated, all percentages are weight percent and all molecular weights are number average molecular weights as determined by gel permeation chromatography (GPC) using commercially available polystyrene standards (having number average molecular weights of 180 to about 18,000) as calibration standards.

[0055] In one embodiment, the dispersant may be derived from a polyalphaolefin (PAO) succinic anhydride. In one embodiment, the dispersant may be derived from an olefin maleic anhydride copolymer. As an example, the dispersant may be described as poly-PIBSA. In an embodiment, the dispersant may be derived from an anhydride grafted to an ethylene-propylene copolymer.

[0056] A suitable class of nitrogen-containing dispersants can be derived from olefin copolymers (OCPs), more specifically ethylene-propylene dispersants that can be grafted with maleic anhydride. A more complete list of nitrogen-containing compounds that can be reacted with functionalized OCPs is described in U.S. Patent Nos. 7,485,603, 7,786,057, 7,253,231, 6,107,257, and 5,075,383, and / or is commercially available.

[0057] One class of suitable dispersants can also be Mannich bases. Mannich bases are materials formed by the condensation of higher molecular weight alkyl-substituted phenols, polyalkylene polyamines, and aldehydes such as formaldehyde. Mannich bases are described in more detail in U.S. Pat. No. 3,634,515.

[0058] A suitable class of dispersants may also be high molecular weight esters or half-ester amides. Suitable dispersants may also be post-treated by conventional methods with any of a variety of agents. Among these are boron, urea, thiourea, dimercaptothiadiazole, carbon disulfide, aldehydes, ketones, carboxylic acids, hydrocarbon-substituted succinic anhydrides, maleic anhydride, nitriles, epoxides, carbonates, cyclic carbonates, hindered phenol esters, and phosphorus compounds. U.S. Patent Nos. 7,645,726, 7,214,649, and 8,048,831 are incorporated herein by reference in their entireties.

[0059] In addition to the carbonate and boric acid post-treatments, any of the compounds may be post-treated or further post-treated with a variety of post-treatments designed to improve or impart different properties. Such post-treatments include those summarized in columns 27-29 of U.S. Pat. No. 5,241,003, which is incorporated herein by reference. Such treatments include treatment with inorganic phosphoric acids or anhydrides (e.g., U.S. Pat. Nos. 3,403,102 and 4,648,980), organic phosphorus compounds (e.g., U.S. Pat. No. 3,502,677), phosphorus pentasulfide, boron compounds as already described above (e.g., U.S. Pat. Nos. 3,178,663 and 4,652,387), carboxylic acids, polycarboxylic acids, anhydrides, and / or acid halides (e.g., U.S. Pat. Nos. 3,708,522 and 4,909,910). No. 48,386), epoxide polyepoxides or thioepoxides (e.g., U.S. Pat. Nos. 3,859,318 and 5,026,495), aldehydes or ketones (e.g., U.S. Pat. No. 3,458,530), carbon disulfide (e.g., U.S. Pat. No. 3,256,185), glycidol (e.g., U.S. Pat. No. 4,617,137), urea, thiourea, or guanidine (e.g., U.S. Pat. Nos. 3,312,619, 3,865,813, and British Patent No. 1,065, ,595), organic sulfonic acids (e.g., U.S. Pat. No. 3,189,544 and British Patent No. 2,140,811), alkenyl cyanides (e.g., U.S. Pat. Nos. 3,278,550 and 3,366,569), diketenes (e.g., U.S. Pat. No. 3,546,243), diisocyanates (e.g., U.S. Pat. No. 3,573,205), alkanesultones (e.g., U.S. Pat. No. 3,749,695), 1,3-dicarbonyl compounds (e.g., U.S. Pat. No. 4,579,675), No. 3,954,639), sulfates of alkoxylated alcohols or phenols (e.g., U.S. Pat. No. 3,954,639), cyclic lactones (e.g., U.S. Pat. Nos. 4,617,138, 4,645,515, 4,668,246, 4,963,275, and 4,971,711), cyclic carbonates or thiocarbonates, linear monocarbonates or polycarbonates, or chloroformates (e.g., U.S. Pat. Nos. 4,612,132, 4,647,390, 4,648,886, 4,670,170), nitrogen-containing carboxylic acids (e.g., U.S. Pat. No. 4,971,598 and British Patent No. 2,140,811), hydroxy-protected chlorodicarbonyloxy compounds (e.g., U.S. Pat. No. 4,614,522), lactams, thiolactams, thiolactones, or dithiolactones (e.g., U.S. Pat. Nos. 4,614,603 and 4,666,460), cyclic carbonates or thiocarbonates, linear monocarbonates or polycarbonates, or chloroformates (e.g., Nos. 4,612,132, 4,647,390, 4,646,860, and 4,670,170), nitrogen-containing carboxylic acids (e.g., U.S. Pat. No. 4,971,598 and British Patent No. 2,440,811), hydroxy-protected chlorodicarbonyloxy compounds (e.g., U.S. Pat. No. 4,614,522), lactams, thiolactams, thiolactones, or dithiolactones (e.g., U.S. Pat. Nos. 4,614,603 and 4,666,460), cyclic carbamates, cyclic thiocarbamates, or cyclic dithiocarbamates (e.g., U.S. Pat. Nos. 4,663,062 and 4,666,459), hydroxyaliphatic carboxylic acids (e.g., U.S. Pat. Nos. 4,482,464, 4,521,318, and 4,713,189), oxidizing agents (e.g., U.S. Pat. No. 4,379,064), combinations of phosphorus pentasulfide and polyalkylene polyamines (e.g., U.S. Pat. No. 3,185,647), combinations of carboxylic acids or aldehydes or ketones and sulfur or sulfur chloride (e.g., U.S. Pat. Nos. 3,390,086 and 3,470,098), hydrazine and disulfide Combinations of carbon (e.g., U.S. Pat. No. 3,519,564), combinations of aldehydes and phenols (e.g., U.S. Pat. Nos. 3,649,229, 5,030,249, and 5,039,307), combinations of aldehydes and O-diesters of dithiophosphoric acids (e.g., U.S. Pat. No. 3,865,740), combinations of hydroxyaliphatic carboxylic acids and boric acid (e.g., U.S. Pat. No. 4,554,086), combinations of hydroxyaliphatic carboxylic acids followed by formaldehyde and phenols (e.g., U.S. Pat. No. 4,636,No. 322), a combination of a hydroxyaliphatic carboxylic acid and then an aliphatic dicarboxylic acid (e.g., U.S. Pat. No. 4,663,064), a combination of formaldehyde and a phenol and then glycolic acid (e.g., U.S. Pat. No. 4,699,724), a combination of a hydroxyaliphatic carboxylic acid or oxalic acid and then a diisocyanate (e.g., U.S. Pat. No. 4,713,191), a combination of an inorganic acid or anhydride of phosphorus or its partial or total sulfur analog and a boron compound (e.g., U.S. Pat. No. 4,857,211), a combination of a hydroxyaliphatic carboxylic acid and then an aliphatic dicarboxylic acid (e.g., U.S. Pat. No. 4,663,064), a combination of a hydroxyaliphatic carboxylic acid and then an aliphatic dicarboxylic acid (e.g., U.S. Pat. No. 4,699,724), a combination of a hydroxyaliphatic carboxylic acid or an oxalic acid and then a diisocyanate (e.g., U.S. Pat. No. 4,713,191), a combination of an inorganic acid or anhydride of phosphorus or its partial or total sulfur analog and a boron compound (e.g., U.S. Pat. No. 4,857,211), a combination of a hydroxyaliphatic carboxylic acid and then an aliphatic dicarboxylic acid ... No. 4), an organic diacid, followed by an unsaturated fatty acid, followed by a nitrosoaromatic amine, optionally followed by a boron compound, and then a glycolating agent (e.g., U.S. Pat. No. 4,973,412), a combination of an aldehyde and a triazole (e.g., U.S. Pat. No. 4,963,278), a combination of an aldehyde and a triazole, followed by a boron compound (e.g., U.S. Pat. No. 4,981,492), a combination of a cyclic lactone and a boron compound (e.g., U.S. Pat. Nos. 4,963,275 and 4,971,711). The patents referenced above are incorporated herein in their entirety.

[0060] The TBN of suitable dispersants may be from about 10 to about 65 mg KOH / g dispersant on an oil-free basis, which equates to about 5 to about 30 TBN when measured on a dispersant sample containing about 50% diluent oil. TBN is measured by the method of ASTM D2896.

[0061] In yet another embodiment, the optional dispersant additive may be a hydrocarbyl-substituted succinamide or succinimide dispersant. In some approaches, the hydrocarbyl-substituted succinamide or succinimide dispersant may be derived from a hydrocarbyl-substituted acylating agent reacted with a polyalkylene polyamine, wherein the hydrocarbyl substituent of the succinamide or succinimide dispersant is a linear or branched hydrocarbyl group having a number average molecular weight of from about 250 to about 5,000 as determined by GPC using polystyrene as a calibration standard.

[0062] In some approaches, the polyalkylene polyamine used to form the dispersant has the following formula:

[0063] [ka] wherein each R and R' is independently a divalent C1-C6 alkylene linker, and each R1 and R2 is independently hydrogen, a C1-C6 alkyl group, or together with the nitrogen atom to which they are attached form a 5- or 6-membered ring optionally fused with one or more aromatic or non-aromatic rings, and n is an integer from 0 to 8. In another approach, the polyalkylene polyamine is selected from the group consisting of a mixture of polyethylene polyamines having an average of 5 to 7 nitrogen atoms, triethylenetetramine, tetraethylenepentamine, and combinations thereof.

[0064] Dispersants, when present, may be used in an amount sufficient to provide up to about 20 wt. %, based on the final weight of the lubricating oil composition. Alternative amounts of dispersant that may be used may be from about 0.1 wt. % to about 15 wt. %, or from about 0.1 wt. % to about 10 wt. %, or from about 0.1 wt. % to about 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 single type or a mixture of two or more types of dispersants in any desired ratio may be used.

[0065] Antioxidants: The lubricating oil compositions herein may also optionally contain one or more antioxidants. Antioxidant compounds are known and include, for example, phenates, phenate sulfides, sulfurized olefins, phosphosulfurized terpenes, sulfurized esters, aromatic amines, alkylated diphenylamines (e.g., nonyldiphenylamine, di-nonyldiphenylamine, octyldiphenylamine, di-octyldiphenylamine), phenyl-alpha-naphthylamines, alkylated phenyl-alpha-naphthylamines, hindered non-aromatic amines, phenols, hindered phenols, oil-soluble molybdenum compounds, polymeric antioxidants, or mixtures thereof. The antioxidant compounds may be used alone or in combination.

[0066] The hindered phenol antioxidant may contain a secondary butyl group and / or a tertiary butyl group as a steric hindering group. The phenol group may be further substituted with a hydrocarbyl group and / or a bridging group connecting to a second aromatic group. Examples of suitable hindered phenol antioxidants include 2,6-di-tert-butylphenol, 4-methyl-2,6-di-tert-butylphenol, 4-ethyl-2,6-di-tert-butylphenol, 4-propyl-2,6-di-tert-butylphenol, 4-butyl-2,6-di-tert-butylphenol, or 4-dodecyl-2,6-di-tert-butylphenol. In one embodiment, the hindered phenol antioxidant may be an ester, but may include, for example, Irganox™ L-135 available from BASF, or an addition product derived from 2,6-di-tert-butylphenol and an alkyl acrylate, where the alkyl group may contain from about 1 to about 18, or from about 2 to about 12, or from about 2 to about 8, or from about 2 to about 6, or about 4 carbon atoms. Another commercially available hindered phenol antioxidant may be an ester, but may include Ethanox™ 4716 available from Albemarle Corporation.

[0067] Useful antioxidants may include diarylamines and high molecular weight phenols. In embodiments, the lubricating oil composition may contain a mixture of diarylamines and high molecular weight phenols, such that each antioxidant may be present in an amount sufficient to provide up to about 5 wt. %, based on the final weight of the lubricating oil composition. In embodiments, the antioxidant may be a mixture of about 0.3 to about 1.5 wt. % diarylamines and about 0.4 to about 2.5 wt. % high molecular weight phenols, based on the final weight of the lubricating oil composition.

[0068] Examples of suitable olefins that can be sulfurized to form sulfurized olefins include propylene, butylene, isobutylene, polyisobutylene, pentene, hexene, heptene, octene, nonene, decene, undecene, dodecene, tridecene, tetradecene, pentadecene, hexadecene, heptadecene, octadecene, nonadecene, eicosene, or mixtures thereof. In one embodiment, hexadecene, heptadecene, octadecene, nonadecene, eicosene, or mixtures thereof, as well as their dimers, trimers, and tetramers, are particularly useful olefins. Alternatively, the olefin can be a Diels-Alder adduct of a diene, such as 1,3-butadiene, and an unsaturated ester, such as butyl acrylate.

[0069] Another class of sulfurized olefins includes sulfurized fatty acids and their esters. The fatty acids are often derived from vegetable or animal oils and typically contain from about 4 to about 22 carbon atoms. Examples of suitable fatty acids and their esters include triglycerides, oleic acid, linoleic acid, palmitoleic acid, or mixtures thereof. Often, the fatty acids are derived from lard oil, tall oil, peanut oil, soybean oil, cottonseed oil, sunflower seed oil, or mixtures thereof. The fatty acids and / or esters may be mixed with an olefin, such as an α-olefin.

[0070] In another alternative embodiment, the antioxidant composition also contains a molybdenum-containing antioxidant in addition to the phenolic and / or aminic antioxidants discussed above. When a combination of these three antioxidants is used, preferably the treat rate ratio of the phenol to the amine to the molybdenum-containing component is (0-3):(0-3):(0-3).

[0071] The one or more antioxidants may be present in the range of from about 0% to about 20%, or from about 0.1% to about 10%, or from about 1% to about 5% by weight of the lubricating oil composition.

[0072] Antiwear Agents: The lubricating oil compositions herein may also optionally contain one or more antiwear agents. Examples of suitable antiwear agents include, but are not limited to, metal thiophosphates; metal dialkyldithiophosphates; phosphoric acid esters or salts thereof; phosphoric acid esters; phosphites; phosphorus-containing carboxylic acid esters, ethers, or amides; sulfurized olefins; thiocarbamate-containing compounds, such as thiocarbamate esters, alkylene-linked thiocarbamates, and bis(S-alkyldithiocarbamyl) disulfides; and mixtures thereof. A suitable antiwear agent may be molybdenum dithiocarbamate. Phosphorus-containing antiwear agents are more fully described in EP 612839. The metal in the dialkylphosphate salt may be an alkali metal, alkaline earth metal, aluminum, lead, tin, molybdenum, manganese, nickel, copper, titanium, or zinc. A useful antiwear agent may be zinc dialkyldithiophosphate.

[0073] Further examples of suitable antiwear agents include titanium compounds, tartrates, tartrimides, oil-soluble amine salts of phosphorus compounds, sulfurized olefins; (e.g., dibutyl phosphite), phosphonates, thiocarbamate-containing compounds such as thiocarbamate esters, thiocarbamate amides, thiocarbamic acid ethers, alkylene-linked thiocarbamates, and bis(S-alkyldithiocarbamyl) disulfides. The tartrates or tartrimides may contain alkyl-ester groups, and the total number of carbon atoms on the alkyl group may be at least 8. In one embodiment, the antiwear agent may include citrate.

[0074] The antiwear agent may be present in a range including from about 0% to about 15%, or from about 0.01% to about 10%, or from about 0.05% to about 5%, or from about 0.1% to about 3% by weight of the lubricating oil composition.

[0075] Boron-Containing Compounds: The lubricating oil compositions herein may optionally contain one or more boron-containing compounds. Examples of boron-containing compounds include borate esters, borated fatty amines, borated epoxides, borated detergents, and borated dispersants, such as borated succinimide dispersants, as disclosed in U.S. Patent No. 5,883,057. When present, the boron-containing compounds may be used in an amount sufficient to provide up to about 8 wt. %, from about 0.01 wt. % to about 7 wt. %, from about 0.05 wt. % to about 5 wt. %, or from about 0.1 wt. % to about 3 wt. % of the lubricating oil composition.

[0076] Detergents: Subject to the limitations set forth above, the lubricating oil composition may optionally further comprise one or more neutral, low-based, or overbased detergents, and mixtures thereof. Suitable detergent bases 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 more detail in numerous patent publications, including U.S. Pat. No. 7,732,390 and the references cited therein.

[0077] The detergent base may be salified with an alkali metal or alkaline earth metal, such as, but not limited to, calcium, magnesium, potassium, sodium, lithium, barium, or mixtures thereof. In some embodiments, the detergent is barium-free. In some embodiments, the detergent may contain trace amounts of other metals, such as magnesium or calcium, in amounts such as 50 ppm or less, 40 ppm or less, 30 ppm or less, 20 ppm or less, or 10 ppm or less. Suitable detergents may include alkali or alkaline earth metal salts of petroleum sulfonic acids and long-chain mono- or di-alkylaryl sulfonic acids in which the aryl group is benzyl, tolyl, and xylyl. Examples of suitable detergents include, but are not limited to, calcium phenate, sulfur-containing calcium phenate, calcium sulfonate, calcium calixarate, calcium salixarate, calcium salicylate, calcium carboxylate, calcium phosphate, calcium mono- and / or di-thiophosphate, calcium alkyl phenol, calcium sulfur-bound alkyl phenol compound, calcium methylene bridged phenol, magnesium phenate, sulfur-containing magnesium phenate, magnesium sulfonate, magnesium calixarate, magnesium salixarate, magnesium salicylate, magnesium carboxylate, magnesium phosphate, magnesium mono- and / or di-thiophosphate, magnesium alkyl phenol, magnesium sulfur-bound alkyl phenol compound, magnesium methylene bridged phenol, sodium phenate, sulfur-containing sodium phenate, sodium sulfonate, sodium calixarate, sodium salixarate, sodium salicylate, sodium carboxylate, sodium phosphate, sodium mono- and / or di-thiophosphate, sodium alkyl phenol, sodium sulfur-bound alkyl phenol compound, or sodium methylene bridged phenol.

[0078] Overbased detergent additives are well known in the art and can be alkali or alkaline earth metal overbased detergent additives. Such detergent additives can be prepared by reacting a metal oxide or metal hydroxide with a base and carbon dioxide gas. The base is typically an acid, such as an aliphatic-substituted sulfonic acid, aliphatic-substituted carboxylic acid, or aliphatic-substituted phenol.

[0079] The term "overbased" refers to metal salts, such as metal salts of sulfonates, carboxylates, and phenates, in which the amount of metal present exceeds the stoichiometric amount. Such salts can have conversion levels greater than 100% (i.e., they can contain more than 100% of the theoretical amount of metal required to convert the acid to its "standard" or "neutral" salt). The expression "metal ratio," often abbreviated as MR, is used to indicate the ratio of the total chemical equivalents of metal in an overbased salt to the chemical equivalents of metal in a neutral salt, according to known chemical reactivity and stoichiometry. In standard or neutral salts, the metal ratio is 1; in overbased salts, the MR is greater than 1. They are commonly referred to as overbased, overbased, or superbased salts and can be salts of organic sulfur acids, carboxylic acids, or phenols.

[0080] The overbased detergent of the lubricating oil composition may have a Total Base Number (TBN) of about 200 mg KOH / g or greater, or, as a further example, about 250 mg KOH / g or greater, or about 350 mg KOH / g or greater, or about 375 mg KOH / g or greater, or about 400 mg KOH / g or greater, as measured by the method of ASTM D2896.

[0081] Examples of suitable overbased detergents include, but are not limited to, overbased calcium phenates, overbased calcium sulfur-containing phenates, overbased calcium sulfonates, overbased calcium calixarates, overbased calcium salixarates, overbased calcium salicylates, overbased calcium carboxylic acids, overbased calcium phosphates, overbased calcium mono- and / or di-thiophosphates, overbased calcium alkylphenols, overbased calcium sulfur-bound alkylphenol compounds, overbased calcium methylene-bridged phenols, overbased magnesium phenates, overbased magnesium sulfonates, overbased magnesium calixarates, overbased magnesium salixarates, overbased magnesium salicylates, overbased magnesium carboxylic acids, overbased magnesium phosphates, overbased magnesium mono- and / or di-thiophosphates, overbased magnesium alkylphenols, overbased magnesium sulfur-bound alkylphenol compounds, or overbased magnesium methylene-bridged phenols.

[0082] The overbased calcium phenate detergents have a total base number of at least about 150 mg KOH / g, at least about 225 mg KOH / g, at least about 225 mg KOH / g to about 400 mg KOH / g, at least about 225 mg KOH / g to about 350 mg KOH / g, or about 230 mg KOH / g to about 350 mg KOH / g, all as measured by the method of ASTM D 2896. When such detergent compositions are formed in an inert diluent, such as a process oil, usually a mineral oil, the total base number reflects the basicity of the entire composition, including the diluent and any other materials (e.g., accelerators, etc.) that may be included in the detergent composition.

[0083] Overbased detergents may have a metal-to-base ratio of 1.1:1 or greater, or 2:1 or greater, or 4:1 or greater, or 5:1 or greater, or 7:1 or greater, or 10:1 or greater. In some embodiments, the detergent is effective in reducing or preventing rust in engines or other automotive components such as transmissions or gears. The detergent may be present in the lubricating composition from about 0 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 from greater than about 4 wt % to about 8 wt %.

[0084] Extreme Pressure Agents: The lubricating oil compositions herein may also optionally contain one or more extreme pressure agents. Oil-soluble extreme pressure (EP) agents include sulfur and chlorosulfur-containing EP agents, chlorinated hydrocarbon EP agents, and phosphorus EP agents. Examples of such EP agents include chlorinated waxes; organic sulfides and polysulfides such as dibenzyl disulfide, bis(chlorobenzyl) disulfide, dibutyl tetrasulfide, sulfurized methyl ester of oleic acid, sulfurized alkylphenols, sulfurized dipentene, sulfurized terpene, and sulfurized Diels-Alder adducts; phosphorus sulfurized hydrocarbons such as the reaction products of phosphorus sulfide with turpentine or methyl oleate; dihydrocarbyl and trihydrocarbyl phosphites, for example, phosphate esters such as dibutyl phosphite, diheptyl phosphite, dicyclohexyl phosphite, pentyl phenyl phosphite; dipentyl phenyl phosphite, tridecyl phosphite, distearyl phosphite, and polypropylene-substituted phenyl phosphites; metal thiocarbamates such as zinc dioctyldithiocarbamate and barium heptylphenol diacid; amine salts of alkyl and dialkyl phosphates, including, for example, the amine salt of the reaction product of a dialkyl dithiophosphate with propylene oxide; and mixtures thereof.

[0085] Friction Modifiers: The lubricating oil compositions herein may also optionally contain one or more friction modifiers. Suitable friction modifiers may include metal-containing and metal-free friction modifiers and may include, but are not limited to, imidazolines, amides, amines, succinimides, alkoxylated amines, alkoxylated ether amines, amine oxides, amidoamines, nitriles, betaines, quaternary amines, imines, amine salts, aminoguanidines, alkanolamides, phosphonates, metal-containing compounds, glycerol esters, sulfurized fatty compounds and olefins, sunflower oil, other naturally occurring vegetable or animal oils, dicarboxylic acid esters, esters or partial esters of polyols with one or more aliphatic or aromatic carboxylic acids, and the like.

[0086] Suitable friction modifiers may contain hydrocarbyl groups selected from linear, branched, or aromatic hydrocarbyl groups, or mixtures thereof, and may be saturated or unsaturated. The hydrocarbyl groups may be composed of carbon and hydrogen or heteroatoms such as sulfur or oxygen. The hydrocarbyl groups may range from about 12 to about 25 carbon atoms. In some embodiments, the friction modifier may be a long-chain fatty acid ester. In other embodiments, the long-chain fatty acid ester may be a mono-ester, a di-ester, or a (tri)glyceride. The friction modifier may be a long-chain fatty amide, a long-chain fatty ester, a long-chain fatty epoxide derivative, or a long-chain imidazoline.

[0087] Other suitable friction modifiers may include organic, ashless (metal-free), nitrogen-free organic friction modifiers. Such friction modifiers include esters formed by reacting carboxylic acids and anhydrides with alkanols, and may generally contain polar end groups (e.g., carboxyl or hydroxyl) covalently bonded to an oleophilic hydrocarbon chain. An example of an organic ashless, nitrogen-free friction modifier is commonly known as glycerol monooleate (GMO), which may contain mono-, di-, and tri-esters of oleic acid. Other suitable friction modifiers are described in U.S. Patent No. 6,723,685, the entire contents of which are incorporated herein by reference.

[0088] Aminic friction modifiers may include amines or polyamines. Such compounds may have hydrocarbyl groups that are linear, saturated, unsaturated, or a mixture thereof, and may contain from about 12 to about 25 carbon atoms. Further examples of suitable friction modifiers include alkoxylated amines and alkoxylated ether amines. Such compounds may have hydrocarbyl groups that are linear, saturated, unsaturated, or a mixture thereof. They may contain from about 12 to about 25 carbon atoms. Examples include ethoxylated amines and ethoxylated ether amines.

[0089] The amines and amides may be used as such or in the form of an adduct or reaction product with a boron compound such as boron oxide, boron halides, metaborates, boric acid, or mono-, di-, or tri-alkylborates. Other suitable friction modifiers are described in U.S. Patent No. 6,300,291, the entire contents of which are incorporated herein by reference.

[0090] Friction modifiers may optionally be present in ranges such as from about 0% to about 10% by weight, or from about 0.01% to about 8% by weight, or from about 0.1% to about 4% by weight.

[0091] Other Molybdenum-Containing Components: The lubricating oil compositions herein may also optionally contain one or more molybdenum-containing compounds. The oil-soluble molybdenum compounds may have the functional properties of antiwear agents, antioxidants, friction modifiers, or mixtures thereof. The oil-soluble molybdenum compounds may include molybdenum dithiocarbamates, molybdenum dialkyldithiophosphates, molybdenum dithiophosphinates, amine salts of molybdenum compounds, molybdenum xanthates, molybdenum thioxanthates, molybdenum sulfides, molybdenum carboxylates, molybdenum alkoxides, trinuclear organomolybdenum compounds, and / or mixtures thereof. Molybdenum sulfides include molybdenum disulfide. The molybdenum disulfide may be in the form of a stable dispersion. In one embodiment, the oil-soluble molybdenum compound may be selected from the group consisting of molybdenum dithiocarbamates, molybdenum dialkyldithiophosphates, amine salts of molybdenum compounds, and mixtures thereof. In one embodiment, the oil-soluble molybdenum compound can be a molybdenum dithiocarbamate.

[0092] Suitable examples of molybdenum compounds that can be used include commercially available materials sold under trade names such as Molyvan® 822, Molyvan® A, Molyvan® 2000, and Molyvan® 855 from R.T. Vanderbilt Co., Ltd., and Adeka Sakura-Lube® S-165, S-200, S-300, S-310G, S-525, S-600, S-700, and S-710 available from Adeka Corporation, and mixtures thereof. Suitable molybdenum components are described in U.S. Pat. No. 5,650,381, U.S. Reissue Pat. No. 37,363 (E1), U.S. Reissue Pat. No. 38,929 (E1), and U.S. Reissue Pat. No. 40,595 (E1), the entire contents of which are incorporated herein by reference.

[0093] Additionally, the molybdenum compound can be an acidic molybdenum compound, including molybdic acid, ammonium molybdate, sodium molybdate, potassium molybdate, and other alkali metal molybdates and other molybdenum salts, such as sodium hydrogen molybdate, MoOCl, MoOBr, MoOCl, molybdenum trioxide, or similar acidic molybdenum compounds. Alternatively, the composition can provide the molybdenum via molybdenum / sulfur complexes of basic nitrogen compounds, as described, for example, in U.S. Pat. Nos. 4,263,152, 4,285,822, 4,283,295, 4,272,387, 4,265,773, 4,261,843, 4,259,195, and 4,259,194, and WO 94 / 06897, the foregoing patents being incorporated herein by reference in their entireties.

[0094] Another class of suitable organo-molybdenum compounds is the trinuclear molybdenum compounds, e.g., those of the formula Mo3S k L n Q z and mixtures thereof, wherein S represents sulfur, L represents an independently selected ligand having an organic group having a sufficient number of carbon atoms to render the compound soluble or dispersible in oil, n is 1 to 4, k varies from 4 to 7, Q is selected from the group of neutral electron donor compounds, e.g., water, amines, alcohols, phosphines, and ethers, and z ranges from 0 to 5, including non-stoichiometric values. There may be at least 21 total carbon atoms among all of the ligand organic groups, such as at least 25, at least 30, or at least 35 carbon atoms. Additional suitable molybdenum compounds are described in U.S. Pat. No. 6,723,685, the entire contents of which are incorporated herein by reference.

[0095] The oil-soluble molybdenum compound may be present in an amount sufficient to provide from about 0.5 ppm to about 2000 ppm, from about 1 ppm to about 700 ppm, from about 1 ppm to about 550 ppm, from about 5 ppm to about 300 ppm, or from about 20 ppm to about 250 ppm of molybdenum.

[0096] Transition Metal-Containing Compound: In another embodiment, the oil-soluble compound can be a transition metal-containing compound or metalloid. Transition metals can 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.

[0097] In embodiments, the oil-soluble transition metal-containing compound may function as an anti-wear agent, a friction modifier, an antioxidant, an adhesion control additive, or one or more of these functions. In embodiments, the oil-soluble transition metal-containing compound may be an oil-soluble titanium compound such as a titanium(IV) alkoxide. Titanium-containing compounds that can be used in or for preparing oil-soluble materials in the technology of the present disclosure include, but are not limited to, various Ti(IV) compounds such as titanium(IV) oxide; titanium(IV) sulfide; titanium(IV) nitrate; titanium(IV) alkoxides, such as titanium methoxide, titanium ethoxide, titanium propoxide, titanium isopropoxide, titanium butoxide, and titanium 2-ethylhexoxide; and other titanium compounds or complexes, such as titanium phenate; titanium carboxylates, such as titanium(IV) 2-ethyl-1,3-hexanedioate, titanium citrate, or titanium oleate; and titanium(IV) (triethanolaminato)isopropoxide. Other forms of titanium encompassed by the disclosed technology include titanium phosphates, such as titanium dithiophosphates (e.g., dialkyldithiophosphates) and titanium sulfonates (e.g., alkylbenzene sulfonates), or generally reaction products of titanium compounds with various acidic materials to form salts, such as oil-soluble salts. Thus, titanium compounds can be derived from organic acids, alcohols, and glycols, among others. Ti compounds can also exist in dimeric or oligomeric forms containing Ti-O-Ti structures. Such titanium materials are commercially available or can be readily prepared by suitable synthetic techniques apparent to those skilled in the art. They can exist at room temperature as solids or liquids, depending on the particular compound. They can also be provided in solution form in a suitable inert solvent.

[0098] In one embodiment, titanium can be provided as a Ti-modified dispersant, such as a succinimide dispersant. Such materials can be prepared by forming a titanium mixed anhydride between a titanium alkoxide and a hydrocarbyl-substituted succinic anhydride, such as an alkenyl-(or alkyl) succinic anhydride. The resulting titanate-succinate intermediate can be used directly or reacted with any of several materials, such as (a) polyamine-based succinimide / amide dispersants having free condensable —NH functional groups; (b) components of polyamine-based succinimide / amide dispersants, i.e., alkenyl-(or alkyl) succinic anhydrides and polyamines; or (c) hydroxy-containing polyester dispersants prepared by reacting a substituted succinic anhydride with a polyol, aminoalcohol, polyamine, or mixtures thereof. Alternatively, the titanate-succinate intermediate can be reacted with other agents, such as alcohols, amino alcohols, ether alcohols, polyether alcohols or polyols, or fatty acids, and the product can be used directly to impart Ti to lubricating oils or further reacted with a succinic dispersant as described above. As an example, one part (mole) of tetraisopropyl titanate can be reacted with approximately two parts (mole) of polyisobutene-substituted succinic anhydride for 5-6 hours at 140-150°C to provide a titanium-modified dispersant or intermediate. The resulting material (30 g) can be further reacted with a succinimide dispersant from a polyisobutene-substituted succinic anhydride and polyethylene polyamine mixture (127 grams + diluent oil) for 1.5 hours at 150°C to produce a titanium-modified succinimide dispersant.

[0099] Another titanium-containing compound is titanium alkoxide and C6-C 25 The reaction product may be a reaction product with a carboxylic acid, the reaction product having the following formula:

[0100] [ka] wherein n is an integer selected from 2, 3, and 4, and R is a hydrocarbyl group containing from about 5 to about 24 carbon atoms, or may be represented by the following formula:

[0101] [ka] or the titanium compound may be represented by the formula: wherein m+n=4, n ranging 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;

[0102] [ka] wherein x ranges from 0 to 3; R1 is selected from hydrocarbyl groups containing about 6 to 25 carbon atoms; R2 and R3 are the same or different and are selected from hydrocarbyl groups containing about 1 to 6 carbon atoms; and R4 is selected from H, C6 to C8 25 and the carboxylic acid moiety of

[0103] Suitable carboxylic acids may include, but are not limited to, caproic acid, caprylic acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachic acid, oleic acid, erucic acid, linoleic acid, linolenic acid, cyclohexanecarboxylic acid, phenylacetic acid, benzoic acid, neodecanoic acid, and the like.

[0104] In embodiments, the oil-soluble titanium compound may be present in the lubricating oil composition in an amount to provide from about 0 to about 3000 ppm by weight of titanium, or from 25 to about 1500 ppm by weight of titanium, or from about 35 ppm to about 500 ppm by weight of titanium, or from about 50 ppm to about 300 ppm.

[0105] Viscosity index improver: The lubricating oil compositions herein may also optionally contain one or more viscosity index improvers. Suitable viscosity index improvers may include polyolefins, olefin copolymers, ethylene / propylene copolymers, polyisobutene, hydrogenated styrene-isoprene polymers, styrene / maleic acid ester copolymers, hydrogenated styrene / butadiene copolymers, hydrogenated isoprene polymers, alpha-olefin maleic anhydride copolymers, polymethacrylates, polyacrylates, polyalkylstyrenes, hydrogenated alkenylaryl conjugated diene copolymers, or mixtures thereof. Viscosity index improvers may include star polymers, suitable examples of which are described in U.S. Patent Application Publication No. 20120101017(A1).

[0106] The lubricating oil compositions herein may also optionally contain one or more dispersant viscosity index improvers in addition to or in place of a viscosity index improver. Suitable viscosity index improvers may include functionalized polyolefins, such as ethylene-propylene copolymers functionalized with the reaction product of an acylating agent (such as maleic anhydride) and an amine, amine-functionalized polymethacrylates, or esterified maleic anhydride-styrene copolymers reacted with amines.

[0107] The total amount of viscosity index improver and / or dispersant viscosity index improver can be from about 0% to about 20%, from about 0.1% to about 15%, from about 0.1% to about 12%, or from about 0.5% to about 10% by weight of the lubricating oil composition.

[0108] Other optional additives: Other additives may be selected to perform one or more functions required in a lubricating fluid. Furthermore, one or more of the additives mentioned may be multifunctional and may provide functions in addition to or other than those described herein.

[0109] Lubricating oil compositions according to the present disclosure may optionally contain other performance additives. The other performance additives may be in addition to the specified additives of this disclosure and / or may include one or more of metal deactivators, viscosity index improvers, detergents, ashless TBN boosters, friction modifiers, antiwear agents, corrosion inhibitors, rust inhibitors, dispersants, dispersant viscosity index improvers, extreme pressure agents, antioxidants, foam suppressants, demulsifiers, emulsifiers, pour point depressants, seal swell agents, and mixtures thereof. Typically, fully formulated lubricating oils will contain one or more of these performance additives.

[0110] Suitable metal deactivators may include derivatives of benzotriazole (typically tolyltriazole), dimercaptothiadiazole derivatives, 1,2,4-triazole, benzimidazole, 2-alkyldithiobenzimidazole, or 2-alkyldithiobenzothiazole; foam suppressors including copolymers of ethyl acrylate, 2-ethylhexyl acrylate, and optionally vinyl acetate; demulsifiers including trialkyl phosphate, polyethylene glycol, polyethylene oxide, polypropylene oxide, and (ethylene oxide-propylene oxide) polymers; pour point depressants including esters of maleic anhydride-styrene, polymethacrylate, polyacrylate, or polyacrylamide.

[0111] Suitable suds suppressors include silicon-based compounds such as siloxanes.

[0112] 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.

[0113] Suitable rust inhibitors can be a single compound or a mixture of compounds that have the property of inhibiting corrosion of ferrous metal surfaces. Non-limiting examples of rust inhibitors useful herein include oil-soluble high molecular weight organic acids such as 2-ethylhexanoic acid, lauric acid, myristic acid, palmitic acid, oleic acid, linoleic acid, linolenic acid, behenic acid, and cerotic acid, as well as oil-soluble polycarboxylic acids, including dimer and trimer acids such as those produced from tall oil fatty acid, oleic acid, and linoleic acid. Other suitable corrosion inhibitors include long-chain alpha- and omega-dicarboxylic acids in the molecular weight range of about 600 to about 3000, and alkenyl succinic acids in which the alkenyl group contains about 10 or more carbon atoms, such as tetrapropenyl succinic acid, tetradecenyl succinic acid, and hexadecenyl succinic acid. Another useful type of acidic corrosion inhibitor is the half ester of an alkenyl succinic acid having about 8 to about 24 carbon atoms in the alkenyl group with an alcohol, such as a polyglycol. The corresponding half amides of such alkenyl succinic acids are also useful. Useful rust inhibitors are high molecular weight organic acids.

[0114] When present, the rust inhibitor may 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.

[0115] Generally speaking, suitable lubricants containing detergent metals herein may contain additive components in the ranges listed in the table below.

[0116] [Table 2]

[0117] The percentages of each component above represent the weight percent of each component based on the weight of the final lubricating oil composition. The remainder of the lubricating oil composition consists of one or more base oils. The additives used in formulating the compositions described herein can be blended into the base oil individually or in various partial combinations. However, it may be preferred to blend all of the components simultaneously using an additive concentrate (i.e., additives plus a diluent such as a hydrocarbon solvent). Fully formulated lubricants conventionally contain an additive package, referred to herein as a dispersant / inhibitor package or DI package, that supplies the properties required in the formulation.

[0118] definition For purposes of this disclosure, chemical elements are identified according to the Periodic Table of the Elements, CAS version, Handbook of Chemistry and Physics, 75th Ed. Additionally, general principles of organic chemistry are described in "Organic Chemistry," Thomas Sorrell, University Science Books, Sausolito: 1999, and "March's Advanced Organic Chemistry," 5th Ed., Ed.: Smith, M.B. and March, J., John Wiley & Sons, New York: 2001, the entire contents of which are incorporated herein by reference.

[0119] As described herein, compounds can be optionally substituted with one or more substituents as illustrated generally above or as illustrated by the specific classes, subclasses, and species of the present disclosure.

[0120] Unless otherwise clear from the context, the term "major amount" is understood to mean an amount of 50 weight percent or more, for example, about 80 to about 98 weight percent, based on the total weight of the composition, and the term "minor amount" as used herein is understood to mean an amount of less than 50 weight percent, based on the total weight of the composition.

[0121] As used herein, the term "hydrocarbyl group" or "hydrocarbyl" is used in its ordinary sense, which is well known to those skilled in the art. Specifically, it refers to a group having a carbon atom directly attached to the remainder of the molecule and having predominantly hydrocarbon character. Examples of hydrocarbyl groups include (1) hydrocarbon substituents, i.e., aliphatic (e.g., alkyl or alkenyl) substituents, alicyclic (e.g., cycloalkyl, cycloalkenyl) substituents, and aromatic, aliphatic, and alicyclic-substituted aromatic substituents, as well as cyclic substituents in which the ring is completed through another portion of the molecule (e.g., two substituents together form an alicyclic radical); (2) substituted hydrocarbon substituents, i.e., substituents containing non-hydrocarbon groups (e.g., halo (especially chloro and fluoro), hydroxy, alkoxy, mercapto, alkylmercapto, nitro, nitroso, amino, alkylamino, and sulfoxy) that do not alter the predominantly hydrocarbon substituent in the context of this disclosure; and (3) heterosubstituents, i.e., substituents that, while predominantly hydrocarbon in the context of this disclosure, contain other than carbon in the ring or chain or are otherwise composed of carbon atoms. Heteroatoms include sulfur, oxygen, and nitrogen, and include substituents such as pyridyl, furyl, thienyl, and imidazolyl. Generally, no more than two, or as a further example, only one, non-hydrocarbon substituent will be present for every ten carbon atoms in the hydrocarbyl group, and in some embodiments, there will be no non-hydrocarbon substituents in the hydrocarbyl group.

[0122] As used herein, the term "aliphatic" encompasses the terms alkyl, alkenyl, alkynyl, each of which is optionally substituted as described below.

[0123] As used herein, an "alkyl" group refers to a saturated aliphatic hydrocarbon group containing 1 to 12 (e.g., 1 to 8, 1 to 6, or 1 to 4) carbon atoms. The alkyl group can be linear or branched. Examples of alkyl groups include, but are not limited to, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, n-heptyl, or 2-ethylhexyl. An alkyl group can have one or more substituents, such as halo, phospho, alicyclic [e.g., cycloalkyl or cycloalkenyl], heteroalicyclic [e.g., heterocycloalkyl or heterocycloalkenyl], aryl, heteroaryl, alkoxy, aroyl, heteroaroyl, acyl [e.g., (aliphatic)carbonyl, (alicyclic)carbonyl, or (heteroalicyclic)carbonyl], nitro, cyano, amido [e.g., (cycloalkylalkyl)carbonylamino, arylcarbonylamino, aralkylcarbonylamino, (heterocycloalkyl)carbonylamino, (heterocycloalkylalkyl)carbonylamino, heteroarylcarbonylamino, heteroaralkylcarbonylamino], or the like.

[0039] The aryl group may be substituted (i.e., optionally substituted) with an alkylaminocarbonyl, cycloalkylaminocarbonyl, heterocycloalkylaminocarbonyl, arylaminocarbonyl, or heteroarylaminocarbonyl, amino, [e.g., aliphatic amino, alicyclic amino, or heteroalicyclic amino], sulfonyl [e.g., aliphatic -SO2-], sulfinyl, sulfanyl, sulfoxy, urea, thiourea, sulfamoyl, sulfamido, oxo, carboxy, carbamoyl, alicyclicoxy, heterocycloaliphaticoxy, aryloxy, heteroaryloxy, aralkyloxy, heteroarylalkoxy, alkoxycarbonyl, alkylcarbonyloxy, or hydroxy.Some examples of substituted alkyls include, but are not limited to, carboxyalkyl (e.g., HOOC-alkyl, alkoxycarbonylalkyl, and alkylcarbonyloxyalkyl), cyanoalkyl, hydroxyalkyl, alkoxyalkyl, acylalkyl, aralkyl, (alkoxyaryl)alkyl, (sulfonylamino)alkyl (e.g., (alkyl-SO2-amino)alkyl), aminoalkyl, amidoalkyl, (alicyclic)alkyl, or haloalkyl.

[0124] As used herein, an "alkenyl" group refers to an aliphatic carbon group containing 2 to 8 (e.g., 2 to 12, 2 to 6, or 2 to 4) carbon atoms and at least one double bond. Like an alkyl group, an alkenyl group can be linear or branched. Examples of alkenyl groups include, but are not limited to, allyl, isoprenyl, 2-butenyl, and 2-hexenyl. Alkenyl groups can have one or more substituents, such as halo, phospho, alicyclic [e.g., cycloalkyl or cycloalkenyl], heteroalicyclic [e.g., heterocycloalkyl or heterocycloalkenyl], aryl, heteroaryl, alkoxy, aroyl, heteroaroyl, acyl [e.g., (aliphatic)carbonyl, (alicyclic)carbonyl, or (heteroalicyclic)carbonyl], nitro, cyano, amido [e.g., (cycloalkylalkyl)carbonylamino, arylcarbonylamino, aralkylcarbonylamino, (heterocycloalkyl)carbonylamino, (heterocycloalkylalkyl)carbonylamino, heteroarylcarbonylamino, heteroaralkylcarbonylaminoalkylaminocarbonyl], or heteroarylcarbonylamino. and optionally substituted by alkyl, cycloalkylaminocarbonyl, heterocycloalkylaminocarbonyl, arylaminocarbonyl, or heteroarylaminocarbonyl], amino, [e.g., aliphatic amino, alicyclic amino, heteroalicyclic amino, or aliphatic sulfonylamino], sulfonyl [e.g., alkyl-SO2-, alicyclic-SO2-, or aryl-SO2-], sulfinyl, sulfanyl, sulfoxy, urea, thiourea, sulfamoyl, sulfamido, oxo, carboxy, carbamoyl, alicyclicoxy, heteroalicyclicoxy, aryloxy, heteroaryloxy, aralkyloxy, heteroaralkoxy, alkoxycarbonyl, alkylcarbonyloxy, or hydroxy. Some examples of substituted alkenyls include, but are not limited to, cyanoalkenyl, alkoxyalkenyl, acylalkenyl, hydroxyalkenyl, aralkenyl, (alkoxyaryl)alkenyl, (sulfonylamino)alkenyl (e.g., (alkyl-SO2-amino)alkenyl), aminoalkenyl, amidoalkenyl, (alicyclic)alkenyl, or haloalkenyl.

[0125] As used herein, an "alkynyl" group refers to an aliphatic carbon group containing 2 to 8 (e.g., 2 to 12, 2 to 6, or 2 to 4) carbon atoms and having at least one triple bond. Alkynyl groups can be linear or branched. Examples of alkynyl groups include, but are not limited to, propargyl and butynyl. Alkynyl groups can be substituted with one or more groups, such as aroyl, heteroaroyl, alkoxy, cycloalkyloxy, heterocycloalkyloxy, aryloxy, heteroaryloxy, aralkyloxy, nitro, carboxy, cyano, halo, hydroxy, sulfo, mercapto, sulfanyl [e.g., aliphatic sulfanyl or alicyclic sulfanyl], sulfinyl [e.g., aliphatic sulfinyl or alicyclic sulfinyl], sulfonyl [e.g., aliphatic -SO2-, aliphatic amino-SO2-, or alicyclic -SO2-], amido [e.g., aminocarbonyl, alkylaminocarbonyl, alkylcarbonylamino, cycloalkylaminocarbonyl, heterocycloalkylaminocarbonyl, cycloalkylcarbonylamino, aryl aminocarbonyl, arylcarbonylamino, aralkylcarbonylamino, (heterocycloalkyl)carbonylamino, (cycloalkylalkyl)carbonylamino, heteroaralkylcarbonylamino, heteroarylcarbonylamino, or heteroarylaminocarbonyl], urea, thiourea, sulfamoyl, sulfamido, alkoxycarbonyl, alkylcarbonyloxy, alicyclic, heteroalicyclic, aryl, heteroaryl, acyl [e.g., (alicyclic)carbonyl or (heteroalicyclic)carbonyl], amino [e.g., aliphatic amino], sulfoxy, oxo, carboxy, carbamoyl, (alicyclic)oxy, (heteroalicyclic)oxy, or (heteroaryl)alkoxy.

[0126] As used herein, an "amino" group refers to an -NR X R Y In the formula, R X and R Yis independently hydrogen, alkyl, cycloalkyl, (cycloalkyl)alkyl, aryl, aralkyl, heterocycloalkyl, (heterocycloalkyl)alkyl, heteroaryl, carboxy, sulfanyl, sulfinyl, sulfonyl, (alkyl)carbonyl, (cycloalkyl)carbonyl, ((cycloalkyl)alkyl)carbonyl, arylcarbonyl, (aralkyl)carbonyl, (heterocycloalkyl)carbonyl, ((heterocycloalkyl)alkyl)carbonyl, (heteroaryl)carbonyl, or (heteroaralkyl)carbonyl, each of which is defined herein and optionally substituted. Examples of amino groups include alkylamino, dialkylamino, or arylamino. When the term "amino" is not a terminal group (e.g., alkylcarbonylamino), it is not -NR X - represented by R X has the same meaning as defined above.

[0127] As used herein, a "cycloalkyl" group refers to a saturated carbocyclic monocyclic or bicyclic (fused or bridged) ring of 3 to 10 (e.g., 5 to 10) carbon atoms. Examples of cycloalkyl groups include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, adamantyl, norbornyl, cubyl, octahydroindenyl, decahydronaphthyl, bicyclo[3.2.1]octyl, bicyclo[2.2.2]octyl, bicyclo[3.3.1]nonyl, bicyclo[3.3.2]decyl, bicyclo[2.2.2]octyl, adamantyl, or ((aminocarbonyl)cycloalkyl)cycloalkyl.

[0128] As used herein, a "heterocycloalkyl" group refers to a 3- to 10-membered mono- or bicyclic (fused or bridged) (e.g., 5- to 10-membered mono- or bicyclic) saturated ring structure in which one or more of the ring atoms is a heteroatom (e.g., N, O, S, or combinations thereof). Examples of heterocycloalkyl groups include piperidyl, piperazyl, tetrahydropyranyl, tetrahydrofuryl, 1,4-dioxolanyl, 1,4-dithianyl, 1,3-dioxolanyl, oxazolidyl, isoxazolidyl, morpholinyl, thiomorpholyl, octahydrobenzofuryl, octahydrochromenyl, octahydrothiochromenyl, octahydroindolyl, octahydropyrindinyl, decahydroquinolinyl, octahydrobenzo[b]thiophenyl, 2-oxa-bicyclo[2.2.2]octyl, 1-aza-bicyclo[2.2.2]octyl, 3-aza-bicyclo[3.2.1]octyl, and 2,6-dioxa-tricyclo[3.3.1.0]nonyl. Monocyclic heterocycloalkyl groups can be fused with a phenyl moiety to form structures such as tetrahydroisoquinoline, which would be classified as heteroaryls.

[0129] As used herein, a "heteroaryl" group refers to a monocyclic, bicyclic, or tricyclic ring system having 4 to 15 ring atoms, where one or more ring atoms are heteroatoms (e.g., N, O, S, or a combination thereof), and the monocyclic ring system is aromatic, or at least one of the rings in the bicyclic or tricyclic ring system is aromatic. Heteroaryl groups include benzo-fused ring systems having 2 to 3 rings. For example, a benzo-fused group includes benzo fused to one or two 4- to 8-membered heterocyclic aliphatic moieties (e.g., indolyl, indolyl, isoindolyl, 3H-indolyl, indolinyl, benzo[b]furyl, benzo[b]thiophenyl, quinolinyl, or isoquinolinyl). Some examples of heteroaryl are pyridyl, 1H-indazolyl, furyl, pyrrolyl, thienyl, thiazolyl, oxazolyl, imidazolyl, tetrazolyl, benzofuryl, isoquinolinyl, benzthiazolyl, xanthene, thioxanthene, phenothiazine, dihydroindole, benzo[1,3]dioxole, benzo[b]furyl, benzo[b]thiophenyl, indazolyl, benzimidazolyl, benzthiazolyl, puryl, cinnolyl, quinolyl, quinazolyl, cinnolyl, phthalazyl, quinazolyl, quinoxalyl, isoquinolyl, 4H-quinolidyl, benzo-1,2,5-thiadiazole, or 1,8-naphthyridyl.

[0130] Monocyclic heteroaryls include, but are not limited to, furyl, thiophenyl, 2H-pyrrolyl, pyrrolyl, oxazolyl, thazolyl, imidazolyl, pyrazolyl, isoxazolyl, isothiazolyl, 1,3,4-thiadiazolyl, 2H-pyranyl, 4H-pyranyl, pyridyl, pyridazyl, pyrimidyl, pyrazolyl, pyrazyl, or 1,3,5-triazyl. Monocyclic heteroaryls are numbered according to standard chemical nomenclature.

[0131] Bicyclic heteroaryls include indolizyl, indolyl, isoindolyl, 3H-indolyl, indolinyl, benzo[b]furyl, benzo[b]thiophenyl, quinolinyl, isoquinolinyl, indolizinyl, isoindolyl, indolyl, benzo[b]furyl, bexo[b]thiophenyl, indazolyl, benzimidazyl, benzthiazolyl, purinyl, 4H-quinolizyl, quinolyl, isoquinolyl, cinnolyl, phthalazyl, quinazolyl, quinoxalyl, 1,8-naphthyridyl, or pteridyl. Bicyclic heteroaryls are numbered according to standard chemical nomenclature.

[0132] As used herein, the term "treat rate" refers to the weight percent of a component in a lubricating and cooling fluid.

[0133] The weight average molecular weight (Mw) and / or number average molecular weight (Mn) can be determined using a gel permeation chromatography (GPC) instrument from Waters or similar instrumentation and Waters Empower Software or similar software. The GPC instrument can be equipped with a Waters Separation Module and a Waters Refractive Index Detector (or similar optional instrumentation). GPC operating conditions can include a guard column, four Agilent PLgel columns (300 x 7.5 mm long, 5 μm particle size, and pore sizes ranging from 100 to 10,000 Å), and a column temperature of approximately 40°C. Unstabilized HPLC-grade tetrahydrofuran (THF) can be used as the solvent at a flow rate of 1.0 mL / min. The GPC instrument can be calibrated with commercially available poly(methyl methacrylate) (PMMA) standards with narrow molecular weight distributions ranging from 960 to 1,568,000 g / mol. The calibration curve can be extrapolated for samples with masses less than 500 g / mol. Samples and PMMA standards can be dissolved in THF, prepared at concentrations of 0.1 to 0.5 wt. %, and used without filtration. GPC measurements are also described in U.S. Pat. No. 5,266,223, which is incorporated herein by reference. The GPC method additionally provides molecular weight distribution information; see, for example, W.W. Yau, J.J. Kirkland, and D.B. Ly, "Modern Size Exclusion Liquid Chromatography," John Wiley and Sons, New York, 1979, which is incorporated herein by reference. [Example]

[0134] A better understanding of the present disclosure and its many advantages can be clarified with the following examples. The following examples are illustrative and not limiting in scope or spirit. Those skilled in the art will readily understand that variations of the components, methods, steps, and devices described in these examples can be used. Unless otherwise stated or apparent from the context of the following examples and discussion throughout this disclosure, all percentages, ratios, and parts described in this disclosure are by weight. Any standardized test method described in the examples, disclosure, or claims refers to the version of the test method publicly available at the time of filing this disclosure, unless apparent from the context of its use.

[0135] Example 1 The lubricating compositions of the present invention and the comparative lubricating compositions were each evaluated for fuel economy improvement in accordance with the JASO M365 motoring engine test. The lubricating composition of the present invention in this example contained approximately 1160 ppm of calcium provided by a hydrocarbyl-substituted sulfonate compound, while the comparative lubricating composition of this example provided approximately 1160 ppm of calcium from a salicylate compound. The calcium sulfonate compound in the inventive composition was an overbased hydrocarbyl-substituted calcium sulfonate having a TBN of approximately 300 mg KOH / gram, approximately 11.9% calcium, and a hydrocarbyl substituent derived from a blend of C14 to C26 olefins having a number average molecular weight of approximately 250 to approximately 300. The calcium salicylate compound in the comparative composition had a TBN of approximately 177 mg KOH / gram, approximately 6.6 percent calcium, and a hydrocarbyl substituent derived from a blend of C14 to C18 olefins. Each of the inventive and comparative compositions was also combined with a molybdenum dialkyldithiocarbamate compound and / or an organomolybdenum nitrogen complex as the oil-soluble molybdenum compound to provide the total amount of molybdenum in each of the inventive and comparative compositions.

[0136] All compositions contained the same additive package of dispersant, antiwear additive, aminic antioxidant, phenolic antioxidant, friction modifier, antifoam agent, pour point depressant, and processing oil. The inventive and comparative compositions also contained about 600 ppm phosphorus, about 2500 ppm sulfur, about 150 ppm boron, and about 650 ppm zinc. The inventive and comparative lubricating compositions each contained a base oil selected from about 4 to about 8 cSt Group III base oils. The only material change between the inventive and comparative samples was the sulfonate compound versus the salicylate compound.

[0137] Table 3 below provides further details for the lubricants of the present invention and the comparative lubricants, including the JASO fuel economy improvement for each. Fuel economy for this example was performed in accordance with the JASO M365 motoring fuel economy test using a Nissan MR20DD 2.0L engine (e.g., a Nissan Sentra equipped with a 1997cc inline 4-cylinder 16-valve engine with direct injection and twin variable valve timing control) and measured using the Japan WLTC cycle.

[0138] [Table 3]

[0139] As shown in Table 3 above, lubricants containing calcium provided by salicylate compounds were unable to pass the M365 fuel reformulation test, while methods including lubricants containing selected hydrocarbyl-substituted calcium sulfonate compounds in combination with oil-soluble molybdenum compounds were unexpectedly able to pass the M365 fuel reformulation test.

[0140] Example 2 The lubricating compositions of the present invention and the comparative lubricating compositions were each evaluated for fuel economy improvement in accordance with the JASO M366 combustion engine test. The lubricating compositions of the present invention contained approximately 1200 ppm of calcium provided by a hydrocarbyl-substituted sulfonate compound, while the comparative lubricating compositions provided approximately 1200 ppm of calcium from a calcium salicylate compound. The hydrocarbyl-substituted calcium sulfonate compound in the inventive composition was an overbased calcium sulfonate having approximately 300 mg KOH / gram TBN, approximately 11.9% calcium, and a hydrocarbyl substituent derived from a blend of C14-C26 olefins having a number average molecular weight of approximately 250 to approximately 300 g / mol. The calcium salicylate compound in the comparative composition had approximately 177 mg KOH / gram TBN, approximately 6.6 percent calcium, and a hydrocarbyl substituent derived from a blend of C14-C18 olefins. Each composition was also combined with a molybdenum dialkyldithiocarbamate compound and / or an organomolybdenum nitrogen complex to provide the total amount of molybdenum in each of the inventive and comparative compositions.

[0141] All compositions contained the same additive package of dispersant, antiwear additive, aminic antioxidant, phenolic antioxidant, friction modifier, antifoam agent, pour point depressant, and processing oil. The inventive and comparative compositions also contained about 600 ppm phosphorus, about 2200 ppm sulfur, about 100 ppm boron, and about 700 ppm zinc. The inventive and comparative lubricants each contained a base oil blend selected from about 4 to about 8 cSt Group III base oils. The only material change between the inventive and comparative samples was the sulfonate compound versus the salicylate compound.

[0142] Table 4 below provides further details, including JASO fuel economy improvement, for the lubricants of the present invention and the comparative lubricants. Fuel economy was performed according to JASO M366 using a Toyota 2ZR-FXE engine (e.g., a 1.8 liter, inline 5, Toyota Prius with port fuel injection).

[0143] [Table 4]

[0144] As shown in Table 4 above, lubricants containing calcium provided by salicylates were unable to pass the M366 fuel reformulation test, while lubricants containing selected hydrocarbyl-substituted calcium sulfonate compounds in combination with oil-soluble molybdenum compounds were unexpectedly able to pass the M366 fuel reformulation test.

[0145] Example 3 Further comparative lubricating compositions were evaluated for fuel economy improvement according to the JASO M365 motoring engine test. The comparative lubricating composition of this example used magnesium sulfonate instead of calcium sulfonate and provided approximately 1000 ppm of magnesium from a hydrocarbyl-substituted magnesium sulfonate compound. The magnesium sulfonate compound was an overbased hydrocarbyl-substituted magnesium sulfonate having approximately 400 mg KOH / gram TBN, approximately 9.6% magnesium, and a hydrocarbyl substituent derived from a blend of C14 to C26 olefins having a number average molecular weight of approximately 250 to approximately 300. As with the other examples, the comparative composition of this example also provided the total amount of molybdenum in combination with a molybdenum dialkyldithiocarbamate compound and / or an organomolybdenum nitrogen complex. This composition also had an additive package similar to that of Example 1, including a dispersant, an antiwear additive, an aminic antioxidant, a phenolic antioxidant, a friction modifier, an antifoam agent, a pour point depressant, and a processing oil. The comparative composition of this example also had about 600 ppm phosphorus, about 2500 ppm sulfur, about 150 ppm boron, and about 650 ppm zinc. The comparative lubricant included a base oil blend selected from about 4 to about 8 cSt Group III base oils.

[0146] Table 5 below provides further details, including JASO fuel economy improvement, for the comparative lubricants of this example. Fuel economy was performed for this example in accordance with the JASO M365 motoring fuel economy test using a Nissan MR20DD 2.0L engine (e.g., a Nissan Sentra with a 1997cc inline 4-cylinder 16-valve engine with direct injection and twin variable valve timing control).

[0147] [Table 5]

[0148] As shown in Table 5 above, lubricants containing magnesium provided by a sulfonate compound were unable to pass the M365 fuel improvement test, even when combined with the oil-soluble molybdenum compound of Example 1. Thus, comparing the results of Example 1 to this example, a comparable amount of metal provided by a magnesium sulfonate unexpectedly failed to achieve the same M365 fuel economy performance pass compared to a composition containing a calcium sulfonate compound.

[0149] It should be noted that, as used in this specification and the appended claims, the singular forms "a," "an," and "the" include plural referents unless expressly and unambiguously limited to one referent. Thus, for example, a reference to an "antioxidant" includes two or more different antioxidants. As used herein, the term "comprises" and grammatical variations thereof are intended to be open-ended such that the recitation of items in a list does not exclude other similar items that may be substituted for or added to the listed items.

[0150] For purposes of this specification and the appended claims, unless otherwise indicated, all numbers expressing quantities, percentages, or proportions, and other numerical values ​​used in the specification and claims should be understood in all instances to be modified by the term "about." Accordingly, unless indicated to the contrary, the numerical parameters set forth in the following specification and appended claims are approximations that may vary depending upon the desired properties sought to be obtained by the present disclosure. At the very least, and not as an attempt to limit the application of the doctrine of equivalents to the scope of the claims, each numerical parameter should at least be construed in light of the number of reported significant digits and by applying ordinary rounding techniques.

[0151] It is understood that each component, compound, substituent, or parameter disclosed herein should be construed as disclosed for use alone or in combination with one or more of any and all other components, compounds, substituents, or parameters disclosed herein.

[0152] It is further understood that each range disclosed herein should be construed as a disclosure of each specific value within the disclosed range having the same number of significant digits. Thus, for example, a range of 1 to 4 should be construed as an explicit disclosure of not only the values ​​1, 2, 3, and 4, but also any range of such values.

[0153] It should be further understood that each lower limit of each range disclosed herein should be interpreted as being disclosed in combination with each upper limit of each range and each specific value within each range for the same component, compound, substituent, or parameter. Thus, the present disclosure should be interpreted as a disclosure of all ranges derived by combining each lower limit of each range with each upper limit of each range, or each specific value within each range, or by combining each upper limit of each range with each specific value within each range. It should also be further understood that any range between the endpoints within a broad range is also contemplated herein. Thus, a range of 1 to 4 also means ranges of 1 to 3, 1 to 2, 2 to 4, 2 to 3, etc.

[0154] Furthermore, a specific amount / value of a component, compound, substituent, or parameter disclosed in the description or examples should be construed as a disclosure of either a lower or upper limit of a range and, therefore, can be combined with any other lower or upper limit or specific amount / value in a range for the same component, compound, substituent, or parameter disclosed elsewhere in this application to form a range for that component, compound, substituent, or parameter.

[0155] While particular embodiments have been described, alternatives, modifications, variations, improvements, and substantial equivalents may occur that are not presently anticipated or presently unforeseeable to applicants or others skilled in the art. It is therefore intended that the appended claims, as filed and as they may be amended, will embrace all such alternatives, modifications, variations, improvements, and substantial equivalents.

Claims

1. 1. A method for improving fuel economy in a passenger vehicle engine using a lubricating oil composition, said method comprising: lubricating an engine crankcase of a passenger vehicle engine with the lubricating oil composition and achieving a positive increase in fuel economy as measured in accordance with one or both of JASO M366 and / or JASO M365; 1. A method for producing a lubricating oil composition comprising: (i) at least one calcium-containing hydrocarbyl-substituted sulfonate compound providing about 900 ppm or more of calcium to the lubricating oil composition, wherein the lubricating oil composition is essentially devoid of sulfur-free detergents; (ii) at least one oil-soluble molybdenum compound providing about 500 to about 1200 ppm of molybdenum to the lubricating oil composition; (iii) an ash-contributing additive in an amount to provide a total measured sulfated ash of about 0.8 weight percent or less, as measured in accordance with ASTM D874; (iv) a total base number (TBN) of the lubricating oil composition of at least about 6.0 mg KOH / gram, as measured in accordance with ASTM D2896; and (v) a high temperature high shear viscosity of about 1.7 to about 2.9 cSt, as measured at 150°C in accordance with ASTM D4683.

2. 2. The method of claim 1, wherein the lubricating oil composition has a positive fuel economy increase of greater than 1.1% when measured in accordance with JASO M366 and / or the lubricating oil composition has a positive fuel economy increase of greater than 1.5% (Japan WLTC mode) when measured in accordance with JASO M365.

3. 10. The method of claim 1, wherein the calcium-containing hydrocarbyl-substituted sulfonate compound provides up to about 1500 ppm of calcium and / or the calcium-containing hydrocarbyl-substituted sulfonate compound has a total base number (TBN) of at least about 175 mg KOH / gram as measured in accordance with ASTM D2896.

4. 4. The method of claim 3, wherein the calcium-containing, hydrocarbyl-substituted sulfonate compound comprises a hydrocarbyl portion thereof having a number average molecular weight of about 80 to 300 g / mole, and / or the hydrocarbyl portion of the calcium-containing, hydrocarbyl-substituted sulfonate component comprises a linear or branched C6 to C30 hydrocarbyl group.

5. The method of claim 1 , wherein the sulfur-free detergent comprises a metal-containing salicylate detergent.

6. 10. The method of claim 1, wherein the lubricating composition has a calcium to molybdenum weight ratio of about 1:1 to about 2:

1.

7. 10. The method of claim 1, wherein the oil-soluble molybdenum compound is selected from molybdenum dithiocarbamates, molybdenum dialkyldithiophosphates, molybdenum sulfides, molybdenum disulfides, molybdenum dithiophosphinates, amine salts of molybdenum compounds, organo-molybdenum nitrogen complexes, molybdenum xanthates, molybdenum thioxanthates, molybdenum sulfides, molybdenum carboxylates, molybdenum alkoxides, trinuclear organo-molybdenum compounds, complexes thereof, esters thereof, and / or mixtures thereof.

8. The method of claim 7, wherein the lubricating composition has a calcium to molybdenum weight ratio of about 1:1 to about 2:

1.

9. 10. The method of claim 1, wherein the lubricating oil composition is essentially devoid of metal salts of phenates, calixarates, salixarates, salicylates, carboxylic acids, or combinations thereof, and / or the lubricating oil composition is substantially free of organic friction modifiers.

10. 10. The method of claim 1, wherein the lubricating oil composition has a KV100 of about 8 cSt or less.

11. 1. A passenger car engine lubricating oil composition configured to achieve a positive fuel economy improvement in accordance with JASO M366 and / or JASO M365, said composition comprising: at least one calcium-containing hydrocarbyl-substituted sulfonate compound providing about 900 ppm or more of calcium to said lubricating oil composition, said lubricating oil composition being essentially devoid of sulfur-free detergents; at least one oil-soluble molybdenum-containing compound providing from about 500 to about 1200 ppm of molybdenum to said lubricating oil composition; an ash contributing additive in an amount to provide a total measured sulfated ash content of about 0.8 weight percent or less, as measured in accordance with ASTM D874; a total base number (TBN) of the lubricating oil composition of at least about 6.0 mg KOH / gram, as measured in accordance with ASTM D2896; and a high temperature, high shear viscosity of about 1.7 to about 2.9 cSt, as measured at 150°C according to ASTM D4683; A passenger car engine lubricating oil composition, wherein said lubricating oil composition has a calcium to molybdenum weight ratio of from about 1:1 to about 2:

1.

12. 12. The composition of claim 11, wherein the lubricating oil composition has a positive fuel economy increase of greater than 1.1% when measured in accordance with JASO M366 and / or the lubricating oil composition has a positive fuel economy increase of greater than 1.5% (Japan WLTC mode) when measured in accordance with JASO M365.

13. 12. The composition of claim 11, wherein the calcium-containing hydrocarbyl-substituted sulfonate compound provides up to about 1500 ppm calcium.

14. 14. The composition of claim 13, wherein the calcium-containing hydrocarbyl-substituted sulfonate compound has a number average molecular weight of about 80 to 300 g / mole and comprises a hydrocarbyl portion thereof derived from a C14 to C30 olefin.

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