Lubricating compositions for durability and improved fuel economy

Abstract

To provide a composition and a method for lubricating a diesel internal combustion engine effective for piston cleanliness and improved fuel economy.SOLUTION: The engine lubricant composition comprises one or more base oils having a combined base oil viscosity of about 5.4 cSt or less at 100°C, and a detergent system providing the engine lubricant composition with a minimum total base number of at least about 4 mg KOH / g as measured according to ASTM D4739, wherein the engine lubricant composition has one or more of (i) a NOACK volatility of about 13% or less, (ii) a total base number of the engine lubricant composition of about 10 mg KOH / g or less as measured according to ASTM D2896, (iii) a calculated sulfated ash (SASH) of about 0.8 weight percent or less as measured according to ASTM D874, (iv) a CCS viscosity at -35°C of about 6200 mPas or less as measured according to ASTM D5292, or (v) a combination thereof.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present disclosure relates to lubricating compositions, and in particular to lubricating compositions that exhibit improved piston cleanliness with improved fuel economy. [Background technology]

[0002] Automotive manufacturers continue to seek improvements in efficiency, fluid life, and fuel economy, which in turn increases the requirements placed 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 an industry and / or manufacturer's application.

[0003] Typically, industry standards and / or automotive manufacturers require certain performance characteristics, so 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 durability (i.e., piston cleanliness). Fuel economy can be evaluated, for example, through the JASO M 366 fuel economy test, and durability can be evaluated through the VW TDi3 piston cleanliness test of CEC L-117-20. Formulations that are good for fuel economy tend to be detrimental to piston cleanliness, and vice versa. Such conflicting standards present a challenge to lubricant manufacturers. Summary of the Invention

[0004] The present disclosure relates to an engine lubricating oil composition comprising one or more base oils of lubricating viscosity, wherein the one or more base oils have a combined base oil viscosity at 100°C of about 5.4 cSt or less, and a detergent system that provides the engine lubricating oil composition with a minimum total base number (TBN) as measured in accordance with ASTM D4739 of at least about 4 mg KOH / g, wherein the engine lubricating oil composition has (i) a NOACK volatility of about 13% or less as measured in accordance with CEC L-40-93 and / or ASTM D5800, (ii) a total base number (TBN) of the engine lubricating oil composition of about 10 mg KOH / g or less as measured in accordance with ASTM D2896, (iii) a calculated sulfated ash (SASH) of about 0.8 weight percent or less as measured in accordance with ASTM D874, (iv) a detergent system that provides the engine lubricating oil composition with a minimum total base number (TBN) as measured in accordance with ASTM D4739 of at least about 4 mg KOH / g, wherein the engine lubricating oil composition has (i) a NOACK volatility of about 13% or less as measured in accordance with CEC L-40-93 and / or ASTM D5800, (ii) a total base number (TBN) of about 10 mg KOH / g or less as measured in accordance with ASTM D2896, (iii) a calculated sulfated ash (SASH) of about 0.8 weight percent or less as measured in accordance with ASTM D874, (iv) a detergent system that provides the engine lubricating oil composition with a minimum total base number (TBN) as measured in accordance with ASTM D4739 of at least about 4 mg KOH / g, or (v) one or more of the following: (i) a CCS viscosity at −35° C. of about 6200 mPas or less, as measured in accordance with CEC L-117-20 (VW TDi3) Piston Cleanliness Test; (ii) a CCS viscosity at −35° C. of about 6200 mPas or less, as measured in accordance with CEC L-117-20 (VW TDi3) Piston Cleanliness Test; and (iii) a piston cleanliness rating of at least about 53 merit, at least about 54 merit, at least about 55 merit, at least about 56 merit, at least about 57 merit, at least about 58 merit, or at least about 59 merit. Such embodiments of the engine lubricating oil compositions herein also have a positive fuel economy increase, as measured in accordance with JASO M 366, and preferably exhibit an improvement in fuel economy of at least about 0.5%, at least about 0.6%, at least about 0.7%, or at least about 0.8%, as measured in accordance with JASO M 366.

[0005] In other approaches or embodiments, the lubricating oil compositions of the preceding paragraphs may include the optional features or embodiments in any combination. These optional features or embodiments include the detergent system being substantially free of phenate detergent additives, and / or the detergent system comprising, consisting of, or consisting essentially of, a sulfonate detergent additive, preferably the detergent system being exclusively sulfonate detergent additives, and / or the detergent system providing calcium, magnesium, or a combination thereof to the engine lubricating oil composition, and preferably the detergent system being exclusively magnesium-containing detergent additives, and / or the detergent system providing from about 800 to about 1800 ppm magnesium, from about 1000 to about 1500 ppm magnesium, or from about 1200 to about 1400 ppm magnesium to the engine lubricating oil composition, and / or the detergent system having a magnesium saturation coefficient of at least about 250 mg KOH / g, preferably at least about 300 mg KOH / g, more preferably at least about 350 mg KOH / g, or most preferably at least about 400 mg KOH / g, as measured in accordance with ASTM D2896. and / or the engine lubricating oil composition has a TBN of about 8 or less as measured in accordance with ASTM D2896, and / or the TBN of the detergent system is from about 4 to about 10 mg KOH / g. KOH / g, and / or further comprising an additive-containing oil-soluble molybdenum, preferably a molybdenum dialkyldithiocarbamate compound, and / or comprising molybdenum but further comprising not more than about 800 ppm molybdenum, not more than about 700 ppm molybdenum, not more than about 600 ppm molybdenum, not more than about 500 ppm molybdenum, not more than about 400 ppm molybdenum, not more than about 300 ppm molybdenum, not more than about 200 ppm molybdenum, not more than about 100 ppm molybdenum, not more than about 50 ppm molybdenum, and / or further comprising one or more polymeric viscosity index improver additives, preferably from about 2 to about 10 weight percent of one or more polymeric viscosity index improver additives, and / or the engine lubricating oil composition has a viscosity index of from 130 to 300, and / or the one or more polymeric viscosity index improver additives are selected from the group consisting of (i) an olefin copolymer,(ii) a dispersant or non-dispersant poly(meth)acrylate copolymer viscosity modifier having a weight average molecular weight of about 500,000 or less, or (iii) one of a combination thereof, and / or the dispersant or non-dispersant poly(meth)acrylate copolymer has a weight average molecular weight of about 200,000 to about 500,000 with a polydispersity index of about 1.5 to about 2.5, and has a hydrogen atom in the monomer ester portion of up to about 700, up to about 1000, up to about 2000, up to about 4000, up to about 8000, or up to about 10000, or a combination thereof. and / or the engine lubricating oil composition is substantially free of polymeric viscosity index improver additives, and / or the one or more gas 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, and / or 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 4 to 8 cSt at 100°C, and / or the engine lubricating oil composition is 0 and / or the engine lubricating oil composition has a viscosity grade of 0W-16, and / or the base oil viscosity is 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, about 4.2 cSt or less, and / or the base oil viscosity is at least about 3 cSt, at least about 3.2 cSt, at least about 3.4 cSt, at least about 3.6 cSt, at least about 3.8 cSt, ... and / or the engine lubricating oil composition further comprises a dispersant inhibitor package, preferably comprising one or more of a dispersant, a detergent, an anti-wear additive, an antioxidant, a friction modifier, a pour point depressant, a seal swell agent, or a combination thereof; and / or the engine lubricating oil composition further comprises from about 5 to about 20 weight percent of a dispersant inhibitor package; and / or the engine lubricating oil composition is substantially free of boron, substantially free of calcium, or a combination thereof; and / or one or more metal disilylcarbyl dithiophosphate compounds, preferablyone or more zinc dihydrocarbyl dithiophosphate compounds, and / or the one or more metal dihydrocarbyl dithiophosphate compounds provide up to about 1000 ppm of phosphorus, up to about 900 ppm of phosphorus, or up to about 800 ppm of phosphorus to the lubricating oil composition; and / or the one or more metal dihydrocarbyl dithiophosphate compounds provide up to about 1000 ppm of zinc, up to about 900 ppm of zinc, or up to about 850 ppm of phosphorus to the lubricating oil composition; and / or the one or more sulfur-containing additives, wherein the one or more sulfur-containing additives provide up to about 2500 ppm of sulfur, up to about 2200 ppm of sulfur, or up to about 2100 ppm of sulfur to the lubricating oil composition.

[0006] In yet another approach or embodiment, described herein are methods for improving fuel economy and piston cleanliness in a passenger vehicle engine using a lubricating oil composition. The method includes lubricating an engine crankcase of the passenger vehicle engine with the lubricating oil composition, where the lubricating oil composition is as specified in any embodiment of the Summary of the Invention, and where the lubricating oil composition meets or exceeds the lubrication performance specified in the CEC L-117-20 (VW TDi3) piston cleanliness test, and the lubricating oil composition has a positive fuel economy increase as measured in accordance with JASO M 366. In some embodiments, the method results in a piston cleanliness rating according to CEC L-117-20 (VW TDi3) of at least about 53 merit, at least about 54 merit, at least about 55 merit, at least about 56 merit, at least about 57 merit, at least about 58 merit, or at least about 59 merit. In other embodiments, the method provides at least about 0.5%, at least about 0.6%, at least about 0.7%, or at least about 0.8% improvement in fuel economy as measured according to JASO M 366. In further embodiments or approaches to the method, any embodiment of the engine oil lubricating composition as described in the Summary of the Invention may be used in the method herein.

[0007] In a further embodiment or approach, described herein is a method of lubricating the crankcase of a passenger car engine using a lubricating oil composition. The method may include lubricating the engine crankcase of a passenger car engine with a lubricating oil composition, wherein the lubricating oil composition is as specified in any embodiment of the Summary of the Invention, and the passenger car engine lubricated with the lubricating oil composition meets or exceeds the lubrication performance specified in the CEC L-117-20 (VW TDi3) piston cleanliness test and has a positive fuel economy increase as measured according to JASO M 366.

[0008] In yet additional approaches or embodiments, any of the methods herein may include optional features, steps, or embodiments, in any combination, which may include one or more of the following: the lubricating oil composition has a piston cleanliness rating according to CEC L-117-20 (VW TDi3) of at least about 53 Merit, at least about 54 Merit, at least about 55 Merit, at least about 56 Merit, at least about 57 Merit, at least about 58 Merit, or at least about 59 Merit; and / or the lubricating oil composition has a fuel economy improvement as measured according to JASO M 366 of at least about 0.5%, at least about 0.6%, at least about 0.7%, or at least about 0.8%.

[0009] In further approaches or embodiments, the use of any embodiment of the engine oil lubricating composition of the present summary is described to achieve a piston cleanliness rating according to CEC L-117-20 (VW TDi3) of at least about 53 merit, at least about 54 merit, at least about 55 merit, at least about 56 merit, at least about 57 merit, at least about 58 merit, or at least about 59 merit, and / or to achieve a fuel economy improvement as measured according to JASO M 366 of at least about 0.5%, at least about 0.6%, at least about 0.7%, or at least about 0.8%. DETAILED DESCRIPTION OF THE INVENTION

[0010] The present disclosure relates to engine lubricating oil compositions and methods for lubricating diesel internal combustion engines that are effective in achieving robust performance in both durability (i.e., piston cleanliness) and improved fuel economy. In one aspect, the engine lubricating oil compositions herein have compositions that are effective in achieving passing piston cleanliness according to CEC L-117-20 (i.e., the VW TDi3 test) and achieving a positive fuel economy increase as measured according to JASO M 366, preferably at least about 0.5 percent fuel economy increase as measured according to JASO M 366. The engine lubricating oil compositions herein may have a viscosity grade of 0W-8, 0W-12, 0W16, and / or 0W-20. The compositions herein may be used in diesel engines.

[0011] In one approach or embodiment, the robust engine lubricating oil compositions described herein have compositions selected to achieve both diesel durability and improved fuel economy. In one aspect, the lubricating oil compositions herein comprise one or more base oils of lubricating viscosity, specifically one or more base oils having a combined base oil viscosity of less than or equal to about 5.4 cSt at 100° C. In another aspect, the lubricating oil compositions herein also comprise a detergent system that provides the engine lubricating oil composition with a minimum Total Base Number (TBN) of at least about 4 mg KOH / g, as measured in accordance with ASTM D4739. In further embodiments, the engine lubricating oil compositions herein may also have a configuration effective to achieve one or more of: (i) a NOACK volatility of about 13% or less, as measured in accordance with CEC L-40-63 and / or ASTM D5800; (ii) a total base number (TBN) of about 10 mg KOH / g or less, as measured in accordance with ASTM D2896; (iii) a calculated sulfated ash (SASH) of about 0.8 weight percent or less, as measured in accordance with ASTM D874; (iv) a CCS viscosity at −35° C. of about 6200 mPas or less, as measured in accordance with ASTM D5292; and / or (v) combinations thereof.

[0012] When so configured, the engine lubricating oil composition meets or exceeds the lubrication performance as evidenced in the CECL-117-20 (VW TDi3) piston cleanliness test, preferably exhibiting a piston cleanliness rating of at least about 53 merit, at least about 54 merit, at least about 55 merit, at least about 56 merit, at least about 57 merit, at least about 58 merit, or at least about 59 merit. At the same time, the engine lubricating oil composition also achieves a positive fuel economy increase as measured in accordance with JASO M 366, preferably a positive fuel economy improvement of at least about 0.5%, at least about 0.6%, at least about 0.7%, or at least about 0.8% as measured in accordance with JASO M 366.

[0013] As discussed in more detail below, the engine lubricating oil compositions herein achieve such performance through the selection of one or more specific base oil blends, detergent systems, and / or one or more polymeric viscosity index improver additives that perform particularly well in one or more viscosity grades of 0W-8, 0W-12, 0W16, and / or 0W-20. In some exemplary approaches, the lubricating oil compositions herein have an additive package contributing about 1000 to about 1800 ppm magnesium, about 10 to about 60 ppm molybdenum, about 500 to about 900 ppm phosphorus, about 1500 to about 1900 ppm sulfur, and / or about 500 to about 900 ppm zinc. In other exemplary approaches, the additive package herein may also provide a lubricant TBN (ASTM 4739) of greater than about 5 mg KOH / g, preferably about 5.2 to about 6.0 mg KOH / g, and a SASH of about 0.7 to about 0.8. Further details regarding lubricant components and additive packages are provided below and illustrated in the Examples herein.

[0014] Detergents The engine lubricating oil compositions herein contain select detergent systems configured to function with the referenced base oil blends to achieve lubricant durability via the VW TDi3 piston cleanliness test with little or no phenate, preferably no phenate detergent additives. In some approaches, piston cleanliness is achieved with the detergents herein when a minimum lubricant TBN level (as measured by ASTM D4739) is maintained with a sulfonate additive, which may be a blend of neutral, underbased, or overbased sulfonate detergents, preferably overbased magnesium and / or calcium sulfonate detergents. In some embodiments, preferred lubricant TBN levels (as measured by ASTM D4739) are at least about 4 mg KOH / g, at least about 5 mg KOH / g, at least about 7 mg KOH / g, or at least about 8 mg KOH / g; lubricant TBN levels (as measured by ASTM D4739) can be about 15 mg KOH / g or less, about 12 mg KOH / g or less, about 10 mg KOH / g or less, or about 9 mg KOH / g or less. ASTM D4739 generally evaluates the impact of detergent additives on lubricant TBN levels. In other approaches, lubricant TBN levels can be about 15 mg KOH / g or less, as measured by ASTM D2896; in other approaches, they can be about 10 mg KOH / g or less, and can be about 6 mg KOH / g or more, about 7 mg KOH / g or more, or about 8 mg KOH / g or more, as measured by ASTM D2896. ASTM D2896 generally evaluates the impact of all sources of base number in a fluid, including additives such as detergents, dispersants, antiwear agents, antioxidants, etc. In embodiments, the detergent systems herein generally comprise one or more alkali or alkali metal salts of sulfonates, with small amounts, residual levels, or no other detergent additives such as phenates, calixarates, salixarates, salicylates, carboxylic acids, sulfurized derivatives thereof, or combinations thereof, so long as the TBN level and metal content are maintained within the desired ranges found to be beneficial when combined with the selected base stocks discussed further below.

[0015] Suitable detergents and methods for their preparation are described in more detail in numerous patent publications, such as U.S. Patent No. 7,732,390 and the references cited therein, which are incorporated herein by reference. The lubricant compositions herein may contain from about 0.1 to about 5 weight percent of individual and / or total detergent additives, in another approach from about 0.15 to about 3 weight percent, and in yet another approach from about 0.15 to 2.6 weight percent of individual and / or total detergent additives, so long as the detergent additives satisfy the sulfonate amount and other relationships described herein.

[0016] As noted above, in some approaches, the detergent system provides a selected amount of sulfonate additive and TBN level along with a certain amount of detergent metal (magnesium and / or calcium, preferably magnesium only). For example, the detergent system herein may provide an amount of total detergent metal greater than about 1000 ppm total metal, based on the total lubricating composition, or in other approaches, from about 1000 ppm to about 5000 ppm total metal, from about 1200 ppm to about 3500 ppm total metal, or from about 1300 to about 2500 ppm total metal. In other approaches, the detergent metal is calcium, sodium, and / or magnesium, preferably calcium and / or magnesium provided by sulfonates, and more preferably calcium, sodium, and / or magnesium sulfonates only. Most preferably, the metal is calcium, magnesium, or a combination thereof. In some embodiments, the detergent metal is preferably magnesium only, provided by an overbased magnesium sulfonate detergent.

[0017] Generally, suitable detergents in the system may include petroleum sulfonic acids, long-chain mono- or di-alkylaryl sulfonic acids in which the aryl groups are benzyl, tolyl, and xylyl, and / or linear or branched alkali or alkaline earth metal salts of various phenates or phenate derivatives, such as calcium, sodium, or magnesium. Examples of suitable detergents include the following detergents, in addition to the required sulfonate, metal, and / or TBN levels: calcium phenates, calcium sulfur-containing phenates, calcium sulfonates, calcium calixarates, calcium salixarates, calcium salicylates, calcium carboxylic acids, calcium phosphates, calcium mono- and / or di-thiophosphates, calcium alkylphenols, calcium sulfur-bound alkylphenol compounds, calcium methylene-bridged phenols, magnesium phenates, magnesium sulfur-containing phenates, magnesium sulfonates, magnesium calixarates, magnesium salixarates, magnesium salicyl ... and overbased variations of sodium carboxylate, magnesium carboxylic acid, magnesium phosphate, magnesium mono- and / or di-thiophosphate, magnesium alkyl phenol, magnesium sulfur-linked alkyl phenol compound, magnesium methylene bridged phenol, sodium phenate, sodium sulfur-containing phenate, sodium sulfonate, sodium calixarate, sodium salixarate, sodium salicylate, sodium carboxylic acid, sodium phosphate, sodium mono- and / or di-thiophosphate, sodium alkyl phenol, sodium sulfur-linked alkyl phenol compound, or sodium methylene bridged phenol.

[0018] The detergent additive may be neutral, underbased, or overbased, preferably an overbased detergent, meeting the minimum detergent TBN number set forth above, as needed. As will be appreciated, overbased detergent additives are well known in the art and may be alkali or alkaline earth metal overbased detergent additives. Such detergent additives may be prepared by reacting a metal oxide or metal hydroxide with a base material and carbon dioxide gas. The base material is typically an acid, such as an aliphatic-substituted sulfonic acid, aliphatic-substituted carboxylic acid, or aliphatic-substituted phenol.

[0019] The term "overbased" refers to metal salts in which the amount of metal present exceeds the stoichiometric amount, such as metal salts of sulfonates, carboxylates, salicylates, and / or phenates. 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 MR is 1, while in overbased salts, the MR is greater than 1. They are commonly referred to as overbased, highly based, or superbased salts and can be salts of organic sulfur acids, carboxylic acids, or phenols.

[0020] As used herein, the term "TBN" is used to represent the total base number in "mg KOH / g" as measured for a lubricant as provided by the detergent system herein by the method of ASTM D4739. The detergent may be neutral or overbased, and as noted above, is an overbased detergent. For example, a neutral detergent may have a total base number (TBN) of up to about 200 mg KOH / gram. In another example, the overbased detergent of the lubricating oil composition herein may have a total base number (TBN) of about 200 mg KOH / gram or more, or about 250 mg KOH / gram or more, or about 350 mg KOH / gram or more, or about 375 mg KOH / gram or more, or about 400 mg KOH / gram or more. The overbased detergent may have a metal to substrate ratio of 1.1:1 or less, or 2:1 or less, or 4:1 or less, or 5:1 or less, or 7:1 or less, or 10:1 or less, or 12:1 or less, or 15:1 or less, or 20:1 or less.

[0021] Examples of suitable overbased detergents (so long as the sulfonate, TBN, metal content, and other relationships described herein are satisfied) 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 dithiophosphates, overbased calcium alkylphenols, and overbased calcium sulfur-bound alkylphenol compounds. overbased magnesium carboxylic acids, overbased magnesium phosphates, overbased magnesium mono- and / or dithiophosphates, overbased magnesium alkylphenols, overbased magnesium sulfur-linked alkylphenol compounds, or overbased magnesium methylene-bridged phenols.

[0022] Optionally, when a low-based or neutral detergent is incorporated into the detergent system, the low-based or neutral detergent generally has a TBN of up to 175 mg KOH / g, up to 150 mg KOH / g, up to 100 mg KOH / g, or up to 50 mg KOH / g. The low-based / neutral detergent may include a calcium- or magnesium-containing detergent. Examples of suitable low-based / neutral detergents include, but are not limited to, calcium sulfonate, calcium phenate, calcium salicylate, magnesium sulfonate, magnesium phenate, and / or magnesium salicylate (as long as the sulfonate soap and other relationships described herein are satisfied).

[0023] In some embodiments, the detergent additives used in the lubricants herein include at least an overbased calcium sulfonate, an overbased sodium sulfonate, and / or an overbased magnesium sulfonate, each having a total base number of 150 to 400, or in other approaches, from about 200 to about 350. In other embodiments, the detergents herein are overbased calcium sulfonate and / or overbased magnesium sulfonate, and most preferably, only overbased magnesium sulfonate. The TBN values ​​above reflect the values ​​of the finished detergent components diluted in the base oil.

[0024] In other embodiments, the TBN of the detergents herein may reflect the neat or undiluted version of the detergent component. For example, the fluids herein may include an overbased calcium or sodium sulfonate as an undiluted additive having a TBN of about 300 to about 450, or in other approaches about 380 to about 420, and / or an overbased magnesium sulfonate as an undiluted additive having a TBN of about 500 to about 700, or in other approaches about 600 to about 700.

[0025] More specifically, the detergent systems herein include overbased calcium sulfonate and / or overbased magnesium sulfonate to achieve a detergent TBN of at least about 4 mg KOH / g, at least about 5 mg KOH / g, or at least about 6 mg KOH / g, as measured by ASTM D4739, and the detergent TBM can be about 15 mg KOH / g or less, about 12 mg KOH / g or less, or about 10 mg KOH / g or less. Preferably, the detergent systems herein also provide at least one of calcium, magnesium, or a combination thereof, most preferably magnesium only, in an amount ranging from about 1000 to about 3500 ppm magnesium, from about 1100 ppm to about 3000 ppm, from about 1200 ppm to about 2000 ppm magnesium, or from 1300 ppm to about 1500 ppm magnesium.

[0026] The detergent systems herein have a selected level of sulfonate soap content, particularly at least about 75 percent sulfonate soap, or alternatively at least about 80 percent sulfonate soap, at least about 85 percent sulfonate soap, at least about 90 percent sulfonate soap, at least about 95 percent sulfonate soap, at least about 98 percent sulfonate soap, at least about 99 percent sulfonate soap, or about 100 percent sulfonate soap (or any range therebetween).

[0027] In other approaches, the detergent systems herein have a selected weight ratio of sulfonate soap to phenate soap of about 75:25 or greater, about 80:20 or greater, about 85:15 or greater, about 90:10 or greater, or even about 95:5 or greater (greater in this ratio context means more sulfonate soap relative to phenate soap). Preferably, the detergent systems herein contain only residual levels, if any, of phenate soap, salicylate soap, calixarate soap, or soaps other than sulfonates.

[0028] Soap content generally refers to the amount of neutral organic acid salts and reflects the cleaning ability or cleaning power of the detergent and its ability to lift dirt. The soap content of a lubricant can be determined by ASTM D3712. Further discussion regarding the determination of soap content can be found in the relevant portions of FUELS AND LUBRICANTS HANDBOOK, TECHNOLOGY, PROPERTIES, PERFORMANCE, AND TESTING, George Totten, editor, ASTM International, 2003, which are incorporated herein by reference.

[0029] Dispersants The lubricating compositions herein also contain one or more optional dispersants, preferably higher molecular weight dispersants. Dispersants are often known as ashless dispersants because they contain no ash-forming metals prior to incorporation into the lubricant composition and because they typically do not contribute any ash upon addition to the lubricant. Ashless dispersants are characterized by a polar group attached to a relatively high molecular weight hydrocarbon chain. Typical ashless dispersants include N-substituted long-chain alkenyl succinimides. Examples of suitable N-substituted long-chain alkenyl succinimides for the lubricants herein include polyisobutylene succinimide dispersants in which the number average molecular weight of the polyisobutylene substituent is in the range of about 1,600 to about 50,000, or about 5,000, or about 3,000, or about 2,500, or about 2,200, as measured by GPC. Succinimide dispersants and their preparation are disclosed, for example, in U.S. Patent Nos. 7,897,696 and 4,234,435, which are incorporated herein by reference. The alkenyl substituents can be prepared from polymerizable monomers containing from about 2 to about 16, or from about 2 to about 8, or from about 2 to about 6 carbon atoms. Succinimide dispersants are typically imides formed from polyamines, typically poly(ethyleneamines).

[0030] In some approaches, preferred amines for dispersants can be selected from polyamines and hydroxylamines. Examples of polyamines that can be used include, but are not limited to, diethylenetriamine (DETA), triethylenetetramine (TETA), tetraethylenepentamine (TEPA), and higher homologues such as pentaethylamine hexamine (PEHA). In some approaches, so-called heavy polyamines can be used, which 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.

[0031] In some embodiments, when included, polyisobutylene (PIB) is a preferred reactant for forming the dispersant and may have a terminal double bond content of greater than 50 mol%, greater than 60 mol%, greater than 70 mol%, greater than 80 mol%, or greater than 90 mol%. Such PIB is also referred to as highly reactive PIB ("HR-PIB"). HR-PIB having a number average molecular weight in the range of about 800 to about 5000 as determined by GPC is suitable for use in embodiments of the present disclosure. Conventional PIB typically has a terminal double bond content of less than 50 mol%, less than 40 mol%, less than 30 mol%, less than 20 mol%, or less than 10 mol%.

[0032] In some approaches, HR-PIB having a number-average molecular weight ranging from about 1,600 to about 3,000, 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. Pat. Nos. 4,152,499 and 5,739,355. When used in the aforementioned thermal ene reaction, HR-PIB can result in higher conversion rates and less precipitate formation in the reaction due to its increased reactivity. A suitable method is described in U.S. Pat. No. 7,897,696. In one embodiment, the present disclosure further includes at least one dispersant derived from polyisobutylene succinic anhydride ("PIBSA"). The PIBSA can have an average of about 1.0 to about 2.0 succinic acid moieties per polymer.

[0033] In some approaches, the dispersants in the lubricants herein may optionally be post-treated by conventional methods by reaction with any of a variety of agents. Suitable post-treatment agents include boron, urea, thiourea, dimercaptothiadiazole, carbon disulfide, aldehydes, ketones, carboxylic acids, hydrocarbon-substituted succinic anhydrides, maleic anhydride, nitriles, epoxides, carbonates, cyclic carbonates, hindered phenol esters, and phosphorus compounds. (See, for example, U.S. Pat. Nos. 7,645,726, 7,214,649, 8,048,831, and 5,241,003, all of which are incorporated herein by reference in their entireties.)

[0034] The boron compounds used as post-treatment reagents can be selected from boron oxide, boron halides, boric acid, and esters of boric acid in amounts to provide from about 0.1 atomic percentage of boron per mole of nitrogen composition to about 20 atomic percentages of boron for each atomic percentage of nitrogen used. In some approaches, dispersants post-treated with boron can contain from about 0.05 weight percent to about 2.0 weight percent, or in other approaches, from about 0.05 weight percent to about 0.7 weight percent boron, based on the total weight of the borate dispersant. In other approaches, the dispersants herein are not post-treated with a boron compound, and the fluid has less than about 10 ppm boron, less than about 5 ppm boron, or preferably no boron.

[0035] In another approach, carboxylic acids can also be used as post-treating reagents and can be saturated or unsaturated mono-, di-, or poly-carboxylic acids. Examples of carboxylic acids include, but are not limited to, maleic acid, fumaric acid, succinic acid, and naphthalic diacids (e.g., 1,8-naphthalic diacid). Anhydrides can also be used as post-treating reagents and can be selected from the group consisting of mono-unsaturated anhydrides (e.g., maleic anhydride), alkyl- or alkylene-substituted cyclic anhydrides (e.g., succinic anhydride or glutamic anhydride), and aromatic carboxylic anhydrides (including naphthalic anhydrides, e.g., 1,8-naphthalic anhydride).

[0036] In one embodiment, the process for post-treating a dispersant includes first forming a succinimide product as described above, and then further reacting the succinimide product with a post-treating agent, such as a boron compound, such as boric acid. In some cases, the dispersants herein may be post-treated with more than one post-treating agent. For example, a dispersant may be post-treated with a boron compound, such as boric acid, and also with an anhydride, such as maleic anhydride and / or 1,8-naphthalic anhydride.

[0037] In another approach, the dispersant may be used in the lubricating composition in an amount of from about 0.1 weight percent to about 15 weight percent, or from about 0.1 weight percent to about 10 weight percent, or from about 0.1 weight percent to about 8 weight percent, or from about 1 weight percent to about 10 weight percent, or from about 1 weight percent to about 8 weight percent, or from about 1 weight percent to about 6 weight percent, based on the final weight of the lubricating oil composition. The dispersant may provide at least about 400 ppm nitrogen and up to about 1,500 ppm nitrogen.

[0038] Oil-soluble molybdenum compounds In some approaches, the engine lubricating oil compositions herein may optionally contain 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, 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.

[0039] In one embodiment, the oil-soluble molybdenum compound can be selected from the group consisting of molybdenum dithiocarbamate, molybdenum dialkyldithiophosphate, sulfur-free organo-molybdenum complexes of organic amides, and mixtures thereof. In one embodiment, the oil-soluble molybdenum compound can be molybdenum dithiocarbamate. Exemplary sulfur-free organo-molybdenum complexes of organic amides are disclosed in U.S. Patent No. 5,137,647.

[0040] In one approach or embodiment, suitable molybdenum dithiocarbamates can be represented by the formula:

[0041] [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 20 a 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 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 18 Included are dialkyl or diaryl dithiocarbamates or alkyl-aryl dithiocarbamates such as dibutyl-, diamyl-di-(2-ethylhexyl)-, dilauryl-, dioleyl-, and dicyclohexyl-dithiocarbamate.

[0042] 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. Nos. 37,363 (E1), 38,929 (E1), and 40,595 (E1), the entire contents of which are incorporated herein by reference.

[0043] In one embodiment, when included in the formulation, the molybdenum compound may be present in the engine lubricating oil composition in an amount providing up to about 800 ppm molybdenum, or from about 5 ppm to 800 ppm molybdenum. By way of further example, the molybdenum compound may be present in an amount providing from about 30 to about 700 ppm molybdenum, or from about 50 to 650 ppm molybdenum, or from about 100 to 625 ppm molybdenum. In another approach, the formulations herein may be devoid of molybdenum dialkyldithiocarbamate; in this context, the formulation may have about 0.05 weight percent or less of molybdenum dialkyldithiocarbamate, about 0.01 weight percent or less of molybdenum dialkyldithiocarbamate, or may have no molybdenum dialkyldithiocarbamate at all.

[0044] Poly(meth)acrylate copolymer In another approach or embodiment, the engine lubricating oil compositions herein may comprise a selected poly(meth)acrylate copolymer. In some approaches, the selected poly(meth)acrylate copolymer is configured to achieve a selected viscosity index for the lubricants herein; in other approaches, the selected poly(meth)acrylate copolymer may also have a specific molecular weight and / or specific pendant side group or arm, which may be a blend of one or more distinct molecular weight pendant arms, such as low-, medium-, and / or high-molecular weight pendant hydrocarbyl groups on the ester moieties of the (meth)acrylate monomer units forming the copolymer. In embodiments, the lubricants herein may comprise up to about 20 weight percent poly(meth)acrylate copolymer; in other approaches, it may be from about 3 to about 18 weight percent, from about 3 to about 16 weight percent, from about 3 to about 10 weight percent, or from about 3 to about 8 weight percent. Polymer treat rates are provided on a liquid (diluted with base oil) basis unless otherwise indicated.

[0045] In one exemplary approach, the poly(meth)acrylate copolymer may have the structure of Formula I below, where z is an integer sufficient to achieve a weight average molecular weight of from about 20,000 to about 1,500,000 (in other approaches, from about 100,000 to about 500,000, or from about 200,000 to about 450,000, or from about 200,000 to about 300,000), where R is hydrogen when the monomer unit is an acrylate or a methyl group when the monomer unit is a methacrylate, and R′ is a linear or branched hydrocarbyl group sized to achieve an arm molecular weight as described herein.

[0046] [ka] Lubricants comprising the poly(meth)acrylate copolymers herein may have a viscosity index (as determined by ASTM D2270) of from about 130 to about 300, or alternatively from about 150 to about 250, or from about 150 to about 200, or more preferably from about 180 to about 200. The poly(meth)acrylate copolymers described herein may have different (meth)acrylate monomer units randomly spaced throughout the polymer, as described below.

[0047] Suitable monomers or reactants for forming the copolymers for the unique motorcycle fluids herein include at least one selected from (1) (meth)acrylate monomers having a low to medium weight average molecular weight hydrocarbyl group in the ester portion of up to about 700, or preferably from about 100 to about 700 or from about 400 to about 700, and, optionally, (2) (meth)acrylate monomers having a high weight average molecular weight hydrocarbyl group in the ester portion of the monomer of from about 6,000 to about 10,000 or from about 6,000 to about 8,000, and, optionally, a blend of at least two different (meth)acrylate monomers or reactants. As used herein, "(meth)acrylate" refers to both the methacrylate and / or acrylate monomer or monomer unit (or mixture). Also, as used herein, the molecular weight of the hydrocarbyl group of the ester in the monomer includes the hydrocarbyl chain as well as the ester oxygen, but not the carbonyl group.

[0048] Typically, the formed or resulting poly(meth)acrylate copolymer has an amount of monomers effective to achieve a total copolymer number average molecular weight of about 20,000 or greater, and in some cases about 250,000 or less, such as about 140,000 to about 240,000 or about 140,000 to about 200,000. The poly(meth)acrylate copolymer may also have a polydispersity index (Mw / Mn) of about 2.8 or less, or about 2.6 or less, and in other approaches, in the range of about 1.8 to about 2.6. In still other approaches, the copolymers herein may have two differently sized pendant arms, and in such situations, have a molecular weight ratio between the higher molecular weight arm and the lower molecular weight arm of about 10:1 to about 50:1, in other approaches, about 11:1 to about 30:1, and in still other approaches, about 12:1 to about 25:1. In other cases, the copolymers herein have a molecular weight ratio between the higher molecular weight arms and the lower molecular weight arms of from about 1.5:1 to about 25:1, and in other approaches, from about 1.5:1 to about 16:1.

[0049] In an approach or embodiment, the poly(meth)acrylate copolymers herein comprise the reaction product in the form of a linear, random copolymer of selected amounts of pendant low to medium and / or (optionally) high molecular weight hydrocarbyl (meth)acrylate monomers. These monomers and monomer units are further described below and contain both linear and / or branched hydrocarbyl groups on each ester chain, forming, in some embodiments, comb copolymers having pendant arms of at least one, and optionally at least two, distinct molecular weights.

[0050] In an embodiment or approach, the low molecular weight hydrocarbyl (meth)acrylate units or monomers are derived from alkyl (meth)acrylates having linear or branched hydrocarbyl groups in the ester portion, preferably linear or branched alkyl groups in the ester portion, having a total carbon chain length in the monomer ester portion (including any branching) of 6 to 20 carbons, and preferably 12 to 16 carbons. An exemplary low molecular weight hydrocarbyl (meth)acrylate monomer may be lauryl (meth)acrylate, which may include a blend of (meth)acrylate monomers or monomer units having alkyl chain lengths in the range of C12 to C16, specifically alkyl chains of 12, 14, and 16 carbons, of which C12 alkyl (meth)acrylate is in the majority. In another embodiment or approach, the low or medium molecular weight hydrocarbyl (meth)acrylate units are derived from hydrocarbyl (meth)acrylate monomers having hydrocarbyl groups or total hydrocarbyl ester length (including any branching) and have a weight average molecular weight of at least about 500 and up to about 700. These molecular weight chains can be derived from macromonomers of olefins or polymeric alcohols, optionally esterified with (meth)acrylic acid. The macromonomers can be derived from alkenes or alkadiene, including ethylene, propylene, butene, butadiene, isoprene, or combinations thereof, and have a molecular weight of about 700 or less, such as from about 500 to about 700.

[0051] In yet another embodiment or approach, the optional high molecular weight hydrocarbyl (meth)acrylate units, or monomers, are derived from hydrocarbyl (meth)acrylate monomers having hydrocarbyl groups or total hydrocarbyl ester lengths (including any branching) with a weight average molecular weight of at least about 6,000 and up to about 10,000, or from about 6,000 to about 8,000. These high molecular weight chains can be derived from macromonomers of polymeric alcohols esterified with (meth)acrylic acid. The macromonomers can be derived from alkenes or alkadiene, including ethylene, propylene, butene, butadiene, isoprene, or combinations thereof, and have a molecular weight of about 10,000 or less, or about 8,000 or less, such as about 500 to about 10,000, or about 6,000 to about 8,000.

[0052] In optional embodiments, the poly(meth)acrylate copolymers herein may also include other optional monomers and monomer units, including, for example, hydroxyalkyl (meth)acrylates and / or various dispersant monomers and monomer units. The poly(meth)acrylate copolymers herein may also optionally be functionalized with one or more dispersant monomers or monomer units; however, it is preferred that the poly(meth)acrylate copolymers are non-dispersant polymers and thus do not include or lack dispersant moieties as referred to herein.

[0053] In one optional approach, the dispersant monomer or monomer unit can be a nitrogen-containing monomer or unit thereof. Such monomers, when used, can impart dispersant functionality to the polymer. In some approaches, the nitrogen-containing monomer can be a (meth)acrylic monomer such as a methacrylate or methacrylamide. In some approaches, the attachment of the nitrogen-containing moiety to the acrylic moiety can be via a nitrogen atom or alternatively an oxygen atom, in which case the nitrogen of the monomer will be located elsewhere in the monomer. The nitrogen-containing monomer can be other than a (meth)acrylic monomer, such as a vinyl-substituted nitrogen heterocyclic monomer and a vinyl-substituted amine. Nitrogen-containing monomers include, for example, those in U.S. Pat. No. 6,331,603. Other suitable dispersant monomers include, but are not limited to, dialkylaminoalkyl acrylates, dialkylaminoalkyl (meth)acrylates, dialkylaminoalkyl acrylamides, dialkylaminoalkyl methacrylamides, N-tertiary alkyl acrylamides, and N-tertiary alkyl methacrylamides, where the alkyl or aminoalkyl groups can independently contain 1 to 8 carbon atoms. For example, the dispersant monomer can be dimethylaminoethyl (meth)acrylate. The nitrogen-containing monomer can be, for example, t-butylacrylamide, dimethylaminopropyl (meth)acrylamide, dimethylaminoethyl methacrylamide, N-vinylpyrrolidone, N-vinylimidazole, or N-vinylcaprolactam. It may also be a (meth)acrylamide based on any of the aromatic amines disclosed in WO 2005 / 087821, including 4-phenylazoaniline, 4-aminodiphenylamine, 2-aminobenzimidazole, 3-nitroaniline, 4-(4-nitrophenylazo)aniline, N-(4-amino-5-methoxy-2-methyl-phenyl)-benzamide, N-(4-amino-2,5-dimethoxy-phenyl)-benzamide, N-(4-amino-2,5-diethoxy-phenyl)-benzamide, N-(4-amino-phenyl)-benzamide, 4-amino-2-hydroxy-benzoic acid.

[0054] The (meth)acrylate copolymers of the present disclosure are typically synthesized to have a number average molecular weight of about 20,000 or more, or in other approaches, about 250,000 or less, or about 200,000 or less. Suitable ranges of number average molecular weight include about 140,000 to about 250,000, and in other approaches, about 150,000 to about 200,000. Such copolymers herein typically have a polydispersity index ranging from about 1 to about 4, and in other approaches, about 1.2 to about 3.5, and in yet other approaches, about 1.5 to about 3, and in yet other approaches, about 1.6 to about 2.5.

[0055] (Meth)acrylate copolymers can be prepared by any suitable conventional or controlled free radical polymerization technique. Examples include conventional free radical polymerization (FRP), reversible addition-fragmentation chain transfer (RAFT), atom transfer radial polymerization (ATRP), and other controlled types of polymerization known in the art. Polymerization procedures are known to those skilled in the art and include, for example, the use of common polymerization initiators (such as Vazo™ 67 (2,2′-azobis(2-methylbutyronitrile)), chain transfer agents (such as dodecyl mercaptan) when using conventional FRP, or RAFT agents (such as 4-cyano-4-[(dodecylsulfanylthiocarbonyl)sulfanyl]pentanoic acid) when using RAFT polymerization. Other initiators, chain transfer agents, RAFT agents, ATRP catalysts, and initiator systems can be used as known in the art, depending on the polymerization method selected, as needed for a particular application.

[0056] Base oil or base oil blend: The base oil used in the lubricating compositions herein can be an oil of lubricating viscosity and can be selected from any of API Groups I to 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.

[0057] [Table 1]

[0058] Group I, Group II, and Group III are mineral oil process feedstocks. Group IV base oils contain true synthetic molecular species produced by the polymerization of olefinically unsaturated hydrocarbons. Many Group V base oils are also true synthetic products and may include diesters, polyol esters, polyalkylene glycols, alkylated aromatics, polyphosphate esters, polyvinyl ethers, and / or polyphenyl ethers, but may also be natural oils such as vegetable oils. Group III base oils are derived from mineral oils, but it should be noted that the rigorous processing these fluids undergo makes their physical properties very similar to some true synthetic oils, such as PAOs. Therefore, oils derived from Group III base oils may be referred to in industry as synthetic fluids. Group II+ may include high viscosity index Group II.

[0059] 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.

[0060] 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 processed in 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.

[0061] Re-refined oils are also known as reclaimed or reprocessed oils. These oils are obtained using the same or similar processes as refined oils. Often, these oils are further processed by techniques directed to the removal of spent additives and oil breakdown products.

[0062] Mineral oils may include oils obtained by drilling, or from plants and animals, or any mixture thereof. For example, such oils may include, but are not limited to, castor oil, lard oil, olive oil, peanut oil, corn oil, soybean oil, and linseed oil, as well as mineral lubricating oils, such as liquid petroleum oils and solvent- or acid-treated mineral lubricating oils of the paraffinic, naphthenic, or mixed paraffinic-naphthenic types. Such oils may be partially or fully hydrogenated, if desired. Oils derived from coal or shale may also be useful.

[0063] Useful synthetic lubricating oils may include hydrocarbon oils such as polymerized, oligomerized, or interpolymerized olefins (e.g., polybutylene, polypropylene, propylene-isobutylene copolymers); poly(1-hexene), poly(1-octene), trimers or oligomers of 1-decene, such as poly(1-decene) (such materials are often referred to as α-olefins), and mixtures thereof; alkyl-benzenes (e.g., dodecylbenzene, tetradecylbenzene, dinonylbenzene, di-(2-ethylhexyl)-benzene); polyphenyls (e.g., biphenyl, terphenyl, alkylated polyphenyls); diphenylalkanes, alkylated diphenylalkanes, alkylated diphenyl ethers, and alkylated diphenyl sulfides, as well as their derivatives, analogs, and homologs, or mixtures thereof. Polyalphaolefins are typically hydrogenated materials.

[0064] Other synthetic lubricating oils include polyol esters, diesters, liquid esters of phosphorus-containing acids (e.g., tricresyl phosphate, trioctyl phosphate, and diethyl ester of decane phosphonic acid), or polymeric tetrahydrofurans. Synthetic oils can be produced by the Fischer-Tropsch reaction and are typically hydroisomerized Fischer-Tropsch hydrocarbons or waxes. In one embodiment, the oils can be prepared by the Fischer-Tropsch gas-to-liquid synthesis procedure, as well as other gas-to-liquid oils.

[0065] 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.

[0066] The amount of oil of lubricating viscosity present may be the remainder remaining after subtracting the sum of the amounts of performance additives, including viscosity index improver(s) and / or pour point depressants and / or other top treat additives, from 100% by weight. For example, the oil of lubricating viscosity may be present in the final fluid in a "major amount," such as greater than about 50% by weight, greater than about 60% by weight, greater than about 70% by weight, greater than about 80% by weight, greater than about 85% by weight, or greater than about 90% by weight.

[0067] 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 yet other approaches, and from about 2.5 to about 4.5 cSt in yet other approaches.

[0068] 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 majority amount of a base oil component and minor amounts of detergents and other optional components.

[0069] Engine lubricating oil composition The fully formulated engine oil compositions herein, comprising the selected base oil blend, detergent system, optional oil-soluble molybdenum compound, and selected poly(meth)acrylate copolymer as described above, have a configuration such that the engine lubricating oil composition has one or more of the following: (i) a NOACK volatility of about 13 percent or less (preferably, from about 12 to about 10 percent) as measured in accordance with CEC L-40-63 and / or ASTM D5800; (ii) a total base number (TBN) of about 10 mg KOH / g or less (preferably, from about 7 to about 9 mg KOH / g per ASTM D2896) and / or a total base number (TBN) of at least about 4 mg KOH / g (preferably, from about 4 to about 7 mg KOH / g per ASTM D4739) as measured in accordance with ASTM D4739; (iii) a NOACK volatility of about 13 percent or less (preferably, from about 12 to about 10 percent) as measured in accordance with CEC L-40-63 and / or ASTM D5800; (iv) a calculated sulfated ash (SASH) of about 0.8 weight percent or less (preferably, about 0.5 weight percent to about 0.8 weight percent) measured in accordance with ASTM D874, (iv) a CCS viscosity at −35° C. of about 6200 mPas or less (preferably, about 3000 to about 5800 mPas) measured in accordance with ASTM D5292, and / or (v) a combination thereof. When an engine lubricating oil composition has such a configuration and meets such performance parameters, as described above, the engine lubricating oil composition meets or exceeds the lubricant durability performance specified in the CECL-117-20 (VW TDi3) Piston Cleanliness Test, preferably a piston cleanliness rating of at least about 53 merit, at least about 54 merit, at least about 55 merit, at least about 56 merit, at least about 57 merit, at least about 58 merit, or at least about 59 merit, and the engine lubricating oil composition also has a positive fuel economy increase as measured in accordance with JASO M 366, preferably an improvement in fuel economy as measured in accordance with JASO M 366 of at least about 0.5%, at least about 0.6%, at least about 0.7%, or at least about 0.8%.

[0070] Optional Additives: The lubricating oil compositions herein may also contain a number of optional additives in combination with the detergent system, sulfurized additives, and borated detergents as needed to meet performance criteria, which optional additives are described in the following paragraphs.

[0071] Other Dispersants: The lubricating oil composition may optionally contain one or more other dispersants or mixtures thereof. Dispersants are often referred to as ashless dispersants because they do not contain ash-forming metals prior to 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).

[0072] Preferred amines are selected from polyamines and hydroxylamines. Examples of polyamines that can be used include, but are not limited to, diethylenetriamine (DETA), triethylenetetramine (TETA), tetraethylenepentamine (TEPA), and higher homologs such as pentaethylaminehexamine (PEHA).

[0073] Suitable heavy polyamines are mixtures of polyalkylene-polyamines containing oligomers with six or more nitrogen atoms, two or more primary amines per molecule, and more extensive branching than conventional polyamine mixtures, although they contain small amounts of lower polyamine oligomers such as TEPA and PEHA (pentaethylenehexamine). Heavy polyamines preferably include polyamine oligomers containing seven or more nitrogen atoms per molecule and two or more primary amines per molecule. Heavy polyamines contain greater than 28% by weight (e.g., greater than 32% by weight) of total nitrogen and an equivalent weight of 120 to 160 g of primary amine groups per equivalent.

[0074] In some approaches, suitable polyamines are commonly known as PAMs and contain a mixture of ethyleneamines, with TEPA and pentaethylenehexamine (PEHA) being the major portion of the polyamine, usually less than about 80%.

[0075] Typically, PAM has 8.7-8.9 milliequivalents of primary amine per gram (115-112 milliequivalents per equivalent of primary amine) and a total nitrogen content of about 33-34% by weight. Heavier cuts of PAM oligomers that are substantially free of TEPA and contain only small amounts of PEHA, but contain primarily oligomers with more than six nitrogen atoms and more extensive branching, may produce dispersants with improved dispersancy.

[0076] In some embodiments, the present disclosure further comprises at least one polyisobutylene succinimide dispersant derived from polyisobutylene having a number average molecular weight ranging from about 350 to about 50,000, or from about 5,000, or from about 3,000, as determined by GPC. The polyisobutylene succinimide may be used alone or in combination with other dispersants.

[0077] In some embodiments, when polyisobutylene is included, the polyisobutylene may have a terminal double bond content of greater than 50 mol%, greater than 60 mol%, greater than 70 mol%, greater than 80 mol%, or greater than 90 mol%. Such PIB is also referred to as highly reactive PIB ("HR-PIB"). HR-PIB having a number average molecular weight in the range of about 800 to about 5000 as determined by GPC is suitable for use in embodiments of the present disclosure. Conventional PIB typically has a terminal double bond content of less than 50 mol%, less than 40 mol%, less than 30 mol%, less than 20 mol%, or less than 10 mol%.

[0078] HR-PIB having a number-average molecular weight ranging from about 900 to about 3000, as determined by GPC, may be suitable. Such HR-PIB is commercially available or can be synthesized by polymerization of isobutene in the presence of a non-chlorinated catalyst, such as boron trifluoride, as described in U.S. Patent No. 4,152,499 to Boerzel et al. and U.S. Patent No. 5,739,355 to Gateau et al. When HR-PIB is used in the thermal ene reaction, it can result in higher conversion and less precipitate formation during the reaction due to increased reactivity. A suitable method is described in U.S. Patent No. 7,897,696.

[0079] 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.

[0080] 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.

[0081] Polyolefin conversion is calculated from the % active ingredient using the formula in columns 5 and 6 of US Pat. No. 5,334,321.

[0082] Unless otherwise specified, all percentages are by weight and all molecular weights are number average molecular weights as determined by gel permeation chromatography (GPC) using commercially available polystyrene standards (having number average molecular weights of 180 to about 18,000) as calibration standards.

[0083] In one embodiment, the dispersant may be derived from a polyalphaolefin (PAO) succinic anhydride. In one embodiment, the dispersant may be derived from an olefin maleic anhydride copolymer. As an example, the dispersant may be described as poly-PIBSA. In one embodiment, the dispersant may be derived from an anhydride grafted to an ethylene-propylene copolymer.

[0084] 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.

[0085] 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.

[0086] 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.

[0087] In addition to the carbonate and boric acid post-treatments, any of the compounds may be post-treated or further post-treated with a variety of post-treatments designed to improve or impart different properties. Such post-treatments include those summarized in columns 27-29 of U.S. Pat. No. 5,241,003, which is incorporated herein by reference. Such treatments include treatment with inorganic phosphoric acids or anhydrides (e.g., U.S. Pat. Nos. 3,403,102 and 4,648,980); organic phosphorus compounds (e.g., U.S. Pat. No. 3,502,677); phosphorus pentasulfide; boron compounds as already mentioned above (e.g., U.S. Pat. Nos. 3,178,663 and 4,652,387); carboxylic acids, polycarboxylic acids, anhydrides, and / or acid halides (e.g., U.S. Pat. Nos. 3,708,522 and 4,909,910). 48,386); epoxide polyepoxides or thioepoxides (e.g., U.S. Pat. Nos. 3,859,318 and 5,026,495); aldehydes or ketones (e.g., U.S. Pat. No. 3,458,530); carbon disulfide (e.g., U.S. Pat. No. 3,256,185); glycidol (e.g., U.S. Pat. No. 4,617,137); urea, thiourea, or guanidine (e.g., U.S. Pat. No. 3,312,61 Nos. 9, 3,865,813, and British Patent No. 1,065,595; organic sulfonic acids (e.g., U.S. Pat. No. 3,189,544 and British Patent No. 2,140,811); alkenyl cyanides (e.g., U.S. Pat. Nos. 3,278,550 and 3,366,569); diketene (e.g., U.S. Pat. No. 3,546,243); diisocyanates (e.g., U.S. Pat. No. 3,573,205); alkanesulf ...546,243); ton (e.g., U.S. Pat. No. 3,749,695); 1,3-dicarbonyl compounds (e.g., U.S. Pat. No. 4,579,675); sulfates of alkoxylated alcohols or phenols (e.g., U.S. Pat. No. 3,954,639); cyclic lactones (e.g., U.S. Pat. Nos. 4,617,138, 4,645,515, 4,668,246, 4,963,275, and 4,971,711);Cyclic carbonates or thiocarbonates, linear monocarbonates or polycarbonates, or chloroformates (e.g., U.S. Pat. Nos. 4,612,132, 4,647,390, 4,648,886, 4,670,170); nitrogen-containing carboxylic acids (e.g., U.S. Pat. No. 4,971,598 and British Patent No. 2,140,811); hydroxy-protected chlorodicarbonyloxy compounds (e.g., U.S. Pat. No. 4,614,522); lactams, thiolactams, thiolactones, or dithiolactones (e.g., U.S. Pat. Nos. 4,614,522, ... Nos. 4,614,603 and 4,666,460; cyclic carbonates or thiocarbonates, linear monocarbonates or polycarbonates, or chloroformates (e.g., U.S. Pat. Nos. 4,612,132, 4,647,390, 4,646,860, and 4,670,170); nitrogen-containing carboxylic acids (e.g., U.S. Pat. No. 4,971,598 and British Patent No. 2,440,811); hydroxy-protected chlorodicarbonyloxy compounds (e.g., U.S. Pat. No. 4,614,522); lactams, thiocarbonates, and the like. olactams, thiolactones, or dithiolactones (e.g., U.S. Pat. Nos. 4,614,603 and 4,666,460); cyclic carbamates, cyclic thiocarbamates, or cyclic dithiocarbamates (e.g., U.S. Pat. Nos. 4,663,062 and 4,666,459); hydroxyaliphatic carboxylic acids (e.g., U.S. Pat. Nos. 4,482,464, 4,521,318, and 4,713,189); oxidizing agents (e.g., U.S. Pat. No. 4,379,064); combinations of phosphorus pentasulfide and polyalkylene polyamines (e.g., U.S. Pat. Nos. 4,379,064, 4,379,064); , U.S. Pat. No. 3,185,647); combinations of carboxylic acids or aldehydes or ketones and sulfur or sulfur chloride (e.g., U.S. Pat. Nos. 3,390,086, 3,470,098); combinations of hydrazine and carbon disulfide (e.g., U.S. Pat. No. 3,519,564); combinations of aldehydes and phenols (e.g., U.S. Pat. Nos. 3,649,229, 5,030,249, 5,039,307); combinations of aldehydes and O-diesters of dithiophosphoric acids (e.g., U.S. Pat. No. 3,865,740);Combinations of hydroxyaliphatic carboxylic acids and boric acid (e.g., U.S. Pat. No. 4,554,086); combinations of hydroxyaliphatic carboxylic acids followed by formaldehyde and phenol (e.g., U.S. Pat. No. 4,636,322); combinations of hydroxyaliphatic carboxylic acids followed by aliphatic dicarboxylic acids (e.g., U.S. Pat. No. 4,663,064); combinations of formaldehyde and phenol followed by glycolic acid (e.g., U.S. Pat. No. 4,699,724); combinations of hydroxyaliphatic carboxylic acids or oxalic acid followed by a diisocyanate (e.g., U.S. Pat. No. 4,713,191); inorganic acids or anhydrides of phosphorus or a combination of its partial or total sulfur analogue and a boron compound (e.g., U.S. Pat. No. 4,857,214); a combination of an organic diacid, followed by an unsaturated fatty acid, followed by a nitrosoaromatic amine, optionally followed by a boron compound, and then a glycosylation agent (e.g., U.S. Pat. No. 4,973,412); a combination of an aldehyde and a triazole (e.g., U.S. Pat. No. 4,963,278); a combination of an aldehyde and a triazole, followed by a boron compound (e.g., U.S. Pat. No. 4,981,492); a combination of a cyclic lactone and a boron compound (e.g., U.S. Pat. Nos. 4,963,275 and 4,971,711). The above-mentioned patents are incorporated herein in their entirety.

[0088] Suitable dispersants may have a TBN of from about 10 to about 65 mg KOH / g on an oil-free basis, which equates to about 5 to about 30 TBN when measured on a dispersant sample containing about 50% diluent oil. TBN is measured by the method of ASTM D2896.

[0089] In yet another embodiment, the optional dispersant additive may be a hydrocarbyl-substituted succinamide or succinimide dispersant. In some approaches, the hydrocarbyl-substituted succinamide or succinimide dispersant may be derived from a hydrocarbyl-substituted acylating agent reacted with a polyalkylene polyamine, wherein the hydrocarbyl substituent of the succinamide or succinimide dispersant is a linear or branched hydrocarbyl group having a number average molecular weight of about 250 to about 5,000 as determined by GPC using polystyrene as a calibration standard.

[0090] In some approaches, the polyalkylene polyamine used to form the dispersant has the following formula:

[0091] [ka] wherein each R and R' is independently a divalent C1-C6 alkylene linker, and each R1 and R2 is independently hydrogen, a C1-C6 alkyl group, or together with the nitrogen atom to which they are attached form a 5- or 6-membered ring optionally fused to one or more aromatic or non-aromatic rings, and n is an integer from 0 to 8. In another approach, the polyalkylene polyamine is selected from the group consisting of a mixture of polyethylene polyamines having an average of 5 to 7 nitrogen atoms, triethylenetetramine, tetraethylenepentamine, and combinations thereof.

[0092] 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 to about 15 wt. %, or from about 0.1 to about 10 wt. %, or from about 0.1 to about 8 wt. %, or from about 1 to about 10 wt. %, or from about 1 to about 8 wt. %, or from about 1 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.

[0093] 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.

[0094] The hindered phenol antioxidant may contain a secondary butyl group and / or a tertiary butyl group as a steric hindering group. The phenol group may be further substituted with a hydrocarbyl group and / or a bridging group connecting to a second aromatic group. Examples of suitable hindered phenol antioxidants include 2,6-di-tert-butylphenol, 4-methyl-2,6-di-tert-butylphenol, 4-ethyl-2,6-di-tert-butylphenol, 4-propyl-2,6-di-tert-butylphenol, 4-butyl-2,6-di-tert-butylphenol, or 4-dodecyl-2,6-di-tert-butylphenol. In one embodiment, the hindered phenol antioxidant may be an ester, such as Irganox® L-135 available from BASF, or an addition product derived from 2,6-di-tert-butylphenol and an alkyl acrylate. wherein the alkyl group can contain from about 1 to about 18, or from about 2 to about 12, or from about 2 to about 8, or from about 2 to about 6, or about 4 carbon atoms. Another commercially available hindered phenol antioxidant, which can be an ester, can include Ethanox™ 4716, available from Albemarle Corporation.

[0095] Useful antioxidants may include diarylamines and high molecular weight phenols. In one embodiment, the lubricating oil composition may contain a mixture of diarylamines and high molecular weight phenols, such that each antioxidant may be present in an amount sufficient to provide up to about 5 wt. %, based on the final weight of the lubricating oil composition. In one embodiment, the antioxidant may be a mixture of about 0.3 to about 1.5 wt. % diarylamines and about 0.4 to about 2.5 wt. % high molecular weight phenols, based on the final weight of the lubricating oil composition.

[0096] 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.

[0097] 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.

[0098] In another alternative embodiment, the antioxidant composition contains a molybdenum-containing antioxidant in addition to the phenolic and / or aminic antioxidants discussed above. When a combination of these three antioxidants is used, preferably the treat rate ratio of the phenol to the amine to the molybdenum-containing component is (0-3):(0-3):(0-3).

[0099] 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.

[0100] 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 ester(s); 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.

[0101] 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, but the total number of carbon atoms on the alkyl group may be at least 8. In one embodiment, the antiwear agent may include citrate.

[0102] The antiwear agent may be present in ranges including from about 0 to about 15 weight percent, or from about 0.01 to about 10 weight percent, or from about 0.05 to about 5 weight percent, or from about 0.1 to about 3 weight percent of the lubricating oil composition.

[0103] Boron-Containing Compounds: The lubricating oil compositions herein may optionally contain one or more boron-containing compounds. Examples of boron-containing compounds include borate esters, borated fatty amines, borated epoxides, borated detergents, and borated dispersants, such as borated succinimide dispersants, as disclosed in U.S. Patent No. 5,883,057. When present, the boron-containing compounds may be used in an amount sufficient to provide up to about 8 wt. %, from about 0.01 to about 7 wt. %, from about 0.05 to about 5 wt. %, or from about 0.1 to about 3 wt. % of the lubricating oil composition.

[0104] Additional Detergents: The lubricating oil composition may optionally further comprise one or more neutral, low-based, or overbased detergents, and mixtures thereof. Suitable detergent substrates include phenates, sulfur-containing phenates, sulfonates, calixarates, salixarates, salicylates, carboxylic acids, phosphoric acids, mono- and / or di-thiophosphoric acids, alkylphenols, sulfur-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.

[0105] The detergent substrate may be salified with an alkali metal or alkaline earth metal, such as, but not limited to, calcium, magnesium, potassium, sodium, lithium, barium, or mixtures thereof. In some embodiments, the detergent is barium-free. In some embodiments, the detergent may contain trace amounts of other metals, such as magnesium or calcium, in amounts of 50 ppm or less, 40 ppm or less, 30 ppm or less, 20 ppm or less, or 10 ppm or less. Suitable detergents may include alkali metal or alkaline earth metal salts of petroleum sulfonic acids and long-chain mono- or di-alkylaryl sulfonic acids in which the aryl groups are benzyl, tolyl, and xylyl. Examples of suitable detergents include, but are not limited to, calcium phenate, calcium sulfonate, calcium calixarate, calcium salixarate, calcium salicylate, calcium carboxylic acid, calcium phosphate, calcium mono- and / or di-thiophosphate, calcium alkyl phenol, calcium sulfur-bound alkyl phenol compound, calcium methylene bridged phenol, magnesium phenate, magnesium sulfonate, magnesium calixarate, magnesium salixarate, magnesium salicylate, magnesium carboxylic acid, magnesium phosphate, magnesium mono- and / or di-thiophosphate, magnesium alkyl phenol, magnesium sulfur-bound alkyl phenol compound, magnesium methylene bridged phenol, sodium phenate, sodium sulfonate, sodium calixarate, sodium salixarate, sodium salicylate, sodium carboxylic acid, sodium phosphate, sodium mono- and / or di-thiophosphate, sodium alkyl phenol, sodium sulfur-bound alkyl phenol compound, or sodium methylene bridged phenol.

[0106] Overbased detergent additives are well known in the art and can be alkali or alkaline earth metal overbased detergent additives. Such detergent additives can be prepared by reacting a metal oxide or metal hydroxide with a base material and carbon dioxide gas. The base material is typically an acid, such as an aliphatic-substituted sulfonic acid, aliphatic-substituted carboxylic acid, or aliphatic-substituted phenol.

[0107] 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 (MR) is 1, while in overbased salts, the MR is greater than 1. They are commonly referred to as overbased, highly based, or superbased salts and can be salts of organic sulfur acids, carboxylic acids, or phenols.

[0108] 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.

[0109] Examples of suitable overbased detergents include, but are not limited to, overbased calcium phenate, overbased calcium sulfur-containing phenate, overbased calcium sulfonate, overbased calcium calixalate, overbased calcium salixarate, overbased calcium salicylate, overbased calcium carboxylic acid, overbased calcium phosphate, overbased calcium mono- and / or di-thiophosphate, overbased calcium alkylphenol, overbased calcium sulfur-bound alkylphenol compound, overbased calcium methylene-bridged phenol, overbased magnesium phenate, overbased magnesium sulfonate, overbased magnesium calixalate, overbased magnesium salixarate, overbased magnesium salicylate, overbased magnesium carboxylic acid, overbased magnesium phosphate, overbased magnesium mono- and / or di-thiophosphate, overbased magnesium alkylphenol, overbased magnesium sulfur-bound alkylphenol compound, or overbased magnesium methylene-bridged phenol.

[0110] The overbased calcium phenate detergents have a total base number of at least about 150 mg KOH / g, at least about 225 mg KOH / g, at least about 225 to about 400 mg KOH / g, at least about 225 to about 350 mg KOH / g, or about 230 to about 350 mg KOH / g, all measured by the method of ASTM D 2896. When such detergent compositions are formed in an inert diluent, such as a process oil, usually a mineral oil, the total base number reflects the basicity of the entire composition, including the diluent and any other materials (e.g., accelerators, etc.) that may be included in the detergent composition.

[0111] Overbased detergents may have a metal-to-substrate ratio of 1.1:1 or greater, or 2:1 or greater, or 4:1 or greater, or 5:1 or greater, or 7:1 or greater, or 10:1 or greater. In some embodiments, the detergent is effective in reducing or preventing rust in engines or other automotive components such as transmissions or gears. The detergent may be present in the lubricating composition from about 0 to about 10 wt. %, or from about 0.1 to about 8 wt. %, or from about 1 to about 4 wt. %, or from greater than about 4 wt. % to about 8 wt. %.

[0112] 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.

[0113] Friction Modifiers: The lubricating oil compositions herein may also optionally contain one or more friction modifiers. Suitable friction modifiers may include metal-containing and metal-free friction modifiers, but may include, but are not limited to, imidazolines, amides, amines, succinimides, alkoxylated amines, alkoxylated ether amines, amine oxides, amidoamines, nitriles, betaines, quaternary amines, imines, amine salts, aminoguanidines, alkanolamides, phosphonates, metal-containing compounds, glycerol esters, sulfurized fatty compounds and olefins, sunflower oil, other naturally occurring vegetable or animal oils, dicarboxylic acid esters, esters or partial esters of polyols with one or more aliphatic or aromatic carboxylic acids, and the like.

[0114] 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.

[0115] Other suitable friction modifiers may include organic, ashless (metal-free), nitrogen-free organic friction modifiers. Such friction modifiers include esters formed by reacting carboxylic acids and anhydrides with alkanols, and generally may contain polar end groups (e.g., carboxyl or hydroxyl) covalently bonded to an oleophilic hydrocarbon chain. An example of an organic ashless, nitrogen-free friction modifier is commonly known as glycerol monooleate (GMO), which may contain mono-, di-, and tri-esters of oleic acid. Other suitable friction modifiers are described in U.S. Patent No. 6,723,685, the entire contents of which are incorporated herein by reference.

[0116] 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.

[0117] The amines and amides may be used as such or in the form of adducts or reaction products with boron compounds such as boron oxide, boron halides, metaborates, boric acid, or mono-, di-, or tri-alkylborates. Other suitable friction modifiers are described in U.S. Patent No. 6,300,291, which is incorporated herein by reference in its entirety.

[0118] 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.

[0119] 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 compounds may be selected from the group consisting of molybdenum dithiocarbamates, molybdenum dialkyldithiophosphates, amine salts of molybdenum compounds, and mixtures thereof. In one embodiment, the oil-soluble molybdenum compound can be a molybdenum dithiocarbamate.

[0120] 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. Nos. 37,363 (E1), 38,929 (E1), and 40,595 (E1), the entire contents of which are incorporated herein by reference.

[0121] Additionally, the molybdenum compound can be an acidic molybdenum compound, including molybdic acid, ammonium molybrate, sodium molybrate, potassium molybrate, and other alkali metal molybdates and other molybdenum salts, such as sodium hydrogen molybrate, 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.

[0122] 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's organic groups, such as at least 25, at least 30, or at least 35 carbon atoms. Additional suitable molybdenum compounds are described in U.S. Pat. No. 6,723,685, incorporated herein by reference in its entirety.

[0123] The oil-soluble molybdenum compound may be present in an amount sufficient to provide from about 0.5 to about 2000 ppm, from about 1 to about 700 ppm, from about 1 to about 550 ppm, from about 5 to about 300 ppm, or from about 20 to about 250 ppm of molybdenum.

[0124] Transition Metal-Containing Compound: In another embodiment, the oil-soluble compound may be a transition metal-containing compound or metalloid. Transition metals may include, but are not limited to, titanium, vanadium, copper, zinc, zirconium, molybdenum, tantalum, tungsten, etc. Suitable metalloids include, but are not limited to, boron, silicon, antimony, tellurium, etc.

[0125] In some embodiments, the oil-soluble transition metal-containing compound may function as an anti-wear agent, a friction modifier, an antioxidant, a deposit control additive, or two or more of these functions. In some embodiments, the oil-soluble transition metal-containing compound may be an oil-soluble titanium compound such as a titanium(IV) alkoxide. Among the titanium-containing compounds that may be used in or for preparing the oil-soluble materials of the disclosed technology are various Ti(IV) compounds such as titanium(IV) oxide; titanium(IV) sulfide; titanium(IV) nitrate; titanium(IV) alkoxides, such as titanium methoxide, titanium ethoxide, titanium propoxide, titanium isopropoxide, titanium butoxide, and titanium 2-ethylhexoxide; and other titanium compounds or complexes, such as, but not limited to, titanium phenate; titanium carboxylates, such as titanium(IV) 2-ethyl-1,3-hexanedioate, titanium citrate, or titanium oleate; and titanium(IV) (triethanolaminato)isopropoxide. Other forms of titanium encompassed by the disclosed technology include titanium phosphates, such as titanium dithiophosphates (e.g., dialkyldithiophosphates) and titanium sulfonates (e.g., alkylbenzene sulfonates), or generally reaction products of titanium compounds with various acidic substances to form salts, such as oil-soluble salts. Thus, titanium compounds can be derived from organic acids, alcohols, and glycols, among others. Ti compounds can also exist in dimeric or oligomeric forms containing Ti-O-Ti structures. Such titanium materials are commercially available or can be readily prepared by suitable synthetic techniques apparent to those skilled in the art. They can exist at room temperature as solids or liquids, depending on the particular compound. They can also be provided in solution form in a suitable inert solvent.

[0126] In one embodiment, titanium can be provided as a Ti-modified dispersant, such as a succinimide dispersant. Such materials can be prepared by forming a titanium mixed anhydride between a titanium alkoxide and a hydrocarbyl-substituted succinic anhydride, such as an alkenyl-(or alkyl) succinic anhydride. The resulting titanate-succinate intermediate can be used directly or reacted with any of several materials, such as (a) polyamine-based succinimide / amide dispersants having free condensable —NH functional groups; (b) components of polyamine-based succinimide / amide dispersants, i.e., alkenyl-(or alkyl) succinic anhydrides and polyamines; or (c) hydroxy-containing polyester dispersants prepared by reacting a substituted succinic anhydride with a polyol, aminoalcohol, polyamine, or mixtures thereof. Alternatively, the titanate-succinate intermediate can be reacted with other agents, such as alcohols, amino alcohols, ether alcohols, polyether alcohols or polyols, or fatty acids, and the product can be used directly to impart Ti to lubricants or further reacted with a succinic dispersant as described above. As an example, one part (mole) of tetraisopropyl titanate can be reacted with approximately two parts (mole) of polyisobutene-substituted succinic anhydride at 140-150°C for 5-6 hours to provide a titanium-modified dispersant or intermediate. The resulting material (30 g) can be further reacted with a succinimide dispersant from a polyisobutene-substituted succinic anhydride and polyethylene polyamine mixture (127 g + diluent oil) at 150°C for 1.5 hours to produce a titanium-modified succinimide dispersant.

[0127] Another titanium-containing compound is titanium alkoxide and C6-C 25 The reaction product may be a reaction product with a carboxylic acid. The reaction product has the following formula:

[0128] [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:

[0129] [ka] where m+n=4, n ranges from 1 to 3, R4 is an alkyl moiety having from 1 to 8 carbon atoms, R1 is selected from hydrocarbyl groups containing from about 6 to 25 carbon atoms, and R2 and R3 are the same or different and are selected from hydrocarbyl groups containing from 1 to 6 carbon atoms. Alternatively, the titanium compound may be represented by the following formula:

[0130] [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

[0131] 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.

[0132] In one embodiment, the oil-soluble titanium compound may be present in the lubricating oil composition in an amount to provide from about 0 to about 3000 ppm by weight of titanium, or from 25 to about 1500 ppm by weight of titanium, or from about 35 to about 500 ppm by weight of titanium, or from about 50 to about 300 ppm by weight.

[0133] Other Viscosity Index Improvers: The lubricating oil compositions herein may also optionally contain one or more viscosity index improvers. Suitable viscosity index improvers may include polyolefins, olefin copolymers, ethylene / propylene copolymers, polyisobutene, hydrogenated styrene-isoprene polymers, styrene / maleic acid ester copolymers, hydrogenated styrene / butadiene copolymers, hydrogenated isoprene polymers, alpha-olefin maleic anhydride copolymers, polymethacrylates, polyacrylates, polyalkylstyrenes, hydrogenated alkenylaryl conjugated diene copolymers, or mixtures thereof. Viscosity index improvers may include star polymers, suitable examples of which are described in U.S. Patent Application Publication No. 2012 / 0101017(A1).

[0134] The lubricating oil compositions herein may also optionally contain one or more dispersant viscosity index improvers in addition to or instead 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.

[0135] The total amount of viscosity index improver and / or dispersant viscosity index improver can be from about 0 to about 20 wt %, from about 0.1 to about 15 wt %, from about 0.1 to about 12 wt %, or from about 0.5 to about 10 wt % of the lubricating oil composition.

[0136] Other optional additives: Other additives may be selected to perform one or more functions required in a lubricating fluid. Furthermore, one or more of the aforementioned additives may be multifunctional and may provide functions in addition to or other than those described herein.

[0137] Lubricating oil compositions according to the present disclosure may optionally contain other performance additives. The other performance additives may be in addition to the specific additives of the present disclosure and / or may include one or more of metal deactivators, viscosity index improvers, detergents, ashless TBN boosters, friction modifiers, antiwear agents, corrosion inhibitors, rust inhibitors, dispersants, dispersant viscosity index improvers, extreme pressure agents, antioxidants, foam suppressants, demulsifiers, emulsifiers, pour point depressants, seal swell agents, and mixtures thereof. Typically, fully formulated lubricating oils will contain one or more of these performance additives.

[0138] 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.

[0139] Suitable suds suppressors include silicon-based compounds such as siloxanes.

[0140] 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.

[0141] 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.

[0142] When present, the rust inhibitor may be used in an amount sufficient to provide from about 0 to about 5 wt. %, from about 0.01 to about 3 wt. %, from about 0.1 to about 2 wt. %, based on the final weight of the lubricating oil composition.

[0143] Generally speaking, suitable lubricants containing detergent metals herein may contain additive components in the ranges listed in the table below.

[0144] [Table 2]

[0145] 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 characteristics required in the formulation.

[0146] 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.

[0147] As described herein, compounds can be optionally substituted with one or more substituents as generally illustrated above or as exemplified by the specific classes, subclasses, and species of the present disclosure.

[0148] Unless otherwise clear from the context, the term "major amount" is understood to mean an amount of 50% by weight or more, for example, about 80 to about 98% by weight, based on the total weight of the composition. Also, as used herein, the term "minor amount" is understood to mean an amount of less than 50% by weight, based on the total weight of the composition.

[0149] As used herein, the term "hydrocarbyl group" or "hydrocarbyl" is used in its ordinary sense, as is well known to those skilled in the art. Specifically, it refers to a group having a carbon atom directly attached to the remainder of the molecule and having 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 encompass 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.

[0150] As used herein, the term "aliphatic" encompasses the terms alkyl, alkenyl, alkynyl, each of which is optionally substituted as described below.

[0151] As used herein, an "alkyl" group refers to a saturated aliphatic hydrocarbon group containing 1 to 12 (e.g., 1 to 8, 1 to 6, or 1 to 4) carbon atoms. The alkyl group can be straight-chained 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.

[0152] As used herein, an "alkenyl" group refers to an aliphatic carbon group containing 2 to 8 (e.g., 2 to 12, 2 to 6, or 2 to 4) carbon atoms and at least one double bond. Like an alkyl group, an alkenyl group can be straight or branched. 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.

[0153] As used herein, an "alkynyl" group refers to an aliphatic carbon group containing 2 to 8 (e.g., 2 to 12, 2 to 6, or 2 to 4) carbon atoms and having at least one triple bond. Alkynyl groups can be straight-chained 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.

[0154] 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 is as defined above.

[0155] 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.

[0156] 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.

[0157] 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 ring 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.

[0158] 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.

[0159] 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.

[0160] As used herein, the term "treat rate" refers to the weight percent of a component in a lubricating and cooling fluid.

[0161] The weight-average molecular weight (Mw) and number-average molecular weight (Mn) can be determined using a gel permeation chromatography (GPC) instrument from Waters or similar equipment 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 equipment). GPC operating conditions can include a guard column, four Agilent PLgel columns (300 x 7.5 mm long, 5 μm particle size, and pore size range 100-10,000 Å), and a column temperature of approximately 40°C. Unstabilized HPLC-grade tetrahydrofuran (THF) can be used as the solvent at a flow rate of 1.0 mL / min. The GPC instrument can be calibrated with commercially available 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 at concentrations of 0.1 to 0.5% by weight and used without filtration. GPC measurements are also described in U.S. Pat. No. 5,266,223, which is incorporated herein by reference. The GPC method also provides molecular weight distribution information. See, for example, W.W. Yau, J.J. Kirkland, and D.D. Bly, "Modern Size Exclusion Liquid Chromatography," John Wiley and Sons, New York, 1979, which is incorporated herein by reference. [Example]

[0162] A better understanding of the present disclosure and its many advantages may 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 specified 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.

[0163] Various lubricating compositions were evaluated for piston cleanliness according to CECL-117-20 (TDi3) and for fuel economy according to JASO M 366. Each lubricating composition evaluated in this example contained the same additive package of dispersant, antiwear additive, amine antioxidant, phenolic antioxidant, molybdenum antioxidant, friction modifier, antifoam agent, pour point depressant, and process oil, contributing approximately 1300 ppm magnesium, approximately 40 ppm molybdenum, approximately 780 ppm phosphorus, approximately 1700 ppm sulfur, and approximately 860 ppm zinc to the lubricant. The additive package also had a detergent TBN (ASTM 4739) of approximately 5.7 mg KOH / gram and a calculated SASH (ASTM D874) of approximately 0.75 wt.%.

[0164] The additive package was blended into the lubricating compositions specified in Table 3 below, which included a molybdenum dialkyldithiocarbamate compound and a polymethacrylate viscosity index improver. Each lubricant also included about 4 to about 8 cSt of a base oil blend selected from Group III and Group IV base oils. Table 3 also provides further details about the lubricants, including VW TDi3 piston cleanliness results and JASO fuel economy improvement. Fuel economy was measured in a Toyota 2ZR-FXE engine (e.g., Toyota Prius, 1.8 L, inline-5, port fuel injection).

[0165] [Table 3] -HTHS is measured via one of D4683, D4741, or D5471.

[0166] It should be noted that, as used in this specification and the appended claims, the singular forms "a," "an," and "the" include plural referents unless expressly and unambiguously limited to one referent. Thus, for example, 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.

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

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

[0169] It is further 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.

[0170] 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. In other words, it is also 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.

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

[0172] While particular embodiments have been described, alternatives, modifications, variations, improvements, and substantial equivalents may occur that are not presently anticipated or presently unforeseeable to Applicants or others skilled in the art. Accordingly, the appended claims as filed, and the appended claims as they may be amended, are intended to cover all such alternatives, modifications, variations, improvements, and substantial equivalents.

Claims

1. An engine lubricating oil composition for lubricating a diesel internal combustion engine, comprising: one or more base oils of lubricating viscosity, said one or more base oils having a combined base oil viscosity of 5.4 cSt or less at 100°C; a detergent system that provides said engine lubricating oil composition with a minimum total base number (TBN), measured in accordance with ASTM D4739, of at least 4 mg KOH / g, wherein the detergent system comprises only magnesium-containing detergent additives; 1. The engine lubricating oil composition, wherein the engine lubricating oil composition has one or more of: (i) a NOACK volatility of 13% or less, as measured in accordance with CEC L-40-90 and / or ASTM D5800; (ii) a total base number (TBN) of the engine lubricating oil composition of 10 mg KOH / g or less, as measured in accordance with ASTM D2896; (iii) a calculated sulfated ash (SASH) of 0.8 weight percent or less, as measured in accordance with ASTM D874; (iv) a CCS viscosity at −35° C. of 6200 mPas or less, as measured in accordance with ASTM D5292; or (v) a combination thereof.

2. 10. The engine lubricating oil composition of claim 1, wherein the engine lubricating oil composition meets or exceeds the lubricating performance specified in the CECL-117-20 (VW TDi3) piston cleanliness test with a piston cleanliness rating of at least 53 Merit.

3. 3. The engine lubricating oil composition of claim 2, wherein the engine lubricating oil composition has a positive fuel economy increase of at least 0.5% as measured according to JASO M 366.

4. 10. The engine lubricating oil composition of claim 1, wherein the detergent system does not include a phenate detergent additive and the detergent system includes a sulfonate detergent additive.

5. The engine lubricating oil composition of claim 4, wherein the detergent system provides 800 to 1800 ppm of magnesium to the engine lubricating oil composition.

6. 6. The engine lubricating oil composition of claim 5, wherein the detergent system comprises one or more overbased detergent additives having a total base number (TBN) of at least 250 mg KOH / g as measured according to ASTM D2896.

7. 2. The engine lubricating oil composition of claim 1, wherein the engine lubricating oil composition has a TBN of less than or equal to 8 as measured according to ASTM D2896 and / or the TBN of the detergent system is from 4 to 10 mg KOH / g as measured according to ASTM D4739.

8. 10. The engine lubricating oil composition of claim 1, further comprising an oil-soluble molybdenum-containing additive providing up to 800 ppm of molybdenum to said engine lubricating oil composition.

9. The engine lubricating oil composition of claim 1, further comprising 2 to 10 weight percent of one or more polymeric viscosity index improver additives, and / or wherein the engine lubricating oil composition has a viscosity index of 130 to 300.

10. 10. The engine lubricating oil composition of claim 9, wherein the one or more polymeric viscosity index improver additives are one of (i) an olefin copolymer, (ii) a dispersant or non-dispersant poly(meth)acrylate copolymer viscosity modifier having a weight average molecular weight of 500,000 or less, or (iii) a combination thereof, and / or the one or more polymeric viscosity index improver additives are the dispersant or non-dispersant poly(meth)acrylate copolymer having a weight average molecular weight of 200,000 to 500,000 with a polydispersity index of 1.5 to 2.5, comprising first (meth)acrylate monomer units having up to 700 hydrocarbyl groups in the monomer ester moiety and second (meth)acrylate monomer units having up to 10,000 hydrocarbyl groups in the monomer ester moiety.

11. 2. The engine lubricating oil composition of claim 1, wherein the engine lubricating oil composition has a viscosity grade of 0W-X, where X is 8, 12, 16, 20, or 30, and / or the base oil viscosity is 5.2 cSt or less.

12. 10. The engine lubricating oil composition of claim 1, wherein the engine lubricating oil composition is boron-free, calcium-free, or a combination thereof, and / or further comprises one or more metal dihydrocarbyl dithiophosphate compounds, wherein the one or more metal dihydrocarbyl dithiophosphate compounds provide up to 1000 ppm of phosphorus to the lubricating oil composition.

13. 10. The engine lubricating oil composition of claim 1, further comprising one or more sulfur-containing additives, said one or more sulfur-containing additives providing up to 2500 ppm sulfur to said lubricating oil composition.

14. 1. A method for improving said fuel economy and said piston cleanliness in a passenger car diesel engine using a lubricating oil composition comprising: lubricating an engine crankcase of a passenger vehicle diesel engine with a lubricating oil composition; The lubricating oil composition is as set forth in claim 1, The lubricating oil composition meets or exceeds the lubrication performance specified in the CECL-117-20 (VW TDi3) piston cleanliness test with a piston cleanliness rating of at least 53 Merit, and the lubricating oil composition has a positive fuel economy improvement as measured in accordance with JASO M 366 with a fuel economy improvement of at least 0.5%.

15. 1. A method of lubricating a crankcase of a passenger vehicle diesel engine using a lubricating oil composition, comprising: lubricating an engine crankcase of a passenger vehicle diesel engine with a lubricating oil composition; The lubricating oil composition is as set forth in claim 1, wherein the passenger car engine lubricated with the lubricating oil composition meets or exceeds the lubrication performance specified in the CECL-117-20 (VW TDi3) piston cleanliness test with a piston cleanliness rating of at least 53 merit and has a positive fuel economy increase as measured in accordance with JASO M 366 with at least a 0.5% fuel economy improvement.

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