Lubricating compositions for motorcycle applications

Abstract

The present disclosure relates to lubricating compositions, and more particularly to lubricating compositions suitable for motorcycle applications, containing selected metal dihydrocarbyl dithiophosphates to achieve low copper corrosion, good TBN retention, and good sulfur retention applicable to motorcycle engines and transmissions.

Description

[Technical Field]

[0001] The present disclosure relates to lubricating compositions, particularly lubricating compositions suitable for motorcycle applications. [Background technology]

[0002] In motorcycles, a common fluid provides lubrication to the engine and driveline components, including the transmission and / or clutch. Therefore, lubricating compositions used in motorcycle engines are formulated to have a balance of both frictional properties suitable for the driveline and lubrication properties suitable for the engine. This contrasts with lubricants for other vehicles, such as passenger cars, where the engine or crankcase is lubricated with one type of lubricant and the driveline is lubricated with a second type of lubricant. This dual-purpose fluid in motorcycle applications poses formulation challenges because, while it is often desirable to reduce viscosity and friction within the engine crankcase to improve fuel economy, it is often important to maintain sufficient friction within the transmission and / or clutch assembly for proper operation. For this reason, lubricants formulated for passenger car applications are generally not suitable for motorcycle applications because passenger car fluids may exhibit, among other characteristics, a coefficient of friction that is too low to lubricate most motorcycle transmission and / or clutch components.

[0003] Given the unique challenges associated with motorcycle lubricants, the industry has developed standards to adequately evaluate the quality and performance of lubricants for motorcycle applications. Specifically, JASO T 903:2016 defines performance requirements for motorcycle lubricants, specifying, among other criteria, the amount of copper due to corrosion, total base number (TBN) retention, and sulfur retention, as measured using the Indiana Stirred Oxidation Test (ISOT) and when performed under the JIS K2514 test standard. Dithiophosphate compounds, and particularly metal dihydrocarbyl dithiophosphates, such as the compound zinc dihydrocarbyl dithiophosphate (ZDDP), are often used as antiwear additives in passenger car crankcase lubricants, but these additives tend to be problematic in motorcycle lubricants due to their adverse effects on copper corrosion, TBN retention, and / or sulfur retention. Summary of the Invention

[0004] The present disclosure relates to motorcycle lubricating compositions that exhibit good copper corrosion, TBN retention, and / or sulfur retention, specifically for motorcycle fluids. In one embodiment or approach, the motorcycle lubricant comprises one or more base oils of lubricating viscosity, a minor additive package including a metal-containing sulfonate, salicylate, and / or phenate detergent, a dispersant providing at least about 400 ppm of nitrogen, at least one amine antioxidant, and one or more metal dihydrocarbyl dithiophosphate compounds, the one or more metal dihydrocarbyl dithiophosphate compounds providing at least about 800 ppm of phosphorus to the motorcycle lubricating composition, the one or more metal dihydrocarbyl dithiophosphate compounds having, on average, at least 14 total carbons per phosphorus atom, and whose hydrocarbyl groups are derived from at least about 80 mole percent straight or branched chain primary alcohols.

[0005] In other approaches or embodiments, the motorcycle lubricant of the preceding paragraph may include other features or embodiments in any combination. These optional features or embodiments may include one or more of the following: the hydrocarbyl groups of the one or more metal dihydrocarbyl dithiophosphate compounds are derived from about 100 mole percent straight or branched chain primary alcohols, and / or the one or more metal dihydrocarbyl dithiophosphate compounds have, on average, at least 16 total carbons per phosphorus atom, and / or the lubricating composition exhibits copper leachability of about 90 ppm or less, a TBN retention of up to about 25 percent (or from about 10 to about 25 percent), and a sulfur retention of at least about 95 percent (or from about 95 to 100 percent), as measured according to the Indiana Stirred Oxidation Test (ISOT) conducted in accordance with JIS K2514 testing standard, and / or the metal dihydrocarbyl dithiophosphate compound has the structure of Formula I:

[0006] [ka] wherein each R is independently a straight or branched chain C8 to C16 hydrocarbyl group, and A is a metal selected from aluminum, lead, tin, molybdenum, manganese, nickel, copper, titanium, tungsten, zirconium, or zinc, and / or each R is a straight or branched chain C8 to C10 hydrocarbyl group derived from a primary alcohol, and / or A is zinc, and each R has about 100 mole percent hydrocarbyl groups derived from C8 to C10 primary alcohols, and / or the one or more metal dihydrocarbyl dithiophosphate compounds provide up to about 3,000 ppm phosphorus to the motorcycle lubricating composition, and / or the detergent is and / or the lubricating composition comprises up to about 1 weight percent of an aminic antioxidant, and / or the aminic antioxidant is selected from the group consisting of aromatic amines, alkylated diphenylamines, nonyl diphenylamines, dinonyl diphenylamines, octyl diphenylamines, dioctyl diphenylamines, phenyl-alpha-naphthylamines, alkylated phenyl-alpha-naphthylamines, hindered non-aromatic ... and / or the lubricating composition comprises from about 0.5 to about 5 weight percent of the dispersant; and / or the dispersant is obtainable by reacting a hydrocarbyl-substituted acylating agent with a nitrogen source; and / or the acylating agent is maleic anhydride and the nitrogen source is selected from ammonia, polyalkylene polyamines, or combinations thereof; and / or the nitrogen source is a polyalkylene polyamine selected from polyethylene polyamines having an average of 5 nitrogen atoms, triethylene tetraamine, tetraethylene pentamine, or mixtures of combinations thereof.

[0007] In another approach or embodiment, described herein are methods of lubricating motorcycle engines, transmissions, and clutch assemblies with the lubricating compositions to achieve good copper corrosion, TBN retention, and / or sulfur retention. In one aspect, the method includes lubricating an engine, a transmission, and a clutch assembly of a motorcycle with a lubricating composition provided from a common lubricant reservoir, the lubricating composition including one or more base oils of lubricating viscosity, a minor amount of an additive package including a metal-containing sulfonate, salicylate, and / or phenate detergent, a dispersant providing at least about 400 ppm of nitrogen, at least one aminic antioxidant, and one or more metal dihydrocarbyl dithiophosphate compounds, the one or more metal dihydrocarbyl dithiophosphate compounds providing at least about 800 ppm of phosphorus to the motorcycle lubricating composition, the one or more metal dihydrocarbyl dithiophosphate compounds having, on average, at least 14 total carbons per phosphorus atom and whose hydrocarbyl groups are derived from at least about 80 mole percent straight or branched chain primary alcohols.

[0008] In other approaches or embodiments, the method described in the preceding paragraph may include one or more optional features, method steps, or embodiments, in any combination. These optional features, steps, or embodiments may include one or more of the following: the hydrocarbyl groups of the one or more metal dihydrocarbyl dithiophosphate compounds are derived from about 100 mole percent straight or branched chain primary alcohols, and / or the one or more metal dihydrocarbyl dithiophosphate compounds have, on average, at least 16 total carbons per phosphorus atom, and / or the lubricating composition exhibits copper leachability of about 90 ppm or less, a TBN retention of up to about 25 percent (or from about 10 to about 25 percent), and a sulfur retention of at least about 95 percent (or from about 95 to about 100 percent), as measured according to the Indiana Stirred Oxidation Test (ISOT) performed under JIS K2514 testing standard, and / or the metal dihydrocarbyl dithiophosphate compound has the structure of Formula I:

[0009] [ka] wherein each R is independently a straight or branched chain C8 to C16 hydrocarbyl group; A is a metal selected from aluminum, lead, tin, molybdenum, manganese, nickel, copper, titanium, tungsten, zirconium, or zinc; and / or each R is a straight or branched chain C8 to C10 hydrocarbyl group derived predominantly from primary alcohols; and / or A is zinc; and each R has about 100 mole percent hydrocarbyl groups derived from C8 to C10 primary alcohols; and / or the one or more metal dihydrocarbyl dithiophosphate compounds provide up to about 3,000 ppm phosphorus to the motorcycle lubricating composition.

[0010] In yet another approach or embodiment, use of a lubricating composition comprising one or more base oils of lubricating viscosity, a minority additive package comprising a metal-containing sulfonate, salicylate, and / or phenate detergent, a dispersant providing at least about 400 ppm of nitrogen, at least one aminic antioxidant, and one or more metal dihydrocarbyl dithiophosphate compounds, wherein the one or more metal dihydrocarbyl dithiophosphate compounds provide at least about 800 ppm of phosphorus to the motorcycle lubricating composition, and the one or more metal dihydrocarbyl dithiophosphate compounds have, on average, at least 14 total carbons per phosphorus atom and the hydrocarbyl groups thereof pass an Indiana Stirred Oxidation Test performed in accordance with JIS K2514 test standard. The alcohol is derived from at least about 80 mole percent straight or branched chain primary alcohols to achieve a copper leach of about 90 ppm or less, a TBN retention of up to about 25 percent (or from about 10 to about 25 percent), and / or a sulfur retention of at least about 95 percent (or from about 95 to 100 percent), as measured in accordance with the ISOT. DETAILED DESCRIPTION OF THE INVENTION

[0011] This disclosure relates to lubricating compositions configured for use in motorcycles and to methods of lubricating the engine, transmission, and clutch assembly of a motorcycle with a single lubricating composition, generally provided from a common sump. As noted in the Background section, motorcycle lubricants are required to do more than simply lubricate the engine crankcase. Motorcycle lubricants also lubricate driveline components, including the transmission and clutch. As a result, the fluid testing and requirements are quite different from typical lubricants for passenger car motor oils.

[0012] In particular, the copper leaching, TBN retention, and sulfur retention in the Indiana Stirred Oxidization Test (ISOT) conducted under the JIS K2514 standard set forth in JASO T 903:2016 are fluid requirements not typically associated with crankcase lubricants for passenger car motor oils. While antiwear agents such as metal dihydrocarbyl dithiophosphate compounds (including but not limited to ZDDP compounds) are commonly used in passenger car motor oils, when used in motorcycle oils, such additives have traditionally not produced very desirable performance in such ISOT tests. Unexpectedly, it has been discovered that certain metal dihydrocarbyl dithiophosphate compounds having specific configurations can provide passing ISOT performance for motorcycle applications. More specifically, metal dihydrocarbyl dithiophosphate compounds having a minimum number of carbons per phosphorus atom and having hydrocarbyl groups derived primarily from straight- or branched-chain primary alcohols surprisingly achieve acceptable ISOT performance when used in motorcycle lubricants, whereas lubricants containing metal dihydrocarbyl dithiophosphate compounds that do not meet such criteria do not achieve acceptable ISOT performance suitable for motorcycle lubrication.

[0013] In one approach or embodiment, a motorcycle lubricating composition is described herein that includes one or more base oils of lubricating viscosity, a minor amount of an additive package including a metal-containing sulfonate, salicylate, and / or phenate detergent, a dispersant providing at least about 400 ppm of nitrogen, at least one aminic antioxidant, and one or more metal dihydrocarbyl dithiophosphate compounds. To achieve acceptable ISOT performance, the one or more metal dihydrocarbyl dithiophosphate compounds provide at least about 800 ppm of phosphorus to the motorcycle lubricating composition and have, on average, at least 14 total carbons per phosphorus atom, the hydrocarbyl groups of which are derived from at least about 80 mole percent straight or branched chain primary alcohols. In another approach or embodiment, the hydrocarbyl groups of the one or more metal dihydrocarbyl dithiophosphate compounds in the motorcycle lubricant are derived from about 100 mole percent straight or branched chain primary alcohols and have, on average, at least 16 total carbons per phosphorus atom. When motorcycle lubricants include such additives, the lubricating compositions exhibit comparable or better performance compared to conventional motorcycle lubricants with respect to copper corrosion / leaching, TBN retention, and / or sulfur retention, and in that context, the fluids herein exhibit copper leaching of about 90 ppm or less (preferably, about 50 to about 90 ppm), TBN retention of up to about 25 percent (preferably, about 10 to about 25 percent, or about 14 to about 25 percent), and sulfur retention of at least about 95 percent (preferably, about 95 percent to about 100 percent), as measured according to the Indiana Stirred Oxidation Test (ISOT) conducted under JIS K2514 testing standard.

[0014] Metal dihydrocarbyl dithiophosphate compounds The motorcycle lubricants herein include one or more metal dihydrocarbyl dithiophosphate compounds, such as, but not limited to, zinc dihydrocarbyl dithiophosphate compounds (ZDDP). In one approach, the one or more metal dihydrocarbyl dithiophosphate compounds provide the motorcycle lubricant with at least about 800 ppm of phosphorus, and in other approaches, from about 800 ppm to about 3,000 ppm of phosphorus, or from about 900 ppm to about 2,500 ppm of phosphorus, or from about 1,000 ppm to about 2,000 ppm of phosphorus, or from about 1,000 to about 1,500 ppm of phosphorus. As noted above, metal dihydrocarbyl dithiophosphate compounds suitable for motorcycle applications have a specific structure, containing at least 14 total carbons per phosphorus atom, and whose hydrocarbyl groups are derived from at least about 80 mole percent straight- or branched-chain primary alcohols. In another approach or embodiment, the hydrocarbyl groups are derived from about 100 mole percent straight-chain or branched-chain primary alcohols and have an average of at least 16 total carbons per phosphorus atom provided by the straight-chain or branched-chain primary alcohols. In yet another approach, the hydrocarbyl groups are derived from about 80 to about 100 mole percent straight-chain or branched-chain primary alcohols and have an average of 14 to 16 total carbons per phosphorus atom provided by the straight-chain or branched-chain primary alcohols, preferably branched-chain primary alcohols. As used herein, the average total carbons per phosphorus atom of the metal dihydrocarbyl dithiophosphate is determined by the following formula: 2 × [(carbons in alcohol 1) (mole percent) + (carbons in alcohol 2) (mole percent) + (carbons in alcohol 3) (mole percent) + ...], so long as the alcohol used in forming the metal dihydrocarbyl dithiophosphate compound also meets the required amount of primary alcohol found herein.

[0015] Suitable metal dihydrocarbyl dithiophosphate compounds may contain 5 to about 10 weight percent metal (such as about 6 to about 9 weight percent metal) and about 8 to about 18 weight percent sulfur (such as about 12 to about 18 weight percent sulfur, or about 8 to about 15 weight percent sulfur). Suitable metal dihydrocarbyl dithiophosphate compounds may include dihydrocarbyl dithiophosphate metal salts, where the metal may be an alkali metal, alkaline earth metal, aluminum, lead, tin, molybdenum, manganese, nickel, copper, titanium, zirconium, zinc, or a combination thereof. Preferably, the metal is zinc.

[0016] The alkyl groups on the metal dihydrocarbyl dithiophosphate compounds herein may be derived from primary alcohols, secondary alcohols, phenols, and / or mixtures thereof, so long as the stated relationship between the average number of carbons per phosphorus atom and the mole percent of the primary alcohol source is satisfied. For example, all of the alkyl groups on the metal dihydrocarbyl dithiophosphate compounds herein may be derived from a primary alcohol (such as 2-ethylhexyl alcohol) or a mixture of primary and secondary alcohols (such as 2-ethylhexanol, isobutanol, and isopropanol), so long as the resulting metal dihydrocarbyl dithiophosphate compound achieves the target carbon content per phosphorus atom and primary alcohol content on the resulting molecule. For example, in one embodiment, about 80 mole percent or more of the alkyl groups are derived from the primary alcohol 2-ethylhexanol, and about 20 mole percent or less of the alkyl groups are derived from a secondary alcohol (such as isopropyl alcohol, methyl isobutyl carbinol, and the like, and combinations thereof). In other embodiments, all of the alkyl groups on the metal dihydrocarbyl dithiophosphate compound may be derived from a primary alcohol, such as 2-ethylhexanol or others described below. Preferably, the metal dihydrocarbyl dithiophosphate compound is a ZDDP derived from 80 to 100 mole percent 2-ethylhexanol and may contain about 6 to about 10 weight percent phosphorus, about 6 to about 9 weight percent zinc, and about 12 to about 18 weight percent sulfur.

[0017] The metal dihydrocarbyl dithiophosphate compounds herein may be derived from an alcohol selected from, but not limited to, 2-ethylhexanol, methylheptanol, heptanol, octanol, nonanol, decanol, dodecanol, and / or their isovariants. Examples of suitable metal dihydrocarbyl dithiophosphate compounds include zinc O,O-di(C 8~14zinc O,O-bis(6-ethylhexyl)dithiophosphate; zinc O,O-dioctyldithiophosphate; zinc O,O-dipentyldithiophosphate; zinc O-(2-methylbutyl)-O-(2-methylpropyl)dithiophosphate; and zinc O-(3-methylbutyl)-O-(2-methylpropyl)dithiophosphate, or combinations thereof.

[0018] In an approach or embodiment, metal dihydrocarbyl dithiophosphate compounds suitable for motorcycle lubricants may also have the structure of Formula I:

[0019] [ka] wherein each R in Formula I independently contains 6 to 18 carbon atoms, or 6 to 12 carbon atoms, or about 8 to 10 carbon atoms, provided that each phosphorus atom has, on average, at least 14 total carbon atoms, preferably at least 16 total carbon atoms, or 14 to 16 total carbon atoms. For example, each R may independently be ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl, amyl, n-hexyl, i-hexyl, n-octyl, decyl, dodecyl, octadecyl, 2-ethylhexyl, phenyl, butylphenyl, cyclohexyl, methylcyclopentyl, propenyl, or butenyl. The number of carbon atoms in each R group in the above formula will generally be about 3 or more, about 4 or more, about 6 or more, or about 8 or more. Each R group may have, on average, 6 to 10 carbon atoms, preferably 8 to 10 carbon atoms. Preferably, each R may be straight or branched chain C8 or 2-ethylhexyl. In Formula I, A is a metal such as aluminum, lead, tin, molybdenum, manganese, nickel, copper, titanium, zirconium, zinc, or a combination thereof; preferably, A is zinc. When the metal dihydrocarbyl dithiophosphate compound has the structure shown in Formula I and A is zinc, the compound may have from about 4 to about 9 weight percent phosphorus and from about 6 to about 9 weight percent zinc.

[0020] In some approaches or embodiments, it is understood in the art that a more accurate representation of the sulfur-zinc coordination array can be represented by the symmetrical array shown below, and that the chemical structure of Formula II as used herein is interchangeable with Formula I shown above. It is also understood that the structures shown in Formulas I and II can exist as monomers, dimers, trimers, or oligomers (e.g., tetramers).

[0021] [ka]

[0022] Dihydrocarbyl dithiophosphate metal salts can be prepared according to known techniques, typically by first forming dihydrocarbyl dithiophosphoric acid (DDPA) by reacting one or more alcohols or phenols with P2S5, followed by neutralization of the resulting DDPA with a metal compound such as zinc oxide. For example, DDPA can be produced by reacting a mixture of alcohols containing a suitable amount of primary alcohol (and, if desired, a suitable blend of primary and secondary alcohols) with P2S5. In this case, the DDPA contains alkyl groups derived primarily from primary alcohols or from both primary and secondary alcohols, as needed to meet the required primary alcohol content in the final product. Alternatively, multiple DDPAs can be prepared, with the alkyl groups on one DDPA derived entirely from secondary alcohols and the alkyl groups on another DDPA derived entirely from primary alcohols. The DDPAs are then blended together to form a mixture of DDPAs with alkyl groups satisfying the above-mentioned primary alcohol content.

[0023] Detergents The motorcycle lubricating compositions herein may also include a detergent or detergent system. In embodiments, the detergent or detergent system comprises one or more detergent additives generally comprising one or more alkali metal or alkaline metal salts of phenates, sulfonates, calixarates, salixarates, salicylates, carboxylic acids, sulfurized derivatives thereof, or combinations thereof. Preferably, the detergent is a metal-containing sulfonate, salicylate, and / or phenate, and most preferably, calcium phenate, calcium sulfonate, or combinations thereof.

[0024] Suitable detergents and methods for their preparation are described in more detail in numerous patent publications, including 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 the individual and / or total detergent additives, in other ways from about 0.15 to about 3 weight percent, and in yet other ways from about 0.5 to 2.6 weight percent of the individual and / or total detergent additives.

[0025] The detergent system provides an amount of total detergent metals that is greater than about 1,000 ppm total metals, or in other approaches from about 1,500 ppm to about 5,000 ppm total metals, from about 2,000 ppm to about 3,500 ppm total metals, from about 2,200 ppm to about 3,000 ppm total metals, or from about 2,200 ppm to about 2,800 ppm total metals, based on the total lubricating composition. In other approaches, the detergent metals are calcium, sodium, and / or magnesium, preferably calcium provided by phenates and sulfonates, more preferably overbased calcium phenates and / or overbased calcium sulfonates.

[0026] Generally, suitable detergents in the system may include petroleum sulfonic acids and long chain mono- or di-alkylaryl sulfonic acids in which the aryl groups are benzyl, tolyl, and xylyl, and / or linear or branched alkali metal or alkaline earth metal salts, such as calcium, sodium, or magnesium, of various phenates or phenate derivatives. Examples of suitable detergents include, but are not limited to, lowbased / neutral and overbased variations of the following detergents: calcium phenate, calcium sulfur-containing phenate, calcium sulfonate, calcium calixarate, calcium salixarate, calcium salicylate, calcium carboxylic acid, calcium phosphate, calcium mono- and / or di-thiophosphate, calcium alkyl phenol, calcium sulfur-bound alkyl phenol compound, calcium methylene bridged phenol, magnesium phenate, magnesium sulfur-containing 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 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-bound alkyl phenol compound, or sodium methylene bridged phenol.

[0027] The detergent additive may be neutral, underbased, or overbased, preferably overbased as described above. As will be appreciated, overbased detergent additives are well known in the art and may be alkali metal or alkaline earth metal overbased detergent additives. Such detergent additives may be prepared by reacting a metal oxide or metal hydroxide with a substrate and carbon dioxide gas. The substrate is typically an acid, such as an aliphatic-substituted sulfonic acid, an aliphatic-substituted carboxylic acid, or an aliphatic-substituted phenol.

[0028] 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 may have a conversion level of greater than 100% (i.e., they may contain more than 100% of the theoretical amount of metal required to convert the acid to its "standard" or "neutral" salt). The expression "metal ratio," often abbreviated as MR, is used to indicate the ratio of the total chemical equivalents of 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. These are commonly referred to as overbased, highly based, or superbased salts and may be salts of organic sulfur acids, carboxylic acids, or phenols.

[0029] As used herein, the term "TBN" is used to represent a total base number in mg KOH / g, as measured by the method of ASTM D2896. The overbased detergent of the lubricating oil composition 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, or from about 200 mg KOH / gram to about 400 mg KOH / gram, or any range therebetween. 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.

[0030] Examples of suitable overbased detergents include, but are not limited to, overbased calcium phenates, overbased sulfur-containing phenates, overbased calcium sulfonates, overbased calcium calixarates, overbased calcium salixarates, overbased calcium salicylates, overbased calcium carboxylic acids, overbased calcium phosphates, overbased calcium mono- and / or di-thiophosphates, overbased calcium alkylphenols, overbased calcium sulfur-bound alkylphenol compounds, overbased calcium methylene-bridged phenols, overbased magnesium phenates, overbased magnesium sulfur-containing phenates, overbased magnesium sulfonates, overbased magnesium calixarates, overbased magnesium salixarates, overbased magnesium salicylates, overbased magnesium carboxylic acids, overbased magnesium phosphates, overbased magnesium mono- and / or di-thiophosphates, overbased magnesium alkylphenols, overbased magnesium sulfur-bound alkylphenol compounds, or overbased magnesium methylene-bridged phenols.

[0031] Preferably, the detergent is overbased, but the motorcycle lubricants herein may also include low-based or neutral detergents. Low-based or neutral detergents, when incorporated into a detergent system, generally have 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. Low-based / neutral detergents may also include detergents containing calcium, sodium, or magnesium. 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.

[0032] In some embodiments, the detergents used in the lubricants herein are overbased calcium sulfonates, overbased calcium phenates, or combinations thereof, each having a Total Base Number of 200 to 400, or alternatively from about 200 to about 350. The TBN values ​​above reflect the values ​​of the finished detergent components diluted in base oil.

[0033] 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, as a neat additive, an overbased calcium or sodium sulfonate or an overbased calcium or sodium sulfonate having a TBN of about 300 to about 450, or in another approach, about 380 to about 420, or, as a neat additive, an overbased magnesium sulfonate having a TBN of about 500 to about 700, or in another approach, about 600 to about 700.

[0034] More specifically, the detergent system herein includes a neutral to overbased calcium sulfonate or phenate, a neutral to overbased sodium sulfonate or phenate, or a neutral to overbased magnesium sulfonate or phenate. Preferably, the detergent provides at least about 1,000 ppm of calcium (preferably, about 1,500 ppm to about 5,000 ppm of calcium) from the overbased phenate or sulfonate. If the detergent provides sodium, it may provide at least about 90 ppm of sodium, at least about 180 ppm of sodium (preferably, about 90 to about 1,000 ppm or about 180 ppm to about 1,000 ppm). If the detergent provides magnesium, it will provide at least about 90 ppm of magnesium, at least about 180 ppm of magnesium (preferably, about 90 to about 1,000 ppm or about 180 ppm to about 1,000 ppm).

[0035] Amine antioxidants Motorcycle lubricants may also include one or more antioxidants, preferably one or more aminic antioxidants. In some embodiments, the aminic antioxidants may include, but are not limited to, antioxidants selected from aromatic amines, alkylated diphenylamines, phenyl-α-naphthylamines, alkylated phenyl-α-naphthylamines, hindered non-aromatic amines, and the like, or combinations thereof. The total amount of antioxidant in the lubricating compositions herein may be present in an amount providing up to about 400 ppm nitrogen, or up to about 300 ppm nitrogen, or up to about 200 ppm nitrogen, or from about 50 to about 400 ppm nitrogen, from about 60 to about 300 ppm nitrogen, from about 70 to about 200 ppm nitrogen, or from about 80 to about 100 ppm nitrogen. In other approaches, the lubricating compositions herein may contain up to about 1 weight percent of the aminic antioxidant, or from about 0.1 to about 1.0 weight percent of the aminic antioxidant, or in other approaches from about 0.2 to about 0.8 weight percent, or from about 0.2 to about 0.6 weight percent of the aminic antioxidant.

[0036] In some approaches, the amine antioxidant may be one or more aromatic amine antioxidants, which may include, but are not limited to, diarylamines having the formula:

[0037] [ka] wherein R' and R" each independently represent a substituted or unsubstituted aryl group having 6 to 30 carbon atoms. When substituted, suitable substituents on the aryl groups of R' and R" include an aliphatic hydrocarbon group such as an alkyl having 1 to 30 carbon atoms, a hydroxy group, a halogen radical, a carboxylic acid or ester group, or a nitro group. The aryl group may be a substituted or unsubstituted phenyl or naphthyl, particularly one in which one or both aryl groups are substituted with at least one alkyl having 4 to 30, preferably 4 to 18, and most preferably 4 to 9 carbon atoms. In some embodiments, one or both aryl groups may be substituted, such as mono-alkylated diphenylamine, di-alkylated diphenylamine, C9 alkylated diphenylamines, or a mixture of mono- and di-alkylated diphenylamines.

[0038] Examples of diarylamines that can be used include, but are not limited to, diphenylamine; various alkylated diphenylamines, 3-hydroxydiphenylamine, N-phenyl-1,2-phenylenediamine, N-phenyl-1,4-phenylenediamine, monobutyldiphenylamine, dibutyldiphenylamine, monooctyldiphenylamine, dioctyldiphenylamine, monononyldiphenylamine, dinonyldiphenylamine, monotetradecyldiphenylamine, ditetradecyldiphenylamine, phenyl-alpha-naphthylamine, monooctylphenyl-alpha-naphthylamine, phenyl-beta-naphthylamine, monoheptyldiphenylamine, diheptyl-diphenylamine, p-oriented styrenated diphenylamines, mixed butyloctyldiphenylamines, and mixed octylstyryldiphenylamines.

[0039] In another approach, suitable antioxidants may include aromatic amine antioxidants. Examples of phenolic antioxidants include N,N'-di-sec-butyl-phenylene-diamine, 4-isopropylaminodiphenylamine, phenyl-alpha-naphthylamine, phenyl-alpha-naphthylamine, and ring-alkylated diphenylamines.

[0040] Dispersants The lubricating compositions herein also include one or more dispersants. In some approaches, the one or more dispersants provide at least about 400 ppm nitrogen or up to about 1200 ppm nitrogen. In other approaches, the one or more dispersants provide from about 400 to about 1000 ppm nitrogen or from about 450 to about 950 ppm nitrogen. In some approaches, one or more dispersants may be post-treated with a boron compound, and such approaches may also provide the lubricating composition with at least about 40 ppm boron, or at least about 80 ppm boron, or in other approaches, from about 40 ppm to about 700 ppm, from about 80 ppm to about 700 ppm, from about 100 ppm to about 700 ppm, from about 40 ppm to about 500 ppm, from about 80 ppm to about 500 ppm, from about 100 ppm to about 500 ppm, from about 150 ppm to about 700 ppm, or from about 150 ppm to about 500 ppm boron. In other approaches, the lubricating composition comprises up to about 5 weight percent dispersant, or from about 0.5 to about 5.0 weight percent dispersant, from about 1 to about 4 weight percent, from about 2 to about 4 weight percent, or from about 2.5 to about 3.5 weight percent dispersant.

[0041] Dispersants are often known as ashless dispersants because they contain no ash-forming metals before being mixed into a lubricant composition and typically do not contribute any ash when added to a 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 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 5000, or from about 3000, or from about 2,000, or from about 1,500, as measured by GPC. Succinimide dispersants and their preparation are disclosed, for example, in U.S. Pat. No. 7,897,696 and U.S. Pat. No. 4,234,435, both of which are incorporated herein by reference. 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).

[0042] In some approaches, preferred amines for dispersants may be selected from polyamines and hydroxyamines. Examples of polyamines that can be used include, but are not limited to, diethylenetriamine (DETA), triethylenetetramine (TETA), tetraethylenepentamine (TEPA), and higher homologs such as pentaethylamine hexamine (PEHA). In some approaches, so-called heavy polyamines may 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.

[0043] 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%.

[0044] HR-PIB having a number average molecular weight ranging from about 900 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 / or 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.

[0045] In some approaches, any of the dispersants herein may 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. Patent Nos. 7,645,726, 7,214,649, 8,048,831, and 5,241,003, all of which are incorporated herein by reference in their entirety.)

[0046] When a boron compound is used as the post-treating reagent, it can be selected from boron oxide, boron halides, boric acid, and esters of boric acid in an amount to provide from about 0.1 atomic percentage of boron per mole of nitrogen composition to about 20 atomic percentages of boron for each atomic percentage of nitrogen used. Boron post-treated dispersants can contain from about 0.05 weight percent to about 2.0 weight percent, or in other words, from about 0.05 weight percent to about 0.7 weight percent, of boron, based on the total weight of the borate dispersant.

[0047] In another approach, carboxylic acids may also be used as post-treating reagents and may 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 may also be used as post-treating reagents and may be selected from the group consisting of mono-unsaturated anhydrides (e.g., maleic anhydride), alkyl- or alkylene-substituted cyclic anhydrides (e.g., succinic anhydride or glutamic anhydride), and aromatic carboxylic anhydrides (including naphthalic anhydrides, e.g., 1,8-naphthalic anhydride).

[0048] 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, the 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.

[0049] Base oil or base oil blend The base oil used in the motorcycle lubricating compositions herein may be an oil of lubricating viscosity and may be selected from any of the base oils in API Groups I to V as defined in the American Petroleum Institute (API) Base Oil Interchangeability Guidelines. The five base oil groups are generally set forth in Table 1 below.

[0050] [Table 1]

[0051] 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.

[0052] The base oil blends used in the disclosed lubricating oil compositions may be mineral, animal, vegetable, synthetic, synthetic oil blends, or mixtures thereof. Suitable oils may be derived from hydrocracked, hydrogenated, hydrofinished, unrefined, refined, and rerefined oils, and mixtures thereof.

[0053] Unrefined oils are derived from natural, mineral, or synthetic sources with little or no further purification processing. Refined oils are similar to unrefined oils except that they have been treated with one or more purification steps, which may result in the improvement of one or more properties. Examples of suitable refining 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.

[0054] Re-refined oils are also known as reclaimed or reprocessed oils. These oils are obtained similarly to refined oils using the same or similar processes. Often, these oils are additionally processed by techniques directed to the removal of spent additives and oil breakdown products.

[0055] 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.

[0056] Useful synthetic lubricating oils may include hydrocarbon oils such as polymerized, oligomerized, or interpolymerized olefins (e.g., polybutylene, polypropylene, propylene-isobutylene copolymers); poly(1-hexene), poly(1-octene), trimers or oligomers of 1-decene, such as poly(1-decene) (such materials are often referred to as α-olefins), and mixtures thereof; alkyl-benzenes (e.g., dodecylbenzene, tetradecylbenzene, dinonylbenzene, di-(2-ethylhexyl)-benzene); polyphenyls (e.g., biphenyl, terphenyl, alkylated polyphenyls); diphenylalkanes, alkylated diphenylalkanes, alkylated diphenyl ethers, and alkylated diphenyl sulfides, as well as derivatives, analogs, and homologs thereof, or mixtures thereof. Polyalphaolefins are typically hydrogenated materials.

[0057] Other synthetic lubricating oils include polyol esters, diesters, liquid esters of phosphorus-containing acids (e.g., tricresyl phosphate, trioctyl phosphate, and diethyl ester of decane phosphonic acid), or polymeric tetrahydrofurans. Synthetic oils may be produced by the Fischer-Tropsch reaction and are typically hydroisomerized Fischer-Tropsch hydrocarbons or waxes. In one embodiment, oils may be prepared by the Fischer-Tropsch gas-to-liquid synthesis procedure, as well as other gas-to-liquid oils.

[0058] 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.

[0059] The amount of oil of lubricating viscosity present may be the difference remaining after subtracting the sum of the amounts of performance additives, including viscosity index improvers and / or pour point depressants and / or other top treat additives, from 100% by weight. For example, the oil of lubricating viscosity may be present in the finished 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.

[0060] The base oil system herein, in some approaches or embodiments, comprises one or more of Group I through Group V base oils, and the lubricating compositions herein may have a KV100 of from about 2 to about 20 cSt, in other approaches from about 2 to about 15 cSt, from about 3 to about 12 cSt, in still other approaches from about 4 to about 12 cSt, and in other approaches from about 6 to about 12 cSt.

[0061] As used herein, the terms "oil composition," "lubricating composition," "lubricating oil composition," "lubricating oil," "lubricant composition," "fully formulated lubricant composition," "lubricant," and "lubricating and cooling fluid" are considered synonymous and fully interchangeable terms that refer to a finished lubricating product that includes a major amount of a base oil component and minor amounts of detergents and other optional components.

[0062] Optional Additives The lubricating oil compositions herein may also contain a number of optional additives to meet performance specifications, which optional additives are described in the following paragraphs.

[0063] Other dispersants The lubricating oil composition may optionally contain one or more other dispersants or mixtures thereof. Dispersants are often known as ashless dispersants because they do not contain ash-forming metals prior to incorporation into the lubricating oil composition and do not typically contribute ash when added to the lubricant. Ashless dispersants are characterized by polar groups attached to a relatively high molecular weight hydrocarbon chain. Typical ashless dispersants include N-substituted long-chain alkenyl succinimides. Examples of N-substituted long-chain alkenyl succinimides include polyisobutylene succinimides in which the number average molecular weight of the polyisobutylene substituent ranges from about 350 to about 50,000, or from about 5,000, or from about 3,000, as measured by GPC. Succinimide dispersants and their preparation are disclosed, for example, in U.S. Pat. Nos. 7,897,696 and 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).

[0064] Preferred amines are selected from polyamines and hydroxyamines. 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).

[0065] 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 grams of primary amine groups per equivalent.

[0066] In some approaches, suitable polyamines are commonly known as PAM and contain a mixture of ethyleneamines, with TEPA and pentaethylene hexamine (PEHA) being the majority of the polyamine, usually less than about 80%.

[0067] Typically, PAM has 8.7-8.9 milliequivalents of primary amine per gram (115-112 gram equivalents per equivalent of primary amine) and a total nitrogen content of about 33-34% by weight. Heavier cuts of PAM oligomers that are substantially free of TEPA and contain only small amounts of PEHA, but contain primarily oligomers with more than six nitrogens and more extensive branching, can produce dispersants with improved dispersancy.

[0068] In embodiments, the present disclosure further includes at least one polyisobutylene succinimide dispersant derived from polyisobutylene having a number average molecular weight, as determined by GPC, ranging from about 350 to about 50,000, or from about 5,000, or from about 3,000. The polyisobutylene succinimide may be used alone or in combination with other dispersants.

[0069] 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%.

[0070] 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 rates and less precipitate formation during the reaction due to increased reactivity. A suitable method is described in U.S. Patent No. 7,897,696.

[0071] In one embodiment, the present disclosure further comprises at least one dispersant derived from polyisobutylene succinic anhydride ("PIBSA"), which may have an average of about 1.0 to about 2.0 succinic acid moieties per polymer.

[0072] 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.

[0073] The percent polyolefin conversion is calculated from the % active ingredient using the formula in columns 5 and 6 of US Pat. No. 5,334,321.

[0074] Unless otherwise stated, all percentages are weight percent and all molecular weights are number average molecular weights as determined by gel permeation chromatography (GPC) using commercially available polystyrene standards (having number average molecular weights of 180 to about 18,000) as calibration standards.

[0075] In one embodiment, the dispersant may be derived from a polyalphaolefin (PAO) succinic anhydride. In one embodiment, the dispersant may be derived from an olefin maleic anhydride copolymer. As an example, the dispersant may be described as poly-PIBSA. In an embodiment, the dispersant may be derived from an anhydride grafted to an ethylene-propylene copolymer.

[0076] A suitable class of nitrogen-containing dispersants may be derived from olefin copolymers (OCPs), more specifically ethylene-propylene dispersants which may be grafted with maleic anhydride. A more complete list of nitrogen-containing compounds which may be reacted with functionalized OCPs is described in U.S. Patent Nos. 7,485,603, 7,786,057, 7,253,231, 6,107,257, and 5,075,383, and / or is commercially available.

[0077] 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.

[0078] Suitable classes 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, including 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.

[0079] 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. 3,178,663 and 4,652,387); and carboxylic acids, polycarboxylic acids, anhydrides, and / or acid halides (e.g., U.S. Pat. Nos. 3,403,102 and 4,648,980). Nos. 3,708,522 and 4,948,386; 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. 4,617,137); US Patent Nos. 3,312,619, 3,865,813, and UK Patent No. 1,065,595; organic sulfonic acids (e.g., US Patent No. 3,189,544 and UK Patent No. 2,140,811); alkenyl cyanides (e.g., US Patent Nos. 3,278,550 and 3,366,569); diketenes (e.g., US Patent No. 3,546,243); diisocyanates (e.g., US Patent No. 3,573,205); Alkanesultones (e.g., U.S. Pat. No. 3,749,695); 1,3-dicarbonyl compounds (e.g., U.S. Pat. No. 4,579,675); 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. 4,612,132, 4,647,390, 4,648,886, 4,670,170); US Patent Nos. 4,614,603 and 4,666,460; cyclic carbonates or thiocarbonates, linear monocarbonates or polycarbonates, or chloroformates (e.g., US Patent Nos. 4,612,132, 4,647,390, 4,646,860, and 4,670,170); nitrogen-containing carboxylic acids (e.g., US Patent No. 4,971,598 and British Patent No. 2,440,811); hydroxy-protected chlorodicarbonyloxy compounds (e.g., US Patent No. 4,614,522); lactates hydroxyaliphatic carboxylic acids (e.g., U.S. Pat. Nos. 4,482,464, 4,521,318, 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. 4,614,603 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, 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); For example, U.S. Pat. No. 3,185,647; combinations of carboxylic acids or aldehydes or ketones and sulfur or sulfur chloride (e.g., U.S. Pat. Nos. 3,390,086 and 3,470,098); 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 and 5,039,307); combinations of aldehydes and O-diesters of dithiophosphoric acids (e.g., U.S. Pat. No. 3,865,740);Combinations of hydroxyaliphatic carboxylic acids and boric acid (e.g., U.S. Pat. No. 4,554,086); combinations of hydroxyaliphatic carboxylic acids followed by formaldehyde and 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 glycolating agent (e.g., U.S. Pat. No. 4,973,412); a combination of an aldehyde and a triazole (e.g., U.S. Pat. No. 4,963,278); a combination of an aldehyde and a triazole, followed by a boron compound (e.g., U.S. Pat. No. 4,981,492); a combination of a cyclic lactone and a boron compound (e.g., U.S. Pat. Nos. 4,963,275 and 4,971,711). The above-mentioned patents are incorporated herein in their entirety.

[0080] The TBN of suitable dispersants may be from about 10 to about 65 mg KOH / g dispersant on an oil-free basis, which equates to about 5 to about 30 TBN when measured on dispersant samples containing about 50% diluent oil. TBN is measured by the method of ASTM D2896.

[0081] In yet another embodiment, the optional dispersant additive may be a hydrocarbyl-substituted succinamide or succinimide dispersant. In some approaches, the hydrocarbyl-substituted succinamide or succinimide dispersant may be derived from a hydrocarbyl-substituted acylating agent reacted with a polyalkylene polyamine, wherein the hydrocarbyl substituent of the succinamide or succinimide dispersant is a linear or branched hydrocarbyl group having a number average molecular weight of from about 250 to about 5,000, as determined by GPC using polystyrene as a calibration standard.

[0082] In some approaches, the polyalkylene polyamine used to form the dispersant has the following formula:

[0083] [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.

[0084] Dispersants, when present, may be used in an amount sufficient to provide up to about 20 wt. % dispersant ...

[0085] Other antioxidants The lubricating oil compositions herein may also optionally contain one or more antioxidants. Antioxidant compounds are known and include, for example, phenates, phenate sulfides, sulfurized olefins, phosphosulfurized terpenes, sulfurized esters, aromatic amines, alkylated diphenylamines (e.g., nonyldiphenylamine, di-nonyldiphenylamine, octyldiphenylamine, di-octyldiphenylamine), phenyl-alpha-naphthylamines, alkylated phenyl-alpha-naphthylamines, hindered non-aromatic amines, phenols, hindered phenols, oil-soluble molybdenum compounds, polymeric antioxidants, or mixtures thereof. The antioxidant compounds may be used alone or in combination.

[0086] The hindered phenol antioxidant may contain a secondary butyl group and / or a tertiary butyl group as a steric hindering group. The phenol group may be further substituted with a hydrocarbyl group and / or a bridging group connecting to a second aromatic group. Examples of suitable hindered phenol antioxidants include 2,6-di-tert-butylphenol, 4-methyl-2,6-di-tert-butylphenol, 4-ethyl-2,6-di-tert-butylphenol, 4-propyl-2,6-di-tert-butylphenol, 4-butyl-2,6-di-tert-butylphenol, or 4-dodecyl-2,6-di-tert-butylphenol. In one embodiment, the hindered phenol antioxidant may be an ester but may include, for example, Irganox™ L-135 available from BASF or an addition product derived from 2,6-di-tert-butylphenol and an alkyl acrylate, where the alkyl group may contain from about 1 to about 18, or from about 2 to about 12, or from about 2 to about 8, or from about 2 to about 6, or about 4 carbon atoms. Another commercially available hindered phenol antioxidant may be an ester but may include Ethanox™ 4716 available from Albemarle Corporation.

[0087] Useful antioxidants may include diarylamines and high molecular weight phenols. In embodiments, the lubricating oil composition may contain a mixture of diarylamines and high molecular weight phenols, such that each antioxidant may be present in an amount sufficient to provide up to about 5 wt. %, based on the final weight of the lubricating oil composition. In embodiments, the antioxidant may be a mixture of about 0.3 to about 1.5 wt. % diarylamines and about 0.4 to about 2.5 wt. % high molecular weight phenols, based on the final weight of the lubricating oil composition.

[0088] 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 may be a Diels-Alder adduct of a diene, such as 1,3-butadiene, or an unsaturated ester, such as butyl acrylate.

[0089] 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.

[0090] 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).

[0091] 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.

[0092] Other anti-wear agents The lubricating oil compositions herein may also optionally contain one or more antiwear agents. Examples of suitable antiwear agents include, but are not limited to, metal thiophosphates; metal dialkyldithiophosphates; phosphoric acid esters or salts thereof; phosphoric acid esters; phosphites; phosphorus-containing carboxylic acid esters, ethers, or amides; sulfurized olefins; thiocarbamate-containing compounds, such as thiocarbamate esters, alkylene-linked thiocarbamates, and bis(S-alkyldithiocarbamyl) disulfides; and mixtures thereof. A suitable antiwear agent may be molybdenum dithiocarbamate. Phosphorus-containing antiwear agents are more fully described in EP 612839. The metal in the dialkyldithiophosphate salt may be an alkali metal, alkaline earth metal, aluminum, lead, tin, molybdenum, manganese, nickel, copper, titanium, or zinc. A useful antiwear agent may be zinc dialkyldithiophosphate.

[0093] Further examples of suitable antiwear agents include titanium compounds, tartrates, tartrimides, oil-soluble amine salts of phosphorus compounds, sulfurized olefins, phosphites (e.g., dibutyl phosphite), phosphonates, thiocarbamate-containing compounds such as thiocarbamate esters, thiocarbamate amides, thiocarbamic acid ethers, alkylene-linked thiocarbamates, and bis(S-alkyldithiocarbamyl) disulfides. The tartrates or tartrimides may contain alkyl-ester groups, but the total number of carbon atoms on the alkyl group may be at least 8. The antiwear agent, in one embodiment, may include citrate.

[0094] The antiwear agent may be present in a range including from about 0% to about 15%, or from about 0.01% to about 10%, or from about 0.05% to about 5%, or from about 0.1% to about 3% by weight of the lubricating oil composition.

[0095] Boron-containing compounds The lubricating oil compositions herein may optionally contain one or more boron-containing compounds. Examples of boron-containing compounds include borate esters, borated fatty amines, borated epoxides, borated detergents, and borated dispersants, such as borated succinimide dispersants, as disclosed in U.S. Patent No. 5,883,057. When present, the boron-containing compounds may be used in an amount sufficient to provide up to about 8 wt. %, from about 0.01 wt. % to about 7 wt. %, from about 0.05 wt. % to about 5 wt. %, or from about 0.1 wt. % to about 3 wt. % of the lubricating oil composition.

[0096] Additional cleaning agents The lubricating oil composition may optionally further comprise one or more neutral, underbased, 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.

[0097] The detergent substrate may be salified with an alkali or alkaline earth metal, such as, but not limited to, calcium, magnesium, potassium, sodium, lithium, barium, or mixtures thereof. In some embodiments, the detergent 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 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, sulfur-containing 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, sulfur-containing magnesium phenate, magnesium sulfonate, magnesium calixarate, magnesium salixarate, magnesium salicylate, magnesium carboxylate, magnesium phosphate, magnesium mono- and / or di-thiophosphate, magnesium alkyl phenol, magnesium sulfur-bound alkyl phenol compound, magnesium methylene bridged phenol, sodium phenate, sulfur-containing sodium phenate, sodium sulfonate, sodium calixarate, sodium salixarate, sodium salicylate, sodium carboxylate, sodium phosphate, sodium mono- and / or di-thiophosphate, sodium alkyl phenol, sodium sulfur-bound alkyl phenol compound, or sodium methylene bridged phenol.

[0098] Overbased detergent additives are well known in the art and may be alkali metal or alkaline earth metal overbased detergent additives. Such detergent additives may be prepared by reacting a metal oxide or metal hydroxide with a substrate and carbon dioxide gas. The substrate is typically an acid, such as an aliphatic-substituted sulfonic acid, an aliphatic-substituted carboxylic acid, or an aliphatic-substituted phenol.

[0099] The term "overbased" refers to metal salts, such as metal salts of sulfonic acids, carboxylic acids, and phenols, in which the amount of metal present exceeds the stoichiometric amount. Such salts may have conversion levels greater than 100% (i.e., they may contain more than 100% of the theoretical amount of metal required to convert the acid to its "standard" or "neutral" salt). The expression "metal ratio," often abbreviated as MR, is used to indicate the ratio of the total chemical equivalents of metal in an overbased salt to the chemical equivalents of metal in a neutral salt, according to known chemical reactivity and stoichiometry. In standard or neutral salts, the metal ratio is 1, while in overbased salts, the MR is greater than 1. They are commonly referred to as overbased, highly based, or superbased salts and may be salts of organic sulfur acids, carboxylic acids, or phenols.

[0100] 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.

[0101] Examples of suitable overbased detergents include, but are not limited to, overbased calcium phenates, overbased calcium sulfur-containing phenates, overbased calcium sulfonates, overbased calcium calixarates, overbased calcium salixarates, overbased calcium salicylates, overbased calcium carboxylic acids, overbased calcium phosphates, overbased calcium mono- and / or di-thiophosphates, overbased calcium alkylphenols, overbased calcium sulfur-bound alkylphenol compounds, overbased calcium methylene-bridged phenols, overbased magnesium phenates, overbased magnesium sulfur-containing phenates, overbased magnesium sulfonates, overbased magnesium calixarates, overbased magnesium salixarates, overbased magnesium salicylates, overbased magnesium carboxylic acids, overbased magnesium phosphates, overbased magnesium mono- and / or di-thiophosphates, overbased magnesium alkylphenols, overbased magnesium sulfur-bound alkylphenol compounds, or overbased magnesium methylene-bridged phenols.

[0102] The overbased calcium phenate detergents have a total base number of at least about 150 mg KOH / g, at least about 225 mg KOH / g, at least about 225 mg KOH / g to about 400 mg KOH / g, at least about 225 mg KOH / g to about 350 mg KOH / g, or about 230 mg KOH / g to about 350 mg KOH / g, all 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.

[0103] The overbased detergent may have a metal-to-substrate ratio of 1.1:1 or greater, or 2:1 or greater, or 4:1 or greater, or 5:1 or greater, or 7:1 or greater, or 10:1 or greater. In some embodiments, the detergent is effective in reducing or preventing rust in engines or other automotive components such as transmissions or gears. The detergent may be present in the lubricating composition from about 0 wt % to about 10 wt %, or from about 0.1 wt % to about 8 wt %, or from about 1 wt % to about 4 wt %, or from greater than about 4 wt % to about 8 wt %.

[0104] 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.

[0105] friction modifiers The lubricating oil compositions herein may also optionally contain one or more friction modifiers. Suitable friction modifiers may include metal-containing and metal-free friction modifiers, and may include, but are not limited to, imidazolines, amides, amines, succinimides, alkoxylated amines, alkoxylated ether amines, amine oxides, amidoamines, nitriles, betaines, quaternary amines, imines, amine salts, aminoguanidines, alkanolamides, phosphonates, metal-containing compounds, glycerol esters, sulfurized fatty compounds and olefins, sunflower oil, other naturally occurring vegetable or animal oils, dicarboxylic acid esters, esters or partial esters of polyols with one or more aliphatic or aromatic carboxylic acids, and the like.

[0106] 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.

[0107] Other suitable friction modifiers may include organic, ashless (metal-free), nitrogen-free organic friction modifiers. Such friction modifiers include esters formed by reacting carboxylic acids and anhydrides with alkanols, and may generally include polar end groups (e.g., carboxyl or hydroxyl) covalently bonded to an oleophilic hydrocarbon chain. An example of an organic ashless, nitrogen-free friction modifier is generally known as glycerol monooleate (GMO), which may 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.

[0108] 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.

[0109] The amines and amides may be used per se 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, the entire contents of which are incorporated herein by reference.

[0110] 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.

[0111] Molybdenum-containing ingredients 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 may be a molybdenum dithiocarbamate.

[0112] 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.

[0113] Additionally, the molybdenum compound may be an acidic molybdenum compound, including molybdic acid, ammonium molybdate, sodium molybdate, potassium molybdate, and other alkali metal molybdates and other molybdenum salts, such as sodium hydrogen molybdate, MoOCl, MoOBr, MoOCl, molybdenum trioxide, or similar acidic molybdenum compounds. Alternatively, the composition can provide the molybdenum via molybdenum / sulfur complexes of basic nitrogen compounds, as described, for example, in U.S. Pat. Nos. 4,263,152, 4,285,822, 4,283,295, 4,272,387, 4,265,773, 4,261,843, 4,259,195, and 4,259,194, and WO 94 / 06897, the foregoing patents being incorporated herein by reference in their entireties.

[0114] Another class of suitable organo-molybdenum compounds is the trinuclear molybdenum compounds, e.g., those of the formula MoS k L n Q z and mixtures thereof, wherein S represents sulfur, L represents an independently selected ligand having an organic group having a sufficient number of carbon atoms to render the compound soluble or dispersible in oil, n is 1 to 4, k varies from 4 to 7, Q is selected from the group of neutral electron donor compounds, e.g., water, amines, alcohols, phosphines, and ethers, and z ranges from 0 to 5, including non-stoichiometric values. There may be at least 21 total carbon atoms among all of the ligand organic groups, such as at least 25, at least 30, or at least 35 carbon atoms. Additional suitable molybdenum compounds are described in U.S. Pat. No. 6,723,685, the entire contents of which are incorporated herein by reference.

[0115] The oil-soluble molybdenum compound may be present in an amount sufficient to provide from about 0.5 ppm to about 2000 ppm, from about 1 ppm to about 700 ppm, from about 1 ppm to about 550 ppm, from about 5 ppm to about 300 ppm, or from about 20 ppm to about 250 ppm of molybdenum.

[0116] Transition metal-containing compounds In another embodiment, the oil-soluble compound may be a transition metal-containing compound or a metalloid. Transition metals may include, but are not limited to, titanium, vanadium, copper, zinc, zirconium, molybdenum, tantalum, tungsten, etc. Suitable metalloids include, but are not limited to, boron, silicon, antimony, tellurium, etc.

[0117] In 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 one or more of these functions. In embodiments, the oil-soluble transition metal-containing compound may be an oil-soluble titanium compound such as a titanium(IV) alkoxide. Among the titanium-containing compounds that can be used in or for preparing the oil-soluble material in the technology of the present disclosure 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 titanium phenate; titanium carboxylates, such as titanium(IV) 2-ethyl-1,3-hexanedioate, titanium citrate, or titanium oleate; and titanium(IV) (triethanolaminato)isopropoxide. Other forms of titanium encompassed by the disclosed technology include titanium phosphates, such as titanium dithiophosphates (e.g., dialkyldithiophosphates) and titanium sulfonates (e.g., alkylbenzene sulfonates), or generally reaction products of titanium compounds with various acidic materials to form salts, such as oil-soluble salts. Thus, titanium compounds may be derived from organic acids, alcohols, and glycols, among others. Ti compounds may also exist in dimeric or oligomeric forms containing Ti-O-Ti structures. Such titanium materials are commercially available or can be readily prepared by suitable synthetic techniques apparent to those skilled in the art. They may exist at room temperature as solids or liquids, depending on the particular compound. They may also be provided in solution form in a suitable inert solvent.

[0118] In one embodiment, titanium may be provided as a Ti-modified dispersant, such as a succinimide dispersant. Such materials may be prepared by forming a titanium mixed anhydride between a titanium alkoxide and a hydrocarbyl-substituted succinic anhydride, such as an alkenyl-(or alkyl) succinic anhydride. The resulting titanate-succinate intermediate may be used directly or may be reacted with any of a number of 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 may be reacted with other agents, such as alcohols, amino alcohols, ether alcohols, polyether alcohols or polyols, or fatty acids, and the product may be used directly to impart Ti to lubricating oils or further reacted with a succinic dispersant as described above. As an example, one part (mole) of tetraisopropyl titanate may be reacted with about 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) may be further reacted with a succinimide dispersant from a polyisobutene-substituted succinic anhydride and polyethylene polyamine mixture (127 grams + diluent oil) at 150°C for 1.5 hours to yield a titanium-modified succinimide dispersant.

[0119] Another titanium-containing compound is titanium alkoxide and C6-C 25 It may also be a reaction product with a carboxylic acid. The reaction product has the following formula:

[0120] [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:

[0121] [ka] or the titanium compound may be represented by the formula: wherein m+n=4, n ranging from 1 to 3, R4 is an alkyl moiety having from 1 to 8 carbon atoms, R1 is selected from hydrocarbyl groups containing from about 6 to 25 carbon atoms, and R2 and R3 are the same or different and are selected from hydrocarbyl groups containing from 1 to 6 carbon atoms;

[0122] [ka] wherein x ranges from 0 to 3; R1 is selected from hydrocarbyl groups containing from about 6 to 25 carbon atoms; R2 and R3 are the same or different and are selected from hydrocarbyl groups containing from about 1 to 6 carbon atoms; and R4 is selected from H, C6-C 25 and the carboxylic acid moiety of

[0123] 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.

[0124] In embodiments, the oil-soluble titanium compound may be present in the lubricating oil composition in an amount to provide from 0 to 3000 ppm by weight of titanium, or from 25 to about 1500 ppm by weight of titanium, or from about 35 ppm to 500 ppm by weight of titanium, or from about 50 ppm to about 300 ppm.

[0125] Viscosity Index Improver The lubricating oil compositions herein may also optionally contain one or more viscosity index improvers. Suitable viscosity index improvers may include polyolefins, olefin copolymers, ethylene / propylene copolymers, polyisobutene, hydrogenated styrene-isoprene polymers, styrene / maleic acid ester copolymers, hydrogenated styrene / butadiene copolymers, hydrogenated isoprene polymers, alpha-olefin maleic anhydride copolymers, polymethacrylates, polyacrylates, polyalkylstyrenes, hydrogenated alkenylaryl conjugated diene copolymers, or mixtures thereof. Viscosity index improvers may include star polymers, suitable examples of which are described in U.S. Patent Application Publication No. 20120101017(A1).

[0126] The lubricating oil compositions herein may also optionally contain one or more dispersant viscosity index improvers in addition to or in place of the viscosity index improver. Suitable viscosity index improvers may include functionalized polyolefins, such as ethylene-propylene copolymers functionalized with the reaction product of an acylating agent (such as maleic anhydride) and an amine, amine-functionalized polymethacrylates, or esterified maleic anhydride-styrene copolymers reacted with amines.

[0127] The total amount of viscosity index improver and / or dispersant viscosity index improver may be from about 0% to about 20%, from about 0.1% to about 15%, from about 0.1% to about 12%, or from about 0.5% to about 10% by weight of the lubricating oil composition.

[0128] Other optional additives Other additives may be selected to perform one or more functions required in a lubricating fluid. Additionally, one or more of the aforementioned additives may be multifunctional, providing functions in addition to or other than those described herein.

[0129] Lubricating oil compositions according to the present disclosure may also contain other optional performance additives. The other performance additives may be additional to the specified additives of this disclosure and / or may include one or more of metal deactivators, viscosity index improvers, detergents, ashless TBN boosters, friction modifiers, antiwear agents, corrosion inhibitors, rust inhibitors, dispersants, dispersant viscosity index improvers, extreme pressure agents, antioxidants, foam suppressants, demulsifiers, emulsifiers, pour point depressants, seal swell agents, and mixtures thereof. Typically, fully formulated lubricating oils will contain one or more of these performance additives.

[0130] 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 optional vinyl acetate; demulsifiers including trialkyl phosphates, polyethylene glycol, polyethylene oxide, polypropylene oxide, and (ethylene oxide-propylene oxide) polymers; pour point depressants including esters of maleic anhydride-styrene, polymethacrylate, polyacrylate, or polyacrylamide.

[0131] Suitable suds suppressors include silicon-based compounds such as siloxanes.

[0132] 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.

[0133] 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.

[0134] When present, the rust inhibitor may be used in an amount sufficient to provide from about 0 wt. % to about 5 wt. %, from about 0.01 wt. % to about 3 wt. %, from about 0.1 wt. % to about 2 wt. %, based on the final weight of the lubricating oil composition.

[0135] Broadly speaking, suitable lubricants containing the detergent metals herein may contain additive components in the ranges listed in the table below.

[0136] [Table 2]

[0137] 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 may be blended into the base oil individually or in various partial combinations. However, it may be preferred to blend all of the components simultaneously using an additive concentrate (i.e., additives plus a diluent such as a hydrocarbon solvent). Fully formulated lubricants conventionally contain an additive package, referred to herein as a dispersant / inhibitor package or DI package, that supplies the properties required in the formulation.

[0138] 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.

[0139] As described herein, compounds may be optionally substituted with one or more substituents as illustrated generally above or by specific classes, subclasses, and species of the present disclosure.

[0140] Unless otherwise clear from the context, the term "major amount" is understood to mean an amount of 50 weight percent or more, for example, about 80 to about 98 weight percent, based on the total weight of the composition, and the term "minor amount" as used herein is understood to mean an amount of less than 50 weight percent, based on the total weight of the composition.

[0141] 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. In general, no more than two, or as a further example, no more than 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.

[0142] As used herein, the term "aliphatic" encompasses the terms alkyl, alkenyl, alkynyl, each of which is optionally substituted as described below.

[0143] 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. Alkyl groups 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. It can be substituted (i.e., optionally substituted) with alkylaminocarbonyl, cycloalkylaminocarbonyl, heterocycloalkylaminocarbonyl, arylaminocarbonyl, or heteroarylaminocarbonyl], amino, [e.g., aliphatic amino, alicyclic amino, or heteroalicyclic amino], sulfonyl [e.g., aliphatic -SO2-], sulfinyl, sulfanyl, sulfoxy, urea, thiourea, sulfamoyl, sulfamido, oxo, carboxy, carbamoyl, alicyclicoxy, heterocycloaliphaticoxy, aryloxy, heteroaryloxy, aralkyloxy, heteroarylalkoxy, alkoxycarbonyl, alkylcarbonyloxy, or hydroxy.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.

[0144] As used herein, an "alkenyl" group refers to an aliphatic carbon group containing 2 to 8 (e.g., 2 to 12, 2 to 6, or 2 to 4) carbon atoms and at least one double bond. Like an alkyl group, an alkenyl group can be linear or branched. Examples of alkenyl groups include, but are not limited to, allyl, isoprenyl, 2-butenyl, and 2-hexenyl. Alkenyl groups can have one or more substituents, such as halo, phospho, alicyclic [e.g., cycloalkyl or cycloalkenyl], heteroalicyclic [e.g., heterocycloalkyl or heterocycloalkenyl], aryl, heteroaryl, alkoxy, aroyl, heteroaroyl, acyl [e.g., (aliphatic)carbonyl, (alicyclic)carbonyl, or (heteroalicyclic)carbonyl], nitro, cyano, amido [e.g., (cycloalkylalkyl)carbonylamino, arylcarbonylamino, aralkylcarbonylamino, (heterocycloalkyl)carbonylamino, (heterocycloalkylalkyl)carbonylamino, heteroarylcarbonylamino, heteroaralkylcarbonylamino, alkylaminocarbonyl], or heteroarylcarbonylamino. and optionally substituted by phenyl, 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.

[0145] As used herein, an "alkynyl" group refers to an aliphatic carbon group containing 2 to 8 (e.g., 2 to 12, 2 to 6, or 2 to 4) carbon atoms and having at least one triple bond. Alkynyl groups can be linear or branched. Examples of alkynyl groups include, but are not limited to, propargyl and butynyl. Alkynyl groups can be substituted with one or more substituents, such as, for example, aroyl, heteroaroyl, alkoxy, cycloalkyloxy, heterocycloalkyloxy, aryloxy, heteroaryloxy, aralkyloxy, nitro, carboxy, cyano, halo, hydroxy, sulfo, mercapto, sulfanyl [e.g., aliphatic sulfanyl or 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,

[0039] The heterocycloalkyl group may be optionally substituted with arylaminocarbonyl, 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.

[0146] 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.

[0147] 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.

[0148] As used herein, a "heterocycloalkyl" group refers to a 3- to 10-membered monocyclic or bicyclic (fused or bridged) (e.g., 5- to 10-membered monocyclic 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.

[0149] As used herein, a "heteroaryl" group refers to a monocyclic, bicyclic, or tricyclic ring system having 4 to 15 ring atoms, where one or more ring atoms are heteroatoms (e.g., N, O, S, or a combination thereof), and the monocyclic ring system is aromatic, or at least one of the rings in the bicyclic or tricyclic ring system is aromatic. Heteroaryl groups include benzo-fused ring systems having 2 to 3 rings. For example, a benzo-fused group includes benzo fused to one or two 4- to 8-membered heterocyclic aliphatic moieties (e.g., indolyl, indolyl, isoindolyl, 3H-indolyl, indolinyl, benzo[b]furyl, benzo[b]thiophenyl, quinolinyl, or isoquinolinyl). Some examples of heteroaryl are pyridyl, 1H-indazolyl, furyl, pyrrolyl, thienyl, thiazolyl, oxazolyl, imidazolyl, tetrazolyl, benzofuryl, isoquinolinyl, benzthiazolyl, xanthene, thioxanthene, phenothiazine, dihydroindole, benzo[1,3]dioxole, benzo[b]furyl, benzo[b]thiophenyl, indazolyl, benzimidazolyl, benzthiazolyl, puryl, cinnolyl, quinolyl, quinazolyl, cinnolyl, phthalazyl, quinazolyl, quinoxalyl, isoquinolyl, 4H-quinolidyl, benzo-1,2,5-thiadiazole, or 1,8-naphthyridyl.

[0150] 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.

[0151] Bicyclic heteroaryls include, but are not limited to, 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.

[0152] As used herein, the term "treat rate" refers to the weight percent of a component in a lubricating fluid.

[0153] The weight-average molecular weight (Mw) and number-average molecular weight (Mn) may be determined using a gel permeation chromatography (GPC) instrument from Waters or similar instrumentation and Waters Empower Software or similar software. The GPC instrument may be equipped with a Waters Separation Module and a Waters Refractive Index Detector (or similar optional instrumentation). GPC operating conditions may include a guard column, four Agilent PLgel columns (300 x 7.5 mm long, 5 μm particle size, and pore sizes ranging from 100 to 10,000 Å), and a column temperature of approximately 40°C. Unstabilized HPLC-grade tetrahydrofuran (THF) may be used as the solvent at a flow rate of 1.0 mL / min. The GPC instrument may be calibrated with commercially available poly(methyl methacrylate) (PMMA) standards with narrow molecular weight distributions ranging from 960 to 1,568,000 g / mol. The calibration curve can be extrapolated for samples with masses less than 500 g / mol. Samples and PMMA standards are dissolved in THF at concentrations of 0.1 to 0.5% by weight and can be used without filtration. GPC measurements are also described in U.S. Pat. No. 5,266,223, which is incorporated herein by reference. The GPC method additionally 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]

[0154] 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.

[0155] Example 1 The motorcycle lubricants were evaluated for copper leaching from a hot tube test (HTT) at 280°C, TBN retention, sulfur retention, and lacquer formation when performed according to JASO T 903:2016, Indiana Stirred Oxidation Test (ISOT), and / or JIS K2514 standards. The lubricants are shown in Table 3 below, certain elemental compositions of the lubricants are provided in Table 4, and performance results are provided in Table 5. In addition to the ZDDP antiwear additives in Table 3, each of the fluids contained the same base additive package of dispersants, detergents, antioxidants, and viscosity index improvers, and base oil blends to achieve a KV100 of approximately 10.9 cSt (ASTM D425).

[0156] [Table 3]

[0157] The anti-wear additives in Table 3 include the following zinc dihydrocarbyl dithiophosphate additives: ZDDP1 is a zinc dihydrocarbyl dithiophosphate compound with an average of 8.8 total carbons per phosphorus atom, 60 mole percent primary alcohols, and 40 mole percent secondary alcohols. · ZDDP2 is a zinc dihydrocarbyl dithiophosphate compound having, on average, 16 total carbons per phosphorus atom and 100 mole percent primary alcohols. · ZDDP3 is a zinc dihydrocarbyl dithiophosphate compound having, on average, 16 total carbons per phosphorus atom and 100 mole percent primary alcohols. · ZDDP4 is a zinc dihydrocarbyl dithiophosphate compound with an average of 9 total carbons per phosphorus atom and 100 percent secondary alcohols. ZDDP5 is a zinc dihydrocarbyl dithiophosphate compound having, on average, 9.3 total carbons per phosphorus atom and 100 mole percent primary alcohols. ZDDP6 is a zinc dihydrocarbyl dithiophosphate compound having, on average, 12 total carbons per phosphorus atom and 100 mole percent secondary alcohols.

[0158] [Table 4]

[0159] The fluids summarized in Tables 3 and 4 were evaluated for copper leaching, TBN retention, sulfur retention, and lacquer formation in the hot tube test described above. The results are provided in Table 5.

[0160] [Table 5] * HClO4 method ** HCl *** TBN retention and sulfur retention are calculated by dividing the TBN or sulfur at the start of the test by the TBN or sulfur, respectively, at the end of the test, and multiplying by 100.

[0161] As shown above in Table 5, the fluids of the present invention have lower ISOT copper corrosion, better TNB retention, and higher or equal Hot Tube Test (HTT) ratings than the comparative fluids.

[0162] 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.

[0163] For purposes of this specification and the appended claims, unless otherwise indicated, all numbers expressing quantities, percentages, or proportions, and other numerical values ​​used in the specification and claims should be understood in all instances to be modified by the term "about." Accordingly, unless indicated to the contrary, the numerical parameters set forth in the following specification and appended claims are approximations that may vary depending upon the desired properties sought to be obtained by the present disclosure. At the very least, and not as an attempt to limit the application of the doctrine of equivalents to the scope of the claims, each numerical parameter should at least be construed in light of the number of reported significant digits and by applying ordinary rounding techniques.

[0164] 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.

[0165] 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.

[0166] 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 should also be 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.

[0167] Furthermore, a specific amount / value of a component, compound, substituent, or parameter disclosed in the details or examples should be construed as disclosing either a lower or upper limit of a range and, therefore, can be combined with any other lower or upper limit or specific amount / value in a range for the same component, compound, substituent, or parameter disclosed elsewhere in this application to form a range for that component, compound, substituent, or parameter.

[0168] 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. A lubricating composition for motorcycles, comprising: one or more base oils of lubricating viscosity; a minority additive package including a metal-containing sulfonate, salicylate, and / or phenate detergent; a dispersant providing at least about 400 ppm nitrogen; at least one aminic antioxidant; and one or more metal dihydrocarbyl dithiophosphate compounds; the one or more metal dihydrocarbyl dithiophosphate compounds provide at least about 800 ppm phosphorus to the motorcycle lubricating composition; 1. A motorcycle lubricating composition, wherein the one or more metal dihydrocarbyl dithiophosphate compounds have, on average, at least 14 total carbons per phosphorus atom and the hydrocarbyl groups are derived from at least about 80 mole percent straight or branched chain primary alcohols.

2. 10. The motorcycle lubricating composition of claim 1, wherein the hydrocarbyl groups of the one or more metal dihydrocarbyl dithiophosphate compounds are derived from about 100 mole percent straight or branched chain primary alcohols.

3. 10. The motorcycle lubricating composition of claim 1, wherein the one or more metal dihydrocarbyl dithiophosphate compounds have, on average, at least 16 total carbons per phosphorus atom.

4. 2. The motorcycle lubricating composition of claim 1, wherein the lubricating composition exhibits copper leaching of about 90 ppm or less, a TBN retention of about 10 to about 25 percent, and a sulfur retention of at least about 95 percent, as measured according to the Indiana Stirred Oxidization Test (ISOT) performed in accordance with JIS K2514 testing standard.

5. The metal dihydrocarbyl dithiophosphate compound has the structure of Formula I: 【Chemical 1】 10. The motorcycle lubricating composition of claim 1, wherein each R is independently a straight or branched chain C8 to C16 hydrocarbyl group; A is a metal selected from aluminum, lead, tin, molybdenum, manganese, nickel, copper, titanium, tungsten, zirconium, or zinc; and / or each R is a straight or branched chain C8 to C10 hydrocarbyl group derived from a primary alcohol; and / or A is zinc; and each R has about 100 mole percent of the hydrocarbyl groups derived from C8 to C10 primary alcohols; and / or the one or more metal dihydrocarbyl dithiophosphate compounds provide up to about 3,000 ppm phosphorus to the motorcycle lubricating composition.

6. 10. The motorcycle lubricating composition of claim 1, wherein the detergent is a calcium sulfonate and / or calcium phenate detergent having a TBN of from about 0 to about 500 as measured by ASTM D2896 and providing at least about 1,000 ppm of calcium to the motorcycle lubricating composition.

7. 2. The motorcycle lubricating composition of claim 1, wherein the lubricating composition comprises up to about 1 weight percent of the aminic antioxidant, and / or the aminic antioxidant is selected from the group comprising aromatic amines, alkylated diphenylamines, nonyldiphenylamine, dinonyldiphenylamine, octyldiphenylamine, dioctyldiphenylamine, phenyl-alpha-naphthylamine, alkylated phenyl-alpha-naphthylamine, hindered non-aromatic amines, or combinations thereof.

8. 2. The motorcycle lubricating composition of claim 1, wherein the lubricating composition comprises from about 0.5 to about 5 weight percent of the dispersant, and / or the dispersant is obtainable by reacting a hydrocarbyl-substituted acylating agent with a nitrogen source, and / or the acylating agent is maleic anhydride and the nitrogen source is selected from ammonia, a polyalkylene polyamine, or a combination thereof, and / or the nitrogen source is the polyalkylene polyamine selected from polyethylene polyamine having an average of 5 nitrogen atoms, triethylene tetraamine, tetraethylene pentamine, or a mixture of combinations thereof.

9. 1. A method of lubricating an engine, transmission, and clutch assembly of a motorcycle with a lubricating composition, said method comprising: lubricating the motorcycle engine, the transmission, and the clutch assembly with a lubricating composition provided from a common lubricant reservoir; 1. A method for preparing a lubricating composition comprising: one or more base oils of lubricating viscosity; a minor additive package comprising a metal-containing sulfonate, salicylate, and / or phenate detergent; a dispersant providing at least about 400 ppm nitrogen; at least one aminic antioxidant; and one or more metal dihydrocarbyl dithiophosphate compounds, the one or more metal dihydrocarbyl dithiophosphate compounds providing at least about 800 ppm phosphorus to the motorcycle lubricating composition, the one or more metal dihydrocarbyl dithiophosphate compounds having, on average, at least 14 total carbons per phosphorus atom and whose hydrocarbyl groups are derived from at least about 80 mole percent straight or branched chain primary alcohols.

10. 10. The method of claim 9, wherein the hydrocarbyl groups of the one or more metal dihydrocarbyl dithiophosphate compounds are derived from about 100 mole percent straight or branched chain primary alcohols.

11. 10. The method of claim 9, wherein the one or more metal dihydrocarbyl dithiophosphate compounds have, on average, at least 16 total carbons per phosphorus atom.

12. 10. The method of claim 9, wherein the lubricating composition exhibits copper leaching of about 90 ppm or less, a TBN retention of about 10 to about 25 percent, and a sulfur retention of at least about 95 percent, as measured according to the Indiana Stirred Oxidization Test (ISOT) performed under JIS K2514 testing standard.

13. The metal dihydrocarbyl dithiophosphate compound has the structure of Formula I: 【Chemistry 2】 10. The method of claim 9, wherein each R is independently a straight or branched chain C8 to C16 hydrocarbyl group and A is a metal selected from aluminum, lead, tin, molybdenum, manganese, nickel, copper, titanium, tungsten, zirconium, or zinc.

14. 14. The method of claim 13, wherein each R is a straight or branched chain C8 to C10 hydrocarbyl group derived predominantly from a primary alcohol, and / or A is zinc, and each R has about 100 mole percent of said hydrocarbyl groups derived from C8 to C10 primary alcohols.

15. 10. The method of claim 9, wherein the one or more metal dihydrocarbyl dithiophosphate compounds provide up to about 3,000 ppm phosphorus to the lubricating composition.

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